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Sample records for temperature aqueous sulfuric

  1. Uptake of Hypobromous Acid (HOBr) by Aqueous Sulfuric Acid Solutions: Low-Temperature Solubility and Reaction

    Science.gov (United States)

    Iraci, Laura T.; Michelsen, Rebecca R.; Ashbourn, Samatha F. M.; Rammer, Thomas A.; Golden, David M.

    2005-01-01

    Hypobromous acid (HOBr) is a key species linking inorganic bromine to the chlorine and odd hydrogen chemical families. We have measured the solubility of HOBr in 45 - 70 wt% sulfuric acid solutions representative of upper tropospheric and lower stratospheric aerosol composition. Over the temperature range 201 - 252 K, HOBr is quite soluble in sulfuric acid, with an effective Henry's law coefficient, H* = 10(exp 4) - 10(exp 7) mol/L/atm. H* is inversely dependent on temperature, with Delta H = -46.2 kJ/mol and Delta S = -106.2 J/mol/K for 55 - 70 wt% H2SO4 solutions. Our study includes temperatures which overlap both previous measurements of HOBr solubility. For uptake into aqueous 45 wt% H2SO4, the solubility can be described by log H* = 3665/T - 10.63. For 55 - 70 wt% H2SO4, log H* = 2412/T - 5.55. At temperatures colder than approx. 213 K, the solubility of HOBr in 45 wt% H2SO4 is noticeably larger than in 70 wt% H2SO4. The solubility of HOBr is comparable to that of HBr, indicating that upper tropospheric and lower stratospheric aerosols should contain equilibrium concentrations of HOBr which equal or exceed those of HBr. Our measurements indicate chemical reaction of HOBr upon uptake into aqueous sulfuric acid in the presence of other brominated gases followed by evolution of gaseous products including Br2O and Br2, particularly at 70 wt% H2SO4.

  2. Uptake of hypobromous acid (HOBr by aqueous sulfuric acid solutions: low-temperature solubility and reaction

    Directory of Open Access Journals (Sweden)

    L. T. Iraci

    2005-01-01

    Full Text Available Hypobromous acid (HOBr is a key species linking inorganic bromine to the chlorine and odd hydrogen chemical families. We have measured the solubility of HOBr in 45-70wt% sulfuric acid solutions representative of upper tropospheric and lower stratospheric aerosol composition. Over the temperature range 201-252 K, HOBr is quite soluble in sulfuric acid, with an effective Henry's law coefficient, H*=104-107mol L-1atm-1. H* is inversely dependent on temperature, with ΔH=-45.0±5.4 kJ mol-1 and ΔS=-101±24 J mol-1K-1 for 55-70wt% H2SO4 solutions. Our study includes temperatures which overlap both previous measurements of HOBr solubility. For uptake into 55-70wt% H2SO4, the solubility is described by log H*=(2349±280/T-(5.27±1.24. At temperatures colder than ~213K, the solubility of HOBr in 45wt% H2SO4 is at least a factor of five larger than in 70wt% H2SO4, with log H*=(3665±270/T-(10.63±1.23. The solubility of HOBr is comparable to that of HBr, indicating that upper tropospheric and lower stratospheric aerosols should contain equilibrium concentrations of HOBr which equal or exceed those of HBr. Upon uptake of HOBr into aqueous sulfuric acid in the presence of other brominated gases, particularly for 70wt% H2SO4 solution, our measurements demonstrate chemical reaction of HOBr followed by evolution of gaseous products including Br2O and Br2.

  3. A comparison of dilute aqueous p-toluenesulfonic and sulfuric acid pretreatments and saccharification of corn stover at moderate temperatures and pressures.

    Science.gov (United States)

    Amarasekara, Ananda S; Wiredu, Bernard

    2012-12-01

    Single step pretreatment-saccharification of corn stover was investigated in aqueous p-toluenesulfonic and sulfuric acid media. Dilute aqueous solution of p-toluenesulfonic acid was a better catalyst than aqueous sulfuric acid of the same H(+) ion concentration for single step pretreatment-saccharification of corn stover at moderate temperatures and pressures. For example, 100mg corn stover heated at 150°C for 1h in 0.100 M H(+) aqueous sulfuric acid produced 64 μmol of total reducing sugars (TRS), whereas the sample heated in 0.100 M H(+)p-toluenesulfonic acid produced 165 μmol of TRS under identical conditions. Glucose yield showed a similar trend, as aq. sulfuric acid and p-toluene sulfonic acid media produced 29 and 35 μmol of glucose respectively after 2.5h. Higher catalytic activity of p-toluenesulfonic acid may be due to an interaction with biomass, supported by repulsion of hydrophobic tolyl group by the aqueous phase. Copyright © 2012 Elsevier Ltd. All rights reserved.

  4. 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).

  5. Comparative analysis of the effect of pretreating aspen wood with aqueous and aqueous-organic solutions of sulfuric and nitric acid on its reactivity during enzymatic hydrolysis

    DEFF Research Database (Denmark)

    Dotsenko, Gleb; Osipov, D. O.; Zorov, I. N.

    2016-01-01

    The effect of aspen wood pretreatment methods with the use of both aqueous solutions of sulfuric and nitric acids and aqueous-organic solutions (ethanol, butanol) of sulfuric acid (organosolv) on the limiting degree of conversion of this type of raw material into simple sugars during enzymatic...... hydrolysis are compared. The effects of temperature, acid concentration, composition of organic phase (for sulfuric acid), and pressure (for nitric acid) on the effectiveness of pretreatment were analyzed. It is shown that the use of organosolv with 0.5% sulfuric acid allows us to increase the reactivity...

  6. 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.

  7. Protonation Dynamics and Hydrogen Bonding in Aqueous Sulfuric Acid.

    Science.gov (United States)

    Niskanen, Johannes; Sahle, Christoph J; Juurinen, Iina; Koskelo, Jaakko; Lehtola, Susi; Verbeni, Roberto; Müller, Harald; Hakala, Mikko; Huotari, Simo

    2015-09-03

    Hydration of sulfuric acid plays a key role in new-particle formation in the atmosphere. It has been recently proposed that proton dynamics is crucial in the stabilization of these clusters. One key question is how water molecules mediate proton transfer from sulfuric acid, and hence how the deprotonation state of the acid molecule behaves as a function concentration. We address the proton transfer in aqueous sulfuric acid with O K edge and S L edge core-excitation spectra recorded using inelastic X-ray scattering and with ab initio molecular dynamics simulations in the concentration range of 0-18.0 M. Throughout this range, we quantify the acid-water interaction with atomic resolution. Our simulations show that the number of donated hydrogen bonds per Owater increases from 1.9 to 2.5 when concentration increases from 0 to 18.0 M, in agreement with a rapid disappearance of the pre-edge feature in the O K edge spectrum. The simulations also suggest that for 1.5 M sulfuric acid SO4(2-) is most abundant and that its concentration falls monotonously with increasing concentration. Moreover, the fraction of HSO4(-) peaks at ∼12 M.

  8. 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.

  9. Protonation of maleic and fumaric acid in aqueous sulfuric acid solutions

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    ILINKA SPIREVSKA

    2000-10-01

    Full Text Available The protonations of maleic and fumaric acid in an acidic medium (aqueous solutions of sulfuric acid were followed spectrophotometrically at room temperature. The acid-base equilibria were characterised qualitatively and quantitatively. The pKBH+ values were determined using the Hammett equation, employing several acid functions in order to determine which of them describes best the protonation process of the studied organic acids. The thermodynamic pKBH+ values as well as those of the solvation parameters m, m* and f and of the thermodynamic protonation constants (or, rather, the pKa,p values were also defermined. The method of characteristic vector analysis (CVA was used to reconstruct the experimental spectra.

  10. Solubility of HCL in sulfuric acid at stratospheric temperatures

    Science.gov (United States)

    Williams, Leah R.; Golden, David M.

    1993-01-01

    The solubility of HCl in sulfuric acid was measured using a Knudsen cell technique. Effective Henry's law constants are reported for sulfuric acid concentrations between 50 and 60 weight percent and for temperatures between 220 and 230 K. The measured values indicate that very little HCl will be dissolved in the stratospheric sulfate aerosol particles.

  11. Electrochemical Behavior of Sulfur in Aqueous Alkaline Solutions

    Science.gov (United States)

    Mamyrbekova, Aigul; Mamitova, A. D.; Mamyrbekova, Aizhan

    2018-03-01

    The kinetics and mechanism of the electrode oxidation-reduction of sulfur on an electrically conductive sulfur-graphite electrode in an alkaline solution was studied by the potentiodynamic method. To examine the mechanism of electrode processes occurring during AC polarization on a sulfur-graphite electrode, the cyclic polarization in both directions and anodic polarization curves were recorded. The kinetic parameters: charge transfer coefficients (α), diffusion coefficients ( D), heterogeneous rate constants of electrode process ( k s), and effective activation energies of the process ( E a) were calculated from the results of polarization measurements. An analysis of the results and calculated kinetic parameters of electrode processes showed that discharge ionization of sulfur in alkaline solutions occurs as a sequence of two stages and is a quasireversible process.

  12. Effects of Sulfurization Temperature on Properties of CZTS Films by Vacuum Evaporation and Sulfurization Method

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    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.

  13. Diffusion coefficient and solubility of isobutene and trans-2-butene in aqueous sulfuric acid solutions

    NARCIS (Netherlands)

    Brilman, Derk Willem Frederik; van Swaaij, Willibrordus Petrus Maria; Versteeg, Geert

    2001-01-01

    The diffusion coefficient and the physical solubility of isobutene and trans-2-butene in aqueous sulfuric acid solutions cannot be determined experimentally due to the occurrence of fast chemical reactions. In the present contribution these physicochemical parameters are estimated. For the

  14. Diffusion Coefficient and Solubility of Isobutene and trans-2-Butene in Aqueous Sulfuric Acid Solutions

    NARCIS (Netherlands)

    Brilman, Derk W.F.; Swaaij, Wim P.M. van; Versteeg, Geert F.

    2001-01-01

    The diffusion coefficient and the physical solubility of isobutene and trans-2-butene in aqueous sulfuric acid solutions cannot be determined experimentally due to the occurrence of fast chemical reactions. In the present contribution these physicochemical parameters are estimated. For the

  15. Synthesis and Application of Iron Oxide/Silica Gel Nanocomposite for Removal of Sulfur Dyes from Aqueous Solutions

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    Naser Tavassoli

    2017-03-01

    Full Text Available Background & Aims of the Study: water pollution by synthetic organic dyes is mainly regarded as environmental and ecological critical issues worldwide. In this research, magnetite iron oxide/silica gel nanocomposite (termed as Fe3O4/SG was synthesized chemically and then used as an effective adsorbent for removal of sulfur dyes from aqueous solution. Materials and Methods: The various parameters such as pH, sorbent dosage, initial dye concentration, contact time and dye solution temperature were investigated in a batch system. The equilibrium data were analyzed by Langmuir and Freundlich isotherm models. Results: The experimental data fit well with pseudo-second-order kinetic model (R2≥0.998 and conformed better to Langmuir isotherm model (R2≥0.997. The maximum adsorption capacity for Fe3O4/SG obtained from the Langmuir model was 11.1mg/g. Evaluation of thermodynamic parameters proved that the adsorption process was normally feasible, spontaneous and exothermic. Conclusion: It can be concluded that the Fe3O4/SG can be considered as a cost-effective and an environmental friendly adsorbent for efficient removal of sulfur dyes from aqueous solutions.

  16. Sulphur Kβ emission spectra reveal protonation states of aqueous sulfuric acid.

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    Niskanen, Johannes; Sahle, Christoph J; Ruotsalainen, Kari O; Müller, Harald; Kavčič, Matjaž; Žitnik, Matjaž; Bučar, Klemen; Petric, Marko; Hakala, Mikko; Huotari, Simo

    2016-02-18

    In this paper we report an X-ray emission study of bulk aqueous sulfuric acid. Throughout the range of molarities from 1 M to 18 M the sulfur Kβ emission spectra from H2SO4 (aq) depend on the molar fractions and related deprotonation of H2SO4. We compare the experimental results with results from emission spectrum calculations based on atomic structures of single molecules and structures from ab initio molecular dynamics simulations. We show that the S Kβ emission spectrum is a sensitive probe of the protonation state of the acid molecules. Using non-negative matrix factorization we are able to extract the fractions of different protonation states in the spectra, and the results are in good agreement with the simulation for the higher part of the concentration range.

  17. Sulphur Kβ emission spectra reveal protonation states of aqueous sulfuric acid

    Science.gov (United States)

    Niskanen, Johannes; Sahle, Christoph J.; Ruotsalainen, Kari O.; Müller, Harald; Kavčič, Matjaž; Žitnik, Matjaž; Bučar, Klemen; Petric, Marko; Hakala, Mikko; Huotari, Simo

    2016-01-01

    In this paper we report an X-ray emission study of bulk aqueous sulfuric acid. Throughout the range of molarities from 1 M to 18 M the sulfur Kβ emission spectra from H2SO4 (aq) depend on the molar fractions and related deprotonation of H2SO4. We compare the experimental results with results from emission spectrum calculations based on atomic structures of single molecules and structures from ab initio molecular dynamics simulations. We show that the S Kβ emission spectrum is a sensitive probe of the protonation state of the acid molecules. Using non-negative matrix factorization we are able to extract the fractions of different protonation states in the spectra, and the results are in good agreement with the simulation for the higher part of the concentration range. PMID:26888159

  18. 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...

  19. The partitioning of sulfur between multicomponent aqueous fluids and felsic melts

    Science.gov (United States)

    Binder, Bernd; Wenzel, Thomas; Keppler, Hans

    2018-02-01

    Sulfur partitioning between melt and fluid phase largely controls the environmental impact of volcanic eruptions. Fluid/melt partitioning data also provide the physical basis for interpreting changes in volcanic gas compositions that are used in eruption forecasts. To better constrain some variables that control the behavior of sulfur in felsic systems, in particular the interaction between different volatiles, we studied the partitioning of sulfur between aqueous fluids and haplogranitic melts at 200 MPa and 750-850 °C as a function of oxygen fugacity (Ni-NiO or Re-ReO2 buffer), melt composition (Al/(Na + K) ratio), and fluid composition (NaCl and CO2 content). The data confirm a first-order influence of oxygen fugacity on the partitioning of sulfur. Under "reducing conditions" (Ni-NiO buffer), D fluid/melt is nearly one order of magnitude larger (323 ± 14 for a metaluminous melt) than under "oxidizing conditions" (Re-ReO2 buffer; 74 ± 5 for a metaluminous melt). This effect is likely related to a major change in sulfur speciation in both melt and fluid. Raman spectra of the quenched fluids show the presence of H2S and HS- under reducing conditions and of SO4 2- and HSO4 - under oxidizing conditions, while SO2 is undetectable. The latter observation suggests that already at the Re-ReO2 buffer, sulfur in the fluid is almost completely in the S6+ state and, therefore, more oxidized than expected according to current models. CO2 in the fluid (up to x CO2 = 0.3) has no effect on the fluid/melt partitioning of sulfur, neither under oxidizing nor under reducing conditions. However, the effect of NaCl depends on redox state. While at oxidizing conditions, D fluid/melt is independent of x NaCl, the fluid/melt partition coefficient strongly decreases with NaCl content under reducing conditions, probably due to a change from H2S to NaSH as dominant sulfur species in the fluid. A decrease of D fluid/melt with alkali content in the melt is observed over the entire

  20. High temperature damage of a re-sulfurized stainless steel

    International Nuclear Information System (INIS)

    Tinet, Hougo

    2002-01-01

    After having evoked the industrial problem raised by high-temperature damage in the 303 stainless steel, and outlined that the experimental study of high-temperature damage implies the study of the sane (or non damaged) material, the study of micro-voids germination, growth and coalescence, and the study of the material failure process, the author of this research thesis reports a bibliographical study on the behaviour of sane re-sulfurized stainless steel and different damage models. He presents experimental techniques (thermal-mechanical compression and tensile tests, image analysis in optical microscopy) which have been used in this work, and describes and comments results obtained on axisymmetric samples for micro-void germination, growth and coalescence in case of a damage under low and medium stress triaxiality. The last part addresses the study of the damage of strongly notched samples (stress triaxialities close to those existing at the crack bottom) [fr

  1. Kinetics and mechanism of OsOsub(4) catalyzed oxidation of chalcones by Cesub(4) in aqueous acetic sulfuric acid media

    Energy Technology Data Exchange (ETDEWEB)

    Srinivasulu, P.V.; Adinarayana, M.; Sethuram, B.; Rao, T.N. (Osmania Univ., Hyderabad (India). Dept. of Chemistry)

    1985-01-01

    Kinetics of OsOsub(4) catalyzed oxidation of chalcones by Cesup(4+) was studied in aqueous acetic-sulfuric acid medium in the temperature range 313 to 338 K. The order in oxidant is zero while the order with respect to substrate and catalyst are each fractional. The rate of the reaction decreased with increase in percentage of acetic acid while (Hsup(+)) had practically no effect on the rate. The rates of various substituted chalcones are given. A mechanism in which formation of a cyclic ester between chalcone and OsOsub(4) in a fast step followed by its decomposition in a rate-determining step is envisaged.

  2. On the calculation of the electrolyte aqueous solution freezing temperature

    International Nuclear Information System (INIS)

    Ptitsyn, A.B.

    1995-01-01

    Analytical expression of the dependence of freezing temperature of electrolyte (CdCl 2 , CdSO 4 , BeSO 4 ) aqueous solutions on their composition was found. Three different methods were suggested were suggested for calculation of water activity in multicomponent solution. It was established that sublinear extrapolation of freezing temperature of salt aqueous solutions was possible not up to -5 deg C, but up to -15 deg C, independently of their composition. 6 refs.; 2 figs

  3. Experimental research on sealing performance of sulfur hexafluoride electrical equipment under low-temperature environment

    Science.gov (United States)

    Li, G. X.; Li, L.; Zhang, R.; Jiang, Z. Q.; Zhu, X. C.; Gao, Z. W.; Zhang, H. D.; Zhang, J.

    2018-01-01

    It is discovered that the sealing performance of the sulfur hexafluoride electrical equipment worsens under low temperature, but research in the aspect is reported rarely when corresponding measures are adopted for improving the sealing performance of electrical equipment. Therefore, sealing and leakage test of sulfur hexafluoride electrical equipment was implemented under low-temperature environment according to the analysis on gas sealing methods of sulfur hexafluoride electrical equipment. Causes of gas leakage of sulfur hexafluoride electrical equipment under low temperature environment were analyzed according to test results. Effective measures were proposed for improving the gas sealing performance of the equipment, thereby providing valuable reference for gas sealing design, installation, operation maintenance and failure analysis of sulfur hexafluoride electrical equipment under low - temperature environment.

  4. An Aqueous Inorganic Polymer Binder for High Performance Lithium-Sulfur Batteries with Flame-Retardant Properties.

    Science.gov (United States)

    Zhou, Guangmin; Liu, Kai; Fan, Yanchen; Yuan, Mengqi; Liu, Bofei; Liu, Wei; Shi, Feifei; Liu, Yayuan; Chen, Wei; Lopez, Jeffrey; Zhuo, Denys; Zhao, Jie; Tsao, Yuchi; Huang, Xuanyi; Zhang, Qianfan; Cui, Yi

    2018-02-28

    Lithium-sulfur (Li-S) batteries are regarded as promising next-generation high energy density storage devices for both portable electronics and electric vehicles due to their high energy density, low cost, and environmental friendliness. However, there remain some issues yet to be fully addressed with the main challenges stemming from the ionically insulating nature of sulfur and the dissolution of polysulfides in electrolyte with subsequent parasitic reactions leading to low sulfur utilization and poor cycle life. The high flammability of sulfur is another serious safety concern which has hindered its further application. Herein, an aqueous inorganic polymer, ammonium polyphosphate (APP), has been developed as a novel multifunctional binder to address the above issues. The strong binding affinity of the main chain of APP with lithium polysulfides blocks diffusion of polysulfide anions and inhibits their shuttling effect. The coupling of APP with Li ion facilitates ion transfer and promotes the kinetics of the cathode reaction. Moreover, APP can serve as a flame retardant, thus significantly reducing the flammability of the sulfur cathode. In addition, the aqueous characteristic of the binder avoids the use of toxic organic solvents, thus significantly improving safety. As a result, a high rate capacity of 520 mAh g -1 at 4 C and excellent cycling stability of ∼0.038% capacity decay per cycle at 0.5 C for 400 cycles are achieved based on this binder. This work offers a feasible and effective strategy for employing APP as an efficient multifunctional binder toward building next-generation high energy density Li-S batteries.

  5. Transitions in aqueous solutions of sucrose at subzero temperatures

    Czech Academy of Sciences Publication Activity Database

    Sikora, Antonín; Dupanov, V. O.; Kratochvíl, Jaroslav; Zámečník, J.

    2007-01-01

    Roč. 46, č. 1 (2007), s. 71-85 ISSN 0022-2348 R&D Projects: GA ČR(CZ) GA522/04/0384 Institutional research plan: CEZ:AV0Z40500505 Keywords : aqueous sucrose solutions * subzero temperature * glass transitions Subject RIV: BJ - Thermodynamics Impact factor: 0.809, year: 2007

  6. Removals of aqueous sulfur dioxide and hydrogen sulfide using CeO2-NiAl-LDHs coating activated carbon and its mix with carbon nano-tubes

    KAUST Repository

    Li, Jing

    2015-07-01

    Ce-doped NiAl/layered double hydroxide was coated at activated carbon by urea hydrolysis method (CeO2-NiAl-LDHs/AC) in one pot, which was characterized by X-ray diffraction, infrared spectra, field emission scanning electron microscope and electrochemical techniques. CeO2-NiAl-LDHs/AC shows good uptake for aqueous sulfur dioxide (483.09mg/g) and hydrogen sulfide (181.15mg/g), respectively at 25°C. Meanwhile, the electrochemical removals of aqueous sulfur dioxide and hydrogen sulfide were respectively investigated at the mix of CeO2-NiAl-LDHs/AC and carbon nano-tubes modified homed paraffin-impregnated electrode. Both sulfur dioxide and hydrogen sulfide could be effectively oxidized to sulfuric acid at 1.0V in alkaline aqueous solution. © 2015 Elsevier B.V.

  7. PUMP DESIGN AND COMPUTATIONAL FLUID DYNAMIC ANALYSIS FOR HIGH TEMPERATURE SULFURIC ACID TRANSFER SYSTEM

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    JUNG-SIK CHOI

    2014-06-01

    Full Text Available In this study, we proposed a newly designed sulfuric acid transfer system for the sulfur-iodine (SI thermochemical cycle. The proposed sulfuric acid transfer system was evaluated using a computational fluid dynamics (CFD analysis for investigating thermodynamic/hydrodynamic characteristics and material properties. This analysis was conducted to obtain reliable continuous operation parameters; in particular, a thermal analysis was performed on the bellows box and bellows at amplitudes and various frequencies (0.1, 0.5, and 1.0 Hz. However, the high temperatures and strongly corrosive operating conditions of the current sulfuric acid system present challenges with respect to the structural materials of the transfer system. To resolve this issue, we designed a novel transfer system using polytetrafluoroethylene (PTFE, Teflon® as a bellows material for the transfer of sulfuric acid. We also carried out a CFD analysis of the design. The CFD results indicated that the maximum applicable temperature of PTFE is about 533 K (260 °C, even though its melting point is around 600 K. This result implies that the PTFE is a potential material for the sulfuric acid transfer system. The CFD simulations also confirmed that the sulfuric acid transfer system was designed properly for this particular investigation.

  8. Aqueous Geochemistry at High Pressures and High Temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Bass, Jay D. [Univ. of Illinois, Urbana-Champaign, IL (United States)

    2015-05-21

    This project is aimed at experimental characterization of the sound velocities, equations of state (EOS), and derived physical and chemical properties of aqueous solutions and carbon dioxide at extreme pressure and temperature conditions relevant to processes occurring in the interior of the Earth. Chemical transport, phase changes (including melting), fluid-solid reactions, and formation of magmatic liquids at convergent plat boundaries are a key motivation for this project. Research in this area has long been limited by the extreme experimental challenges and lack of data under the appropriate pressure-temperature (P-T) conditions. The vast majority of studies of aqueous geochemistry relevant to terrestrial problems of fluid-rock interactions have been conducted at 0.3 GPa or less, and the widely used Helgeson-Kirkham-Flowers equation of state for aqueous species is applicable only at ~ < 0.5 GPa. These limits are unfortunate because fluid flow and reactions plays a central role in many deeper environments. Recent efforts including our own, have resulted in new experimental techniques that now make it possible to investigate properties of homogeneous and heterogeneous equilibria involving aqueous species and minerals over a much broader range of pressure and temperature appropriate for deep crustal and upper mantle processes involving water-rich fluids. We carried out 1) Brillouin scattering measurements of the equations of state and molar volume of water and carbon dioxide to over 10 GPa and 870K using precise resistance heating of samples under pressure in the diamond anvil cell, and 2) the phase diagrams of the water and CO2, and 3) Exploring new experimental approaches, including CO2 laser heating of samples in a diamond cell, to measurements of sound velocities, EOS, and phase relations by Brillouin scattering to far greater pressures and temperatures.

  9. Influence of sulfur on the passivity of inconel 600 in aqueous environment at 3000C. Relationship with stress corrosion

    International Nuclear Information System (INIS)

    Vancon, D.

    1989-11-01

    Dissolution kinetics and repassivation of inconel 600 in simulated primary coolant circuits of PWR is studied by fast traction experiment under potentiostatic control. The notion of elementary electrochemical transient is introduced. The model of anodic dissolution - film rupture allows the calculation of crack growth in constant deformation rate tests. When sulfur concentration is smaller than 100 micrograms/g the current is low, above the current is high. Calculation of crack growth from high level current are consistent with experimental data. Influence of pH, temperature, solution composition are determined. A Comparative study with nickel, incoloy 690 and a 19% chromium alloy was carried out to understand fast traction phenomena. Chromium plays an important part without pollution a protecting chromium oxide is formed. In polluted environment sulfur prevent nucleation of this compound and chromium hydroxides are precipitated on the surface. With pure nickel there is no passivity in presence of sulfur [fr

  10. Coagulation-condensation structure formation in aqueous suspensions of mixtures of sulfur and gypsum

    Directory of Open Access Journals (Sweden)

    K. Toshtay

    2013-05-01

    Full Text Available The characteristics of structure formation in hydrosuspensions of powdered sulfur and its mixtures with gypsum was investigated. The effect of cationic (CTAB and anionic (SDBS surfactants on the surface tension of water; ζ-potential of the sulfur particles and wettability of sulfur was learned. Both surfactants at low concentrations; lead to an increase in plastic strength (Pm of the suspension; and at high concentrations (above CMC – they lead to Pm reduce. In addition; it was found that the surfactants substantially change ζ-potential of the sulfur particles – cationic surfactants  lead to charge exchange and anionic surfactants increase the negative charge of the particles. These changes are the result to restructuring in the adsorption layers of surfactants - the formation of a saturated mono-layer while up to Pm maximum; bilayer - after CMC (while the Pm is reducing.

  11. Preparation of levoglucosenone through sulfuric acid promoted pyrolysis of bagasse at low temperature.

    Science.gov (United States)

    Sui, Xian-wei; Wang, Zhi; Liao, Bing; Zhang, Ying; Guo, Qing-xiang

    2012-01-01

    Fast pyrolysis of bagasse pretreated by sulfuric acid was conducted in a fixed bed reactor to prepare levoglucosenone (LGO), a very important anhydrosugar for organic synthesis. The liquid yield and LGO yield were studied at temperatures from 240 to 350 °C and sulfuric acid loadings from 0.92 to 7.10 wt.%. An optimal LGO yield of 7.58 wt.% was obtained at 270 °C with a sulfuric acid pretreatment concentration of 0.05 M (corresponding to 4.28 wt.% sulfuric acid loading). For comparison, microcrystalline cellulose pretreated by 0.05 M sulfuric acid solution was pyrolyzed at temperature from 270 °C to 320 °C, and bagasse loaded with 3-5 wt.% phosphoric acid was pyrolyzed at temperature from 270 °C to 350 °C. The highest yield of LGO from bagasse was 30% higher than that from microcrystalline cellulose, and treatment with sulfuric acid allowed a 21% higher yield than treatment with phosphoric acid. Copyright © 2011 Elsevier Ltd. All rights reserved.

  12. Aqueous geochemistry of low molecular weight hydrocarbons at elevated temperatures and pressures: constraints from mineral buffered laboratory experiments

    Science.gov (United States)

    Seewald, Jeffrey S.

    2001-05-01

    Organic matter, water, and minerals coexist at elevated temperatures and pressures in sedimentary basins and participate in a wide range of geochemical processes that includes the generation of oil and natural gas. A series of laboratory experiments were conducted at 300 to 350°C and 350 bars to examine chemical interactions involving low molecular weight aqueous hydrocarbons with water and Fe-bearing minerals under hydrothermal conditions. Mineral buffers composed of hematite-magnetite-pyrite, hematite-magnetite, and pyrite-pyrrhotite-magnetite were added to each experiment to fix the redox state of the fluid and the activity of reduced sulfur species. During each experiment the chemical system was externally modified by addition of ethene, ethane, propene, 1-butene, or n-heptane, and variations in the abundance of aqueous organic species were monitored as a function of time and temperature. Results of the experiments indicate that decomposition of aqueous n-alkanes proceeds through a series of oxidation and hydration reactions that sequentially produce alkenes, alcohols, ketones, and organic acids as reaction intermediaries. Organic acids subsequently undergo decarboxylation and/or oxidation reactions to form carbon dioxide and shorter chain saturated hydrocarbons. This alteration assemblage is compositionally distinct from that produced by thermal cracking under anhydrous conditions, indicating that the presence of water and minerals provide alternative reaction pathways for the decomposition of hydrocarbons. The rate of hydrocarbon oxidation decreases substantially under reducing conditions and in the absence of catalytically active aqueous sulfur species. These results represent compelling evidence that the stability of aqueous hydrocarbons at elevated temperatures in natural environments is not a simple function of time and temperature alone. Under the appropriate geochemical conditions, stepwise oxidation represents a mechanism for the decomposition of low

  13. Temperature-Invariant Aqueous Microgels as Hosts for Biomacromolecules.

    Science.gov (United States)

    Mastour Tehrani, Sepehr; Lu, Yijie; Guerin, Gerald; Soleimani, Mohsen; Pichugin, Dmitry; Winnik, Mitchell A

    2015-10-12

    Immobilization of enzymes on solid supports has been widely used to improve enzyme recycling, enzyme stability, and performance. We are interested in using aqueous microgels (colloidal hydrogels) as carriers for enzymes used in high-temperature reactions. These microgels should maintain their volume and colloidal stability in aqueous media up to 100 °C to serve as thermo-stable supports for enzymes. For this purpose, we prepared poly(N-hydroxyethyl acrylamide) (PHEAA) microgels via a two-step synthesis. First, we used precipitation polymerization in water to synthesize colloidal poly(diethylene glycol-ethyl ether acrylate) (PDEGAC) particles as a precursor. PDEGAC forms solvent swollen microgels in organic solvents such as methanol and dioxane and in water at temperatures below 15 °C. In the second step, these PDEGAC particles were transformed to PHEAA microgels through aminolysis in dioxane with ethanolamine and a small amount of ethylenediamine. Dynamic laser scattering studies confirmed that the colloidal stability of microgels was maintained during the aminolysis in dioxane and subsequent transfer to water. Characterization of the PHEAA microgels indicated about 9 mol % of primary amino groups. These provide functionality for bioconjugation. As proof-of-concept experiments, we attached the enzyme horseradish peroxidase (HRP) to these aqueous microgels through (i) N-(3-(dimethylamino)propyl)-N'-ethylcarbodiimide hydrochloride (EDC) coupling to the carboxylated microgels or (ii) bis-aryl hydrazone (BAH) coupling to microgels functionalized with 6-hydrazinonicotinate acetone (PHEAA-HyNic). Our results showed that HRP maintained its catalytic activity after covalent attachment (87% for EDC coupling, 96% for BAH coupling). The microgel enhanced the stability of the enzyme to thermal denaturation. For example, the residual activity of the microgel-supported enzyme was 76% after 330 min of annealing at 50 °C, compared to only 20% for the free enzyme under these

  14. Hybrid sulfur cycle operation for high-temperature gas-cooled reactors

    Science.gov (United States)

    Gorensek, Maximilian B

    2015-02-17

    A hybrid sulfur (HyS) cycle process for the production of hydrogen is provided. The process uses a proton exchange membrane (PEM) SO.sub.2-depolarized electrolyzer (SDE) for the low-temperature, electrochemical reaction step and a bayonet reactor for the high-temperature decomposition step The process can be operated at lower temperature and pressure ranges while still providing an overall energy efficient cycle process.

  15. Measuring the Densities of Aqueous Glasses at Cryogenic Temperatures.

    Science.gov (United States)

    Shen, Chen; Julius, Ethan F; Tyree, Timothy J; Dan, Ritwik; Moreau, David W; Thorne, Robert

    2017-06-28

    We demonstrate a method for determining the vitreous phase cryogenic temperature densities of aqueous mixtures, and other samples that require rapid cooling, to prepare the desired cryogenic temperature phase. Microliter to picoliter size drops are cooled by projection into a liquid nitrogen-argon (N2-Ar) mixture. The cryogenic temperature phase of the drop is evaluated using a visual assay that correlates with X-ray diffraction measurements. The density of the liquid N2-Ar mixture is adjusted by adding N2 or Ar until the drop becomes neutrally buoyant. The density of this mixture and thus of the drop is determined using a test mass and Archimedes principle. With appropriate care in drop preparation, management of gas above the liquid cryogen mixture to minimize icing, and regular mixing of the cryogenic mixture to prevent density stratification and phase separation, densities accurate to <0.5% of drops as small as 50 pL can readily be determined. Measurements on aqueous cryoprotectant mixtures provide insight into cryoprotectant action, and provide quantitative data to facilitate thermal contraction matching in biological cryopreservation.

  16. Adsorptive removal of sulfur compounds using IRMOF-3 at ambient temperature

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Xiao-Ling [Key Laboratory of Coal Science and Technology, Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024 (China); Fan, Hui-Ling, E-mail: fanhuiling@tyut.edu.cn [Key Laboratory of Coal Science and Technology, Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024 (China); Tian, Zhen [Shanghai Second Polytechnic University, Shanghai 201209 (China); He, En-Yun; Li, Ye; Shangguan, Ju [Key Laboratory of Coal Science and Technology, Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024 (China)

    2014-01-15

    Zinc-based metal–organic framework (IRMOF-3) was used as adsorbent for removal of dimethyl sulfide, ethyl mercaptan and hydrogen sulfide in fixed bed reactor at ambient temperature. These samples before and after exposure to sulfur compounds were characterized by Fourier transform infrared (FTIR), and X-ray diffraction (XRD), and thermo gravimetric (TG), and X-ray photoelectron spectroscopy (XPS). The results show that IRMOF-3 exhibit the best performance for hydrogen sulfide removal with the highest breakthrough sulfur capacity, followed by ethyl mercaptan and dimethyl sulfide. This is in consistent with the interaction strength between IRMOF-3 and sulfur compounds. In the case of dimethyl sulfide and ethyl mercaptan, the interaction comes from the weak interaction between the amino group in the MOFs and the sulfur atom of the adsorbate. This can also be considered as a hydrogen bond complex in which the amino group in the MOFs and the S atom of the sulfur compounds play the role of H-donor and H-acceptor, respectively. In the case of hydrogen sulfide, the interaction with sulfur atom originates from the amino group and zinc site in the MOFs. The former is more like an acid–base interaction, whereas the latter results in new products of ZnS and H{sub 2}O and serious destruction of the MOFs.

  17. Adsorptive removal of sulfur compounds using IRMOF-3 at ambient temperature

    Science.gov (United States)

    Wang, Xiao-Ling; Fan, Hui-Ling; Tian, Zhen; He, En-Yun; Li, Ye; Shangguan, Ju

    2014-01-01

    Zinc-based metal-organic framework (IRMOF-3) was used as adsorbent for removal of dimethyl sulfide, ethyl mercaptan and hydrogen sulfide in fixed bed reactor at ambient temperature. These samples before and after exposure to sulfur compounds were characterized by Fourier transform infrared (FTIR), and X-ray diffraction (XRD), and thermo gravimetric (TG), and X-ray photoelectron spectroscopy (XPS). The results show that IRMOF-3 exhibit the best performance for hydrogen sulfide removal with the highest breakthrough sulfur capacity, followed by ethyl mercaptan and dimethyl sulfide. This is in consistent with the interaction strength between IRMOF-3 and sulfur compounds. In the case of dimethyl sulfide and ethyl mercaptan, the interaction comes from the weak interaction between the amino group in the MOFs and the sulfur atom of the adsorbate. This can also be considered as a hydrogen bond complex in which the amino group in the MOFs and the S atom of the sulfur compounds play the role of H-donor and H-acceptor, respectively. In the case of hydrogen sulfide, the interaction with sulfur atom originates from the amino group and zinc site in the MOFs. The former is more like an acid-base interaction, whereas the latter results in new products of ZnS and H2O and serious destruction of the MOFs.

  18. Iron and zinc partitioning between coexisting stannite and sphalerite: a possible indicator of temperature and sulfur fugacity

    Science.gov (United States)

    Shimizu, M.; Shikazono, N.

    1985-10-01

    Stannite and sphalerite coexisting with iron sulfides (pyrite and/or pyrrhotite) from Japanese ore deposits associated with tin mineralization were analyzed. Based on the iron and zinc partitioning between stannite and sphalerite, the formation temperature and sulfur fugacity for this mineral assemblage were estimated. A good correlation between stannite-sphalerite temperatures and filling temperatures of fluid inclusions and sulfur isotope temperatures was obtained. This good correlation suggests that the stannite-sphalerite pair is a useful indicator of temperature and sulfur fugacity. It is deduced that the formation temperatures are not different for skarn-type, polymetallic vein-type and Sn-W vein-type deposits, whereas the sulfur fugacities are different; sulfur fugacities increase from the skarn-type through the Sn-W vein-type to the polymetallic vein-type deposits.

  19. Determination of the products from the oxidation of aqueous hydrogen sulfide by sulfur K-edge XANES spectroscopy

    International Nuclear Information System (INIS)

    Vairavamurthy, A.; Manowitz, B.; Jeon, Yongseog; Zhou, Weiqing.

    1993-01-01

    The application of synchrotron radiation based XANES spectroscopy is described for determining the products formed from oxidation of aqueous sulfide.This technique allows simultaneous characterization of all the different forms of sulfur both qualitatively and quantitatively. Thus, it is superior to other commonly used techniques, such as chromatography, which are usually targeted at specific compounds. Since the use of XANES-based technique is relatively new in geochemistry, we present here an overview of the principles of the technique as well as the approach used for quantitative analysis. We studied the sulfide oxidation under conditions of high sulfide to oxygen ratio using 0.1 M sulfide solutions and the catalytic effects of sea sand, Fe 2+ , and Ni 2+ , were also examined. Significant results obtained from this study are presented to illustrate the value of the XANES technique for the determination of the products formed from the oxidation of sulfide at high concentrations

  20. Chemical and spectral behavior of nitric acid in aqueous sulfuric acid solutions: Absorption spectrum and molar absorption coefficient of nitronium ion

    Science.gov (United States)

    Ershov, Boris G.; Panich, Nadezhda M.

    2018-01-01

    The chemical species formed from nitric acid in aqueous solutions of sulfuric acid (up to 18.0 mol L- 1) were studied by optical spectroscopy method. The concentration region of nitronium ion formation was identified and NO2+ ion absorption spectrum was measured (λmax ≤ 190 nm and ε190 = 1040 ± 50 mol- 1 L cm- 1).

  1. High-temperature extraction of rhenium from sulfuric acid solutions with trialkylamines

    International Nuclear Information System (INIS)

    Gladyhev, V.P.; Andreeva, N.N.; Kim, E.M.; Kovaleva, S.V.

    1985-01-01

    This paper attempts to determine the possibility of conducting high-temperature extraction of rhenium from sulfuric acid solutions with trialkylamines (TAA) using higher hydrocarbon-paraffin mixtures as the diluent of the extraction system. Substitution of kerosene by paraffin in the extraction system would permit decreasing the danger of fire and explosions during he extraction process. In extracting rhenium from industrial solutions with a melt of higher paraffins containing TAA and alcohols, the extraction system can be continously heated in heat exchangers through which washing sulfuric acid passes and then goes to the extractor. This permits utilizing the heat and decreases the temperature of the solutions for extraction to the optimum temperatures. Extraction of rhenium with a melt of trioctylamine in paraffin obeys the same mechanisms as high-temperature extraction of ruthenium (IV) by amines in kerosene and aromatic hydrocarbons

  2. Modeling of a Large-Scale High Temperature Regenerative Sulfur Removal Process

    DEFF Research Database (Denmark)

    Konttinen, Jukka T.; Johnsson, Jan Erik

    1999-01-01

    model that does not account for bed hydrodynamics. The pilot-scale test run results, obtained in the test runs of the sulfur removal process with real coal gasifier gas, have been used for parameter estimation. The validity of the reactor model for commercial-scale design applications is discussed.......Regenerable mixed metal oxide sorbents are prime candidates for the removal of hydrogen sulfide from hot gasifier gas in the simplified integrated gasification combined cycle (IGCC) process. As part of the regenerative sulfur removal process development, reactor models are needed for scale......-up. Steady-state kinetic reactor models are needed for reactor sizing, and dynamic models can be used for process control design and operator training. The regenerative sulfur removal process to be studied in this paper consists of two side-by-side fluidized bed reactors operating at temperatures of 400...

  3. Origin of the critical temperature discontinuity in superconducting sulfur under high pressure

    Science.gov (United States)

    Monni, M.; Bernardini, F.; Sanna, A.; Profeta, G.; Massidda, S.

    2017-02-01

    Elemental sulfur shows a superconducting phase at high pressure (above 100 GPa), with critical temperatures that rise up to 20 K [Phys. Rev. B 65, 064504 (2002), 10.1103/PhysRevB.65.064504; Nature (London) 525, 73 (2015), 10.1038/nature14964] and presenting a jump at about 160 GPa, close to a structural phase transition to the β -Po phase. In this work we present a theoretical and fully ab initio characterization of sulfur based on superconducting density functional theory (SCDFT), focusing in the pressure range from 100 to 200 GPa. Calculations result in very good agreement with available experiments and point out that the origin of the critical temperature discontinuity is not related to the structural phase transition but induced by an electronic Lifshitz transition. This brings a strongly (interband) coupled electron pocket available for the superconducting condensation.

  4. 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

  5. Transformation of aqueous sulfonamides under horseradish peroxidase and characterization of sulfur dioxide extrusion products from sulfadiazine.

    Science.gov (United States)

    Yang, Lihua; Shi, Yang; Li, Jinjin; Fang, Ling; Luan, Tiangang

    2018-06-01

    The potential of horseradish peroxidase (HRP) to catalyze the removal of sulfonamides from water and the effects of different H 2 O 2 and HRP concentrations were investigated. Six sulfonamides, each with a five- or six-membered heterocyclic group, including sulfamethoxazole (SMX), sulfathiazole (STZ), sulfapyridine (SPD), sulfadiazine (SDZ), sulfamerazine (SMR) and sulfamethoxypyridazine (SMP) were selected as target compounds. All sulfonamides exhibit a pseudo-first-order dependence of the concentration versus the reaction time. The decay rate (k, h -1 ) of the six sulfonamides spiked individually exhibit a trend following the order of STZ > SMP, SPD > SMR > SDZ » SMX. When spiked together, the coexistent sulfonamides might act as mediators for the enhancement of SMX removal and as competitors for the decreased removal of most sulfonamides. Moreover, six transformation products of SDZ are identified by the Thermo Scientific LTQ Orbitrap Elite technique. SDZ transformation involves two steps: one is the Smiles re-arrangement of the structure, and the other is oxidation and sulfur dioxide extrusion. This study is the first to report the removal dynamics of sulfonamides in HRP-catalyzed reactions and the identified products of SDZ. Copyright © 2018 Elsevier Ltd. All rights reserved.

  6. Temperature shifts for extraction and purification of zygomycetes chitosan with dilute sulfuric acid.

    Science.gov (United States)

    Zamani, Akram; Edebo, Lars; Niklasson, Claes; Taherzadeh, Mohammad J

    2010-08-13

    The temperature-dependent hydrolysis and solubility of chitosan in sulfuric acid solutions offer the possibility for chitosan extraction from zygomycetes mycelia and separation from other cellular ingredients with high purity and high recovery. In this study, Rhizomucor pusillus biomass was initially extracted with 0.5 M NaOH at 120 °C for 20 min, leaving an alkali insoluble material (AIM) rich in chitosan. Then, the AIM was subjected to two steps treatment with 72 mM sulfuric acid at (i) room temperature for 10 min followed by (ii) 120 °C for 45 min. During the first step, phosphate of the AIM was released into the acid solution and separated from the chitosan-rich residue by centrifugation. In the second step, the residual AIM was re-suspended in fresh 72 mM sulfuric acid, heated at 120 °C and hot filtered, whereby chitosan was extracted and separated from the hot alkali and acid insoluble material (HAAIM). The chitosan was recovered from the acid solution by precipitation at lowered temperature and raised pH to 8-10. The treatment resulted in 0.34 g chitosan and 0.16 g HAAIM from each gram AIM. At the start, the AIM contained at least 17% phosphate, whereas after the purification, the corresponding phosphate content of the obtained chitosan was just 1%. The purity of this chitosan was higher than 83%. The AIM subjected directly to the treatment with hot sulfuric acid (at 120 °C for 45 min) resulted in a chitosan with a phosphate impurity of 18.5%.

  7. Effect of temperature on iron leaching from bauxite residue by sulfuric acid.

    Science.gov (United States)

    Liu, Zhi-Rong; Zeng, Kai; Zhao, Wei; Li, Ying

    2009-01-01

    Bauxite residue, as solid waste from alumina production, contains mainly hematite [Fe2O3]. Kinetic study of iron leaching of bauxite residue by diluted sulfuric acid at atmospheric pressure has been investigated. The results have been obtained as following: (i) Temperature play an important role in iron leaching from bauxite residue. Higher temperature is favor of Fe(III) leaching from bauxite residue. (ii) The leaching process is applicable to the intra-particle diffusion model and the apparent activation energy of model of leaching is found to be 17.32 kJ/mol.

  8. Experimental particle formation rates spanning tropospheric sulfuric acid and ammonia abundances, ion production rates, and temperatures

    CERN Document Server

    Kürten, Andreas; Almeida, Joao; Kupiainen-Määttä, Oona; Dunne, Eimear M.; Duplissy, Jonathan; Williamson, Christina; Barmet, Peter; Breitenlechner, Martin; Dommen, Josef; Donahue, Neil M.; Flagan, Richard C.; Franchin, Alessandro; Gordon, Hamish; Hakala, Jani; Hansel, Armin; Heinritzi, Martin; Ickes, Luisa; Jokinen, Tuija; Kangasluoma, Juha; Kim, Jaeseok; Kirkby, Jasper; Kupc, Agnieszka; Lehtipalo, Katrianne; Leiminger, Markus; Makhmutov, Vladimir; Onnela, Antti; Ortega, Ismael K.; Petäjä, Tuukka; Praplan, Arnaud P.; Riccobono, Francesco; Rissanen, Matti P.; Rondo, Linda; Schnitzhofer, Ralf; Schobesberger, Siegfried; Smith, James N.; Steiner, Gerhard; Stozhkov, Yuri; Tomé, António; Tröstl, Jasmin; Tsagkogeorgas, Georgios; Wagner, Paul E.; Wimmer, Daniela; Ye, Penglin; Baltensperger, Urs; Carslaw, Ken; Kulmala, Markku; Curtius, Joachim

    2016-01-01

    Binary nucleation of sulfuric acid and water as well as ternary nucleation involving ammonia arethought to be the dominant processes responsible for new particle formation (NPF) in the cold temperaturesof the middle and upper troposphere. Ions are also thought to be important for particle nucleation inthese regions. However, global models presently lack experimentally measured NPF rates under controlledlaboratory conditions and so at present must rely on theoretical or empirical parameterizations. Here withdata obtained in the European Organization for Nuclear Research CLOUD (Cosmics Leaving OUtdoor Droplets)chamber, we present the first experimental survey of NPF rates spanning free tropospheric conditions. Theconditions during nucleation cover a temperature range from 208 to 298 K, sulfuric acid concentrationsbet ween 5 × 105and 1 × 109cm3, and ammonia mixing ratios from zero added ammonia, i.e., nominally purebinary, to a maximum of ~1400 parts per trillion by volume (pptv). We performed nucleation s...

  9. Oxidation of sulfur (IV by oxygen in aqueous solution: role of some metal ions

    Directory of Open Access Journals (Sweden)

    Martins Claudia R.

    1999-01-01

    Full Text Available Catalytic effect of metal ions: Cr(VI, Cr(III, Cd(II, V(V and chloride anion, on the oxidation of S(IV in aqueous solution, at concentrations of metal ions and S(IV usually found in urban atmospheres, were studied under controlled experimental conditions (pH (2.1 - 4,5, T (25.0 - 35.0 °C, air flow rate, concentration of reactants, etc.... The kinetic constant determined at 25.0 °C and pH range (2.1 - 4.5, using ultra pure water was 8.0 ± 0.5 x 10-4 s-1. This value was considered as a reference for the oxidation reaction rate. The kinetic constants determined in the presence of Cr(VI revealed that the oxidation reaction of S(IV is quite influenced by the acidity. At pH = 2.1 (K = 2.3 x 10-2 mg-1 L s-1 the reaction is carried out with a rate five times greater when compared to pH = 2.6 (K = 4.3 x 10-3 mg-1 L s-1 and thirty times greater when compared to pH = 3.4 (K= 8.0 x 10 -4 mg-1 L s-1. The following rate expression was obtained at pH = 2.6: -r(S(IV =K [Cr(VI] [S(IV] and the activation energy found was: Ea =70.3KJ/mol. No catalytic effects were observed for Cd(II or chloride ion, while inhibitory effects were observed for Cr(III and V(V ions.

  10. Oxyhalogen-sulfur chemistry: kinetics and mechanism of oxidation of captopril by acidified bromate and aqueous bromine.

    Science.gov (United States)

    Kapungu, G P; Rukweza, G; Tran, Thai; Mbiya, Wilbes; Adigun, Risikat; Ndungu, Patrick; Martincigh, Bice; Simoyi, Reuben H

    2013-04-04

    By nature of their nucleophilicity, all thiol-based drugs are oxidatively metabolized in the physiological environment. The key to understanding the physiological role of a hypertension drug, (2S)-1-[(2S)-2-methyl-3-sulfanylpropanoyl]pyrrolidine-2-carboxylic acid, medically known as captopril is through studying its oxidation pathway: its reactive intermediates and oxidation products. The oxidation of captopril by aqueous bromine and acidified bromate has been studied by spectrophotometric and electrospray ionization techniques. The stoichiometry for the reaction of acidic bromate with captopril is 1:1, BrO3(-) + (C4H6N)(COOH)(COCHCH3CH2)-SH → (C4H6N)(COOH)(COCHCH3CH2)-SO3H + Br(-), with reaction occurring only at the thiol center. For the direct reaction of bromine with captopril, the ratio is 3:1; 3Br2 + (C4H6N)(COOH)(COCHCH3CH2)-SH + 3H2O → (C4H6N)(COOH)(COCHCH3CH2)-SO3H + 6HBr. In excess acidic bromate conditions the reaction displays an initial induction period followed by a sharp rise in absorbance at 390 nm due to rapid formation of bromine. The direct reaction of aqueous bromine with captopril was much faster than oxidation of the thiol by acidified bromate, with a bimolecular rate constant of (1.046 (±0.08) × 10(5) M(-1) s(-1). The detection of thiyl radicals confirms the involvement of radicals as intermediates in the oxidation of Captopril by acidified BrO3(-). The involvement of thiyl radicals in oxidation of captopril competes with a nonradical pathway involving 2-electron oxidations of the sulfur center. The oxidation product of captopril under these strong oxidizing conditions is a sulfonic acid as confirmed by electrospray ionization mass spectrometry (ESI-MS), iodometric titrations, and proton nuclear magnetic resonance ((1)H NMR) results. There was no evidence from ESI-MS for the formation of the sulfenic and sulfinic acids in the oxidation pathway as the thiol group is rapidly oxidized to the sulfonic acid. A computer simulation analysis of

  11. High Temperature Corrosion Problem of Boiler Components in presence of Sulfur and Alkali based Fuels

    Science.gov (United States)

    Ghosh, Debashis; Mitra, Swapan Kumar

    2011-04-01

    Material degradation and ageing is of particular concern for fossil fuel fired power plant components. New techniques/approaches have been explored in recent years for Residual Life assessment of aged components and material degradation due to different damage mechanism like creep, fatigue, corrosion and erosion etc. Apart from the creep, the high temperature corrosion problem in a fossil fuel fired boiler is a matter of great concern if the fuel contains sulfur, chlorine sodium, potassium and vanadium etc. This paper discusses the material degradation due to high temperature corrosion in different critical components of boiler like water wall, superheater and reheater tubes and also remedial measures to avoid the premature failure. This paper also high lights the Residual Life Assessment (RLA) methodology of the components based on high temperature fireside corrosion. of different critical components of boiler.

  12. Multi-temperature state-dependent equivalent circuit discharge model for lithium-sulfur batteries

    DEFF Research Database (Denmark)

    Propp, Karsten; Marinescu, Monica; Auger, Daniel J.

    2016-01-01

    pulse profile at four temperatures from 10 °C to 50 °C, giving linearized ECN parameters for a range of states-of-charge, currents and temperatures. These are used to create a nonlinear polynomial-based battery model suitable for use in a battery management system. When the model is used to predict......Lithium-sulfur (Li-S) batteries are described extensively in the literature, but existing computational models aimed at scientific understanding are too complex for use in applications such as battery management. Computationally simple models are vital for exploitation. This paper proposes a non......-linear state-of-charge dependent Li-S equivalent circuit network (ECN) model for a Li-S cell under discharge. Li-S batteries are fundamentally different to Li-ion batteries, and require chemistry-specific models. A new Li-S model is obtained using a ‘behavioural’ interpretation of the ECN model; as Li...

  13. Solubility of acetic acid and trifluoroacetic acid in low-temperature (207-245 k) sulfuric acid solutions: implications for the upper troposphere and lower stratosphere.

    Science.gov (United States)

    Andersen, Mads P Sulbaek; Axson, Jessica L; Michelsen, Rebecca R H; Nielsen, Ole John; Iraci, Laura T

    2011-05-05

    The solubility of gas-phase acetic acid (CH(3)COOH, HAc) and trifluoroacetic acid (CF(3)COOH, TFA) in aqueous sulfuric acid solutions was measured in a Knudsen cell reactor over ranges of temperature (207-245 K) and acid composition (40-75 wt %, H(2)SO(4)). For both HAc and TFA, the effective Henry's law coefficient, H*, is inversely dependent on temperature. Measured values of H* for TFA range from 1.7 × 10(3) M atm(-1) in 75.0 wt % H(2)SO(4) at 242.5 K to 3.6 × 10(8) M atm(-1) in 40.7 wt % H(2)SO(4) at 207.8 K. Measured values of H* for HAc range from 2.2 × 10(5) M atm(-1) in 57.8 wt % H(2)SO(4) at 245.0 K to 3.8 × 10(8) M atm(-1) in 74.4 wt % H(2)SO(4) at 219.6 K. The solubility of HAc increases with increasing H(2)SO(4) concentration and is higher in strong sulfuric acid than in water. In contrast, the solubility of TFA decreases with increasing sulfuric acid concentration. The equilibrium concentration of HAc in UT/LS aerosol particles is estimated from our measurements and is found to be up to several orders of magnitude higher than those determined for common alcohols and small carbonyl compounds. On the basis of our measured solubility, we determine that HAc in the upper troposphere undergoes aerosol partitioning, though the role of H(2)SO(4) aerosol particles as a sink for HAc in the upper troposphere and lower stratosphere will only be discernible under high atmospheric sulfate perturbations.

  14. Aqueous synthesis and characterization of TGA-capped CdSe quantum dots at freezing temperature.

    Science.gov (United States)

    Sun, Qizhuang; Fu, Shasha; Dong, Tingmei; Liu, Shuxian; Huang, Chaobiao

    2012-07-11

    CdSe quantum dots (QDs) have traditionally been synthesized in organic phase and then transferred to aqueous solution by functionalizing their surface with silica, polymers, short-chain thiol ligands, or phospholipid micelles. However, a drastic increase in the hydrodynamic size and biotoxicity of QDs may hinder their biomedical applications. In this paper, the TGA-capped CdSe QDs are directly synthesized in aqueous phase at freezing temperature, and they prove to possess high QY (up to 14%).

  15. HYBRID SULFUR CYCLE FLOWSHEETS FOR HYDROGEN PRODUCTION USING HIGH-TEMPERATURE GAS-COOLED REACTORS

    Energy Technology Data Exchange (ETDEWEB)

    Gorensek, M.

    2011-07-06

    Two hybrid sulfur (HyS) cycle process flowsheets intended for use with high-temperature gas-cooled reactors (HTGRs) are presented. The flowsheets were developed for the Next Generation Nuclear Plant (NGNP) program, and couple a proton exchange membrane (PEM) electrolyzer for the SO2-depolarized electrolysis step with a silicon carbide bayonet reactor for the high-temperature decomposition step. One presumes an HTGR reactor outlet temperature (ROT) of 950 C, the other 750 C. Performance was improved (over earlier flowsheets) by assuming that use of a more acid-tolerant PEM, like acid-doped poly[2,2'-(m-phenylene)-5,5'-bibenzimidazole] (PBI), instead of Nafion{reg_sign}, would allow higher anolyte acid concentrations. Lower ROT was accommodated by adding a direct contact exchange/quench column upstream from the bayonet reactor and dropping the decomposition pressure. Aspen Plus was used to develop material and energy balances. A net thermal efficiency of 44.0% to 47.6%, higher heating value basis is projected for the 950 C case, dropping to 39.9% for the 750 C case.

  16. UV absorption cross-sections of selected sulfur-containing compounds at temperatures up to 500°C

    DEFF Research Database (Denmark)

    Grosch, Helge; Fateev, Alexander; Clausen, Sønnik

    2015-01-01

    The temperature dependence of the ultraviolet absorption cross-sections of three different sulfur containing compounds, hydrogen sulfide (H2S), carbon disulfide (CS2) and carbonyl sulfide (OCS), are presented between 200nm and 360nm at a resolution of 0.018nm. The absorption cross-sections for ea...

  17. AN EFFICIENT AND CHEMOSELECTIVE CBZ-PROTECTION OF AMINES USING SILICA-SULFURIC ACID AT ROOM TEMPERATURE

    Science.gov (United States)

    A simple, facile, and chemoselective N-benzyloxycarbonylation of amines using silica-sulfuric acid that proceeds under solvent-free conditions at room temperature has been achieved. These reactions are applicable to a wide variety of primary (aliphatic, cyclic) secondary amines, ...

  18. Effect of temperature on the behavior of surface properties of alcohols in aqueous solution

    International Nuclear Information System (INIS)

    Romero, Carmen M.; Jimenez, Eulogio; Suarez, Felipe

    2009-01-01

    The influence of temperature on the behavior of surface properties of aqueous solutions has often been used to obtain information about solute structural effects on water. In this work, we present experimental results for surface tension of aqueous solutions of n-pentanol, n-hexanol, n-heptanol, and n-octanol at T = (283.15, 288.15, 293.15, 298.15, 303.15, and 308.15) K at several concentrations. The results were used to evaluate the limiting experimental slopes of surface tension with respect to mole fraction and the hydrophobicity constant of the Connors model at each temperature. The thermodynamic behavior of aqueous alcohol solutions is discussed in terms of the effect of the hydrocarbon chain on water structure. The temperature dependence of the limiting slopes of surface tension with respect to mole fraction, as well as the hydrophobicity constant derived from surface measurements, is interpreted in terms of alcohol hydration

  19. Liquid and Emulsified Sulfur in Submarine Solfatara Fields of two Northern Mariana Arc Volcanoes.

    Science.gov (United States)

    Nakamura, K.; Embley, R. W.; Chadwick, W. W.; Butterfield, D. A.; Takano, B.; Resing, J. A.; de Ronde, C. E.; Lilley, M. D.; Lupton, J. E.; Merle, S. G.; Inagaki, F.

    2006-12-01

    Because elemental sulfur melting point is ca 100 deg C (depend on allotropes and heating rate, S8 triple point temperature: 115 deg C), the evidence of liquid sulfur has been known for many subaerial crater lakes and small ponds in geothermal regions throughout the world. But the milky nature of water (sulfur-in- water emulsion in limited water mass) prohibited the direct observation of on-going processes at the bottom of these subaerial lakes. In the passive degassing environment at the summit craters of Daikoku and Nikko Seamounts of the northern Mariana Arc, the continuous flushing of sulfur emulsion by seawater allowed us to observe on- going submarine solfatara processes and associated chemistry through dives with ROVs during the NT05-18 cruise (JAMSTEC R/V Natsushima and ROV hyper-Dolphin) and the Submarine Ring of Fire 2006 cruise (R/V Melville and ROV JASON II). A higher viscosity for liquid elemental sulfur relative to that of seawater, as well as a limited stability of sulfur emulsion (aqueous sulfur sol) at high temperatures in electrolyte solution (seawater), ensures limited mobility of liquid sulfur in the conduits of hydrothermal vents. The subseafloor boiling depth of hydrothermal fluid limits the locus of any liquid sulfur reservoir. It was observed in an exposed liquid sulfur pond that the penetration of gas bubbles (mostly CO2) created sulfur emulsion while collapsing liquid sulfur film between seawater and gas bubbles. Liquid sulfur pits, encrusted sulfur, liquid sulfur fountain structure, sulfur stalactites and stalagmites, mini-pillow lava-like sulfur flows, accretionary sulfur lapilli and sulfur deltas were also observed at the summits of two volcanoes. Note: Solfatara: Italian. A type of fumarole, the gases of which are characteristically sulfurous. In 'Glossary of geology.'

  20. Multi-temperature state-dependent equivalent circuit discharge model for lithium-sulfur batteries

    Science.gov (United States)

    Propp, Karsten; Marinescu, Monica; Auger, Daniel J.; O'Neill, Laura; Fotouhi, Abbas; Somasundaram, Karthik; Offer, Gregory J.; Minton, Geraint; Longo, Stefano; Wild, Mark; Knap, Vaclav

    2016-10-01

    Lithium-sulfur (Li-S) batteries are described extensively in the literature, but existing computational models aimed at scientific understanding are too complex for use in applications such as battery management. Computationally simple models are vital for exploitation. This paper proposes a non-linear state-of-charge dependent Li-S equivalent circuit network (ECN) model for a Li-S cell under discharge. Li-S batteries are fundamentally different to Li-ion batteries, and require chemistry-specific models. A new Li-S model is obtained using a 'behavioural' interpretation of the ECN model; as Li-S exhibits a 'steep' open-circuit voltage (OCV) profile at high states-of-charge, identification methods are designed to take into account OCV changes during current pulses. The prediction-error minimization technique is used. The model is parameterized from laboratory experiments using a mixed-size current pulse profile at four temperatures from 10 °C to 50 °C, giving linearized ECN parameters for a range of states-of-charge, currents and temperatures. These are used to create a nonlinear polynomial-based battery model suitable for use in a battery management system. When the model is used to predict the behaviour of a validation data set representing an automotive NEDC driving cycle, the terminal voltage predictions are judged accurate with a root mean square error of 32 mV.

  1. Sulfuric acid on Europa and the radiolytic sulfur cycle

    Science.gov (United States)

    Carlson, R. W.; Johnson, R. E.; Anderson, M. S.

    1999-01-01

    A comparison of laboratory spectra with Galileo data indicates that hydrated sulfuric acid is present and is a major component of Europa's surface. In addition, this moon's visually dark surface material, which spatially correlates with the sulfuric acid concentration, is identified as radiolytically altered sulfur polymers. Radiolysis of the surface by magnetospheric plasma bombardment continuously cycles sulfur between three forms: sulfuric acid, sulfur dioxide, and sulfur polymers, with sulfuric acid being about 50 times as abundant as the other forms. Enhanced sulfuric acid concentrations are found in Europa's geologically young terrains, suggesting that low-temperature, liquid sulfuric acid may influence geological processes.

  2. 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.

  3. Isopiestic studies of aqueous solutions at elevated temperatures

    International Nuclear Information System (INIS)

    Holmes, H.F.; Mesmer, R.E.

    1981-01-01

    Isopiestic measurements have been made for LiCl(aq) and CsCl(aq) over the temperature range 382.96 to 473.61 K. NcCl(aq) served as the reference electrolyte for the calculation of osmotic coefficients and the molalities ranged from about 0.6 to 6 mol kg -1 , for NaCl(aq). An ion-interaction model gave an excellent fit to the experimental osmotic coefficients with a standard error of fit ranging from 0.0004 to 0.0016 in the osmotic coefficient. Parameters obtained from the fit were used to calculate the activity coefficients. The osmotic and activity coefficients both decreased with increasing temperature over this temperature range. LiCl(aq) is somewhat unusual among the alkali-metal chlorides in that the osmotic (and activity) coefficient is much more dependent on molality at the higher molalities and there is no maximum between 273.15 and 373.15 K in the osmotic coefficient as a function of temperature. For both LiCl(aq) and CsCl(aq) there is an excellent correlation between the isopiestic results and the vapor pressures of Lindsay and Liu. Existing electrochemical results between 283.15 and 343.15 K are consistent with the calculated activity coefficients for CsCl(aq). (author)

  4. Sulfur Removal in Bio-Briquette Combustion Using Seashell Waste Adsorbent at Low Temperature

    Directory of Open Access Journals (Sweden)

    Mahidin

    2016-09-01

    Full Text Available Presently, biomass is mostly utilized as co-fuel in coal combustion in view of energy diversification and emission reduction. However, since the coal content of bio-briquettes is high (up to 80% in this study, gas emissions such as those of SOx still occur. Therefore, the introduction of SO2 adsorbent is common in coal briquette or bio-briquette combustion. A calcium-based material is usually used for this goal. The aim of this study was to observe the effects of desulfurization temperature and Ca/S ratio (Ca = calcium content in adsorbent; S = sulfur content in coal and biomass on desulfurization efficiency and kinetics. The ratio of coal to biomass (palm kernel shell/PKS was fixed at 90:10 (wt/wt and the ratios of Ca to S were varied at 1:1, 1.25:1, 1.5:1, 1.75:1 and 2:1. The mixtures of coal, PKS and adsorbent were briquetted at a molding pressure of 6 ton/cm2 with Jatropha curcas seeds and starch mixture as binding agents. Desulfurization was performed within a temperature range of 300 to 500°C for 720 seconds at an airflow rate of 1.2 L/min. The results showed that the highest desulfurization efficiency (90.6% was associated with the Ca/S ratio of 2:1 and temperature of 400°C. Moreover, the highest reaction rate constant of desulfurization was 0.280 min-1.

  5. Isopiestic studies of aqueous solutions at elevated temperatures

    International Nuclear Information System (INIS)

    Holmes, H.F.; Mesmer, R.E.

    1981-01-01

    Isopiestic measurements have been made on SrCl 2 (aq) and BaCl 2 (aq) over the temperature range 382.96 to 473.61 K with NaCl(aq) as the reference solution for the calculation of osmotic coefficients. The molalities corresponded to NaCl(aq) molalities ranging from 0.6 to 6.5 mol kg -1 . An ion-interaction model was fitted to the osmotic coefficients of SrCl 2 (aq) and BaCl 2 (aq) with a standard deviation of fit (in the osmotic coefficient) ranging from 0.0007 to 0.0048. Parameters derived from the fit were used to calculate the activity coefficients. The osmotic and activity coefficients decrease with increasing temperature and become less dependent on molality. Previous isopiestic results between 318 and 394 K agree with the present study. Activity coefficients from electrochemical measurements between 283.15 and 343.15 K are not consistent with the isopiestic results. (author)

  6. Quasi-steady model for predicting temperature of aqueous foams circulating in geothermal wellbores

    Energy Technology Data Exchange (ETDEWEB)

    Blackwell, B.F.; Ortega, A.

    1983-01-01

    A quasi-steady model has been developed for predicting the temperature profiles of aqueous foams circulating in geothermal wellbores. The model assumes steady one-dimensional incompressible flow in the wellbore; heat transfer by conduction from the geologic formation to the foam is one-dimensional radially and time-dependent. The vertical temperature distribution in the undisturbed geologic formation is assumed to be composed of two linear segments. For constant values of the convective heat-transfer coefficient, a closed-form analytical solution is obtained. It is demonstrated that the Prandtl number of aqueous foams is large (1000 to 5000); hence, a fully developed temperature profile may not exist for representative drilling applications. Existing convective heat-transfer-coefficient solutions are adapted to aqueous foams. The simplified quasi-steady model is successfully compared with a more-sophisticated finite-difference computer code. Sample temperature-profile calculations are presented for representative values of the primary parameters. For a 5000-ft wellbore with a bottom hole temperature of 375{sup 0}F, the maximum foam temperature can be as high as 300{sup 0}F.

  7. Glass Transition Temperature of Saccharide Aqueous Solutions Estimated with the Free Volume/Percolation Model.

    Science.gov (United States)

    Constantin, Julian Gelman; Schneider, Matthias; Corti, Horacio R

    2016-06-09

    The glass transition temperature of trehalose, sucrose, glucose, and fructose aqueous solutions has been predicted as a function of the water content by using the free volume/percolation model (FVPM). This model only requires the molar volume of water in the liquid and supercooled regimes, the molar volumes of the hypothetical pure liquid sugars at temperatures below their pure glass transition temperatures, and the molar volumes of the mixtures at the glass transition temperature. The model is simplified by assuming that the excess thermal expansion coefficient is negligible for saccharide-water mixtures, and this ideal FVPM becomes identical to the Gordon-Taylor model. It was found that the behavior of the water molar volume in trehalose-water mixtures at low temperatures can be obtained by assuming that the FVPM holds for this mixture. The temperature dependence of the water molar volume in the supercooled region of interest seems to be compatible with the recent hypothesis on the existence of two structure of liquid water, being the high density liquid water the state of water in the sugar solutions. The idealized FVPM describes the measured glass transition temperature of sucrose, glucose, and fructose aqueous solutions, with much better accuracy than both the Gordon-Taylor model based on an empirical kGT constant dependent on the saccharide glass transition temperature and the Couchman-Karasz model using experimental heat capacity changes of the components at the glass transition temperature. Thus, FVPM seems to be an excellent tool to predict the glass transition temperature of other aqueous saccharides and polyols solutions by resorting to volumetric information easily available.

  8. Oxyhalogen-sulfur chemistry: kinetics and mechanism of oxidation of N-acetyl homocysteine thiolactone by acidified bromate and aqueous bromine.

    Science.gov (United States)

    Mbiya, Wilbes; Choi, Boyoung; Martincigh, Bice S; Morakinyo, Moshood K; Simoyi, Reuben H

    2013-12-12

    N-acetyl homocysteine thiolactone (NAHT), medically known as citiolone, can be used as a mucolytic agent and for the treatment of certain hepatic disorders. We have studied the kinetics and mechanisms of its oxidation by acidic bromate and aqueous bromine. In acidic bromate conditions the reaction is characterized by a very short induction period followed by a sudden and rapid formation of bromine and N-acetyl homocysteine sulfonic acid. The stoichiometry of the bromate-NAHT reaction was deduced to be: BrO3(-) + H2O + CH3CONHCHCH2CH2SCO → CH3CONHCHCH2CH2(SO3H)COOH + Br(-) (S1) while in excess bromate it was deduced to be: 6BrO3(-) + 5CH3CONHCHCH2CH2SCO + 6H(+) → 3Br2 + 5CH3CONHCHCH2CH2(SO3H)COOH + 2H2O (S2). For the reaction of NAHT with bromine, a 3:1 stoichiometric ratio of bromine to NAHT was obtained: 3Br2 + CH3CONHCHCH2CH2SCO + 4H2O → 6Br(-) + CH3CONHCHCH2CH2(SO3H)COOH + 6H(+) (S3). Oxidation occurred only on the sulfur center where it was oxidized to the sulfonic acid. No sulfate formation was observed. The mechanism involved an initial oxidation to a relatively stable sulfoxide without ring-opening. Further oxidation of the sulfoxide involved two pathways: one which involved intermediate formation of an unstable sulfone and the other involves ring-opening coupled with oxidation through to the sulfonic acid. There was oligooscillatory production of aqueous bromine. Bromide produced in S1 reacts with excess bromate to produce aqueous bromine. The special stability associated with the sulfoxide allowed it to coexist with aqueous bromine since its further oxidation to the sulfone was not as facile. The direct reaction of aqueous bromine with NAHT was fast with an estimated lower limit bimolecular rate constant of 2.94 ± 0.03 × 10(2) M(-1) s(-1).

  9. Aqueous solutions of proline and NaCl studied by differential scanning calorimetry at subzero temperatures

    DEFF Research Database (Denmark)

    Rasmussen, Peter Have; Jørgensen, Bo; Nielsen, Jette

    1997-01-01

    was not observed during freezing or melting which shows that proline has the ability to stay in solution at subzero temperatures. Samples containing proline-NaCl-water were also investigated by DSC and it was shown that the solubility of proline is maintained in aqueous salt solutions at temperatures as low as -60....../w) indicating a high water solubility of proline at subzero temperatures. No glass transition was observed within the concentration range 0.9-40.1 wt% (w/w), neither at a low scanning rate of 2.5 degrees C/min nor at a higher scanning rate of 10 degrees C/min. Eutectic crystallization of proline...

  10. Adsorption of CI Basic Blue 3 Dye Molecules from Aqueous Media by Sulfuric Acid-Activated Montmorillonite Mineral

    OpenAIRE

    TAŞAR, Şeyda; KAYA, Fatih; ÖZER, Ahmet

    2017-01-01

    Many industries (especially textile, paper, plastic) which use chemicals and colorants, generate considerable amount of waste water since they use excessive amounts of water in their operations. and they These waste waters form a significant reason of worldwide water pollution, and if they are released before being treated, they bring an important harm to these waters.  Therefore, In this paper, adsorption kinetics and equilibrium of CI Basic Blue 3 (BB3) from aqueous media using sul...

  11. 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.

  12. Osmotic potential calculations of inorganic and organic aqueous solutions over wide solute concentration levels and temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Cochrane, T. T., E-mail: agteca@hotmail.com [AGTECA S.A., 230 Oceanbeach Road, Mount Maunganui, Tauranga 3116 (New Zealand); Cochrane, T. A., E-mail: tom.cochrane@canterbury.ac.nz [Department of Civil and Natural Resources Engineering, University of Canterbury, Private Bag 4800, Christchurch 8140 (New Zealand)

    2016-01-15

    Purpose: To demonstrate that the authors’ new “aqueous solution vs pure water” equation to calculate osmotic potential may be used to calculate the osmotic potentials of inorganic and organic aqueous solutions over wide ranges of solute concentrations and temperatures. Currently, the osmotic potentials of solutions used for medical purposes are calculated from equations based on the thermodynamics of the gas laws which are only accurate at low temperature and solute concentration levels. Some solutions used in medicine may need their osmotic potentials calculated more accurately to take into account solute concentrations and temperatures. Methods: The authors experimented with their new equation for calculating the osmotic potentials of inorganic and organic aqueous solutions up to and beyond body temperatures by adjusting three of its factors; (a) the volume property of pure water, (b) the number of “free” water molecules per unit volume of solution, “N{sub f},” and (c) the “t” factor expressing the cooperative structural relaxation time of pure water at given temperatures. Adequate information on the volume property of pure water at different temperatures is available in the literature. However, as little information on the relative densities of inorganic and organic solutions, respectively, at varying temperatures needed to calculate N{sub f} was available, provisional equations were formulated to approximate values. Those values together with tentative t values for different temperatures chosen from values calculated by different workers were substituted into the authors’ equation to demonstrate how osmotic potentials could be estimated over temperatures up to and beyond bodily temperatures. Results: The provisional equations formulated to calculate N{sub f}, the number of free water molecules per unit volume of inorganic and organic solute solutions, respectively, over wide concentration ranges compared well with the calculations of N{sub f

  13. Osmotic potential calculations of inorganic and organic aqueous solutions over wide solute concentration levels and temperatures

    International Nuclear Information System (INIS)

    Cochrane, T. T.; Cochrane, T. A.

    2016-01-01

    Purpose: To demonstrate that the authors’ new “aqueous solution vs pure water” equation to calculate osmotic potential may be used to calculate the osmotic potentials of inorganic and organic aqueous solutions over wide ranges of solute concentrations and temperatures. Currently, the osmotic potentials of solutions used for medical purposes are calculated from equations based on the thermodynamics of the gas laws which are only accurate at low temperature and solute concentration levels. Some solutions used in medicine may need their osmotic potentials calculated more accurately to take into account solute concentrations and temperatures. Methods: The authors experimented with their new equation for calculating the osmotic potentials of inorganic and organic aqueous solutions up to and beyond body temperatures by adjusting three of its factors; (a) the volume property of pure water, (b) the number of “free” water molecules per unit volume of solution, “N f ,” and (c) the “t” factor expressing the cooperative structural relaxation time of pure water at given temperatures. Adequate information on the volume property of pure water at different temperatures is available in the literature. However, as little information on the relative densities of inorganic and organic solutions, respectively, at varying temperatures needed to calculate N f was available, provisional equations were formulated to approximate values. Those values together with tentative t values for different temperatures chosen from values calculated by different workers were substituted into the authors’ equation to demonstrate how osmotic potentials could be estimated over temperatures up to and beyond bodily temperatures. Results: The provisional equations formulated to calculate N f , the number of free water molecules per unit volume of inorganic and organic solute solutions, respectively, over wide concentration ranges compared well with the calculations of N f using recorded

  14. Water and Temperature Stresses Impact Canola (Brassica napus L.) Fatty Acid, Protein, and Yield over Nitrogen and Sulfur.

    Science.gov (United States)

    Hammac, W Ashley; Maaz, Tai M; Koenig, Richard T; Burke, Ian C; Pan, William L

    2017-12-06

    Interactive effects of weather and soil nutrient status often control crop productivity. An experiment was conducted to determine effects of nitrogen (N) and sulfur (S) fertilizer rate, soil water, and atmospheric temperature on canola (Brassica napus L.) fatty acid (FA), total oil, protein, and grain yield. Nitrogen and sulfur were assessed in a 4-yr study with two locations, five N rates (0, 45, 90, 135, and 180 kg ha -1 ), and two S rates (0 and 17 kg ha -1 ). Water and temperature were assessed using variability across 12 site-years of dryland canola production. Effects of N and S were inconsistent. Unsaturated FA, oleic acid, grain oil, protein, and theoretical maximum grain yield were highly related to water and temperature variability across the site-years. A nonlinear model identified water and temperature conditions that enabled production of maximum unsaturated FA content, oleic acid content, total oil, protein, and theoretical maximum grain yield. Water and temperature variability played a larger role than soil nutrient status on canola grain constituents and yield.

  15. Temperature-dependent chemical shift in the aqueous solution of xenon

    OpenAIRE

    Peuravaara, P. (Petri)

    2017-01-01

    Abstract At standard pressure, the chemical shift of Xe-129 in an aqueous solution of xenon exhibits a maximum as a function of temperature at 311 K, which is in contrast to the well-known density maximum of water at 277 K. In the present work, this phenomenon is studied by means of a molecular dynamics simulation, where the xenon chemical shift is computed quantum-chemically for snapshots of the simulation trajectory. Also...

  16. 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

  17. Effect of sulfurization temperature on the property of Cu2ZnSnS4 thin film by eco-friendly nanoparticle ink method

    Science.gov (United States)

    Wang, Wei; Shen, Honglie; Yao, Hanyu; Shang, Huirong; Tang, ZhengXia; Li, Yufang

    2017-09-01

    Cu2ZnSnS4 (CZTS) thin films were fabricated by a low-cost nanoparticle ink method. The eco-friendly hydrophilic CZTS nanoparticles were mixed with low-cost n-propanol to form nanoparticle ink. To improve crystallinity and remove oxygen element, the CZTS thin films were sulfurized further. The effects of sulfurization temperature on the structure, morphologies, and photovoltaic performances of CZTS thin films were investigated. The results showed that the crystallinity of CZTS thin film was improved with increasing sulfurization temperature. The surface morphology studies demonstrated the formation of compact and homogenous CZTS thin film at a sulfurization temperature of 600 °C. By optimizing thickness of CZTS thin film, the CZTS thin-film solar cell with an optimal efficiency of 2.1% was obtained.

  18. Features of the temperature and concentration dependences of the contraction of aqueous solutions of ethanol

    Science.gov (United States)

    Gotsul'skii, V. Ya.; Malomuzh, N. P.; Chechko, V. E.

    2013-10-01

    Temperature and concentration dependences of the contraction of aqueous solutions of ethanol are studied. It is shown that at a molar concentration of x = 0.077, the curves of the temperature dependences of contraction intersect at one point that is interpreted as the singular point of a water-ethanol solution. To reveal the role of intermolecular forces of attraction, our results are compared to the behavior of contraction for hard-sphere mixtures with varying ratios of their radii. The change in the total volume of the solution induced by the formation of hydrogen bonds is analyzed in detail.

  19. Temperature and concentration calibration of aqueous polyvinylpyrrolidone (PVP solutions for isotropic diffusion MRI phantoms.

    Directory of Open Access Journals (Sweden)

    Friedrich Wagner

    Full Text Available To use the "apparent diffusion coefficient" (Dapp as a quantitative imaging parameter, well-suited test fluids are essential. In this study, the previously proposed aqueous solutions of polyvinylpyrrolidone (PVP were examined and temperature calibrations were obtained. For example, at a temperature of 20°C, Dapp ranged from 1.594 (95% CI: 1.593, 1.595 μm2/ms to 0.3326 (95% CI: 0. 3304, 0.3348 μm2/ms for PVP-concentrations ranging from 10% (w/w to 50% (w/w using K30 polymer lengths. The temperature dependence of Dapp was found to be so strong that a negligence seems not advisable. The temperature dependence is descriptively modelled by an exponential function exp(c2 (T - 20°C and the determined c2 values are reported, which can be used for temperature calibration. For example, we find the value 0.02952 K-1 for 30% (w/w PVP-concentration and K30 polymer length. In general, aqueous PVP solutions were found to be suitable to produce easily applicable and reliable Dapp-phantoms.

  20. Removal of P-chloro Phenol from Aqueous Solutions Using Chestnut Shell Modified by Sulfuric Acid: Study of Adsorption Kinetic and Isotherm

    Directory of Open Access Journals (Sweden)

    Hatam Godini

    2015-06-01

    Full Text Available Background: Present of p-chloro phenol in the environment due to high toxicity, mutagenic and carcinogenic effects, powerful odor production and stability in the environment caused to be categorized as priority pollutants. The aim of this study was to investigate the removal of p-chloro phenol from aqueous solution using chestnut shell modified by sulfuric acid. Methods: This study was an experimental study and chestnut shell (Quercus brantii Var. persica was used as an adsorbent. The effects of pH, contact time, adsorbent dosage, and initial concentration on the adsorption process were evaluated, in a batch scale. The characterizations of the raw and modified adsorbent were investigated by Fourier transform infrared (FTIR spectroscopy, scanning electron microscopy (SEM and X-ray diffractometer (XRD. Langmuir and Fruindlich isotherm models and pseudo-first order kinetic, pseudo-second order kinetic were evaluated by experimental data. Results: The results showed that the removal efficiency of p-chloro phenol increased with increasing of the contact time and adsorbent dosage, and had a reverse effect with increasing of pH and p-chloro phenol initial concentration. The maximum adsorption capacity of p-chloro phenol by modified chestnut shell adsorbent was achieved of 3.33 mg/g and the maximum removal efficiency of p-chloro phenol was 87 percent at pH=4. The experimental data were well descripted by Freundlich isotherm (R2>0.92 and pseudo-second order kinetic (R2>0.94. Conclusion: This study showed that the chestnut shell could be effectively used at removal of p-chloro phenol from aqueous solutions. As the chestnut shell is a waste, so it can be applied as an adsorbent for removal of pollutants such as p-chloro phenol.

  1. Interpretation of EIS data on passive steel surfaces in aqueous sulfuric acid solution in terms of carrier migration and recombination

    Energy Technology Data Exchange (ETDEWEB)

    Nagy, Gabor; Kerner, Zsolt; Schiller, Robert [Central Research Institute for Physics, Atomic Energy Research Institute, P.O.B. 49, Budapest H-1525 (Hungary)

    2007-12-31

    A model is proposed for the description of the interplay of charge carrier migration, effected by external voltage and combination within very thin passive oxide layers. This theory is used to describe the electrochemical impedance spectra of passive stainless steel in sulfuric acid, a prototype of such surfaces. A simple R{sub s}-Z{sub mr} vertical stroke vertical stroke R{sub p} circuit is considered with Z{sub mr} accounting for dispersion and R{sub p} for the Faraday process. Z{sub mr} is based on a continuous time random walk (CTRW) expression and it is seen to be independent of voltage. R{sub p} shows a strong voltage dependence which can be understood in the negative voltage range as a Butler-Volmer-Erdey-Gruz process, whereas in the positive range it can be described in terms of tunneling across the oxide. Curve fitting results in parameters characteristic to oxide structure and process kinetics. All fitted quantities are seen to be realistic with the exception of charge carrier density which turned out to be much too high, indicating that mobility might not obey the classical, frequency-independent law. (author)

  2. From lithium to sodium: cell chemistry of room temperature sodium–air and sodium–sulfur batteries

    Directory of Open Access Journals (Sweden)

    Philipp Adelhelm

    2015-04-01

    Full Text Available Research devoted to room temperature lithium–sulfur (Li/S8 and lithium–oxygen (Li/O2 batteries has significantly increased over the past ten years. The race to develop such cell systems is mainly motivated by the very high theoretical energy density and the abundance of sulfur and oxygen. The cell chemistry, however, is complex, and progress toward practical device development remains hampered by some fundamental key issues, which are currently being tackled by numerous approaches. Quite surprisingly, not much is known about the analogous sodium-based battery systems, although the already commercialized, high-temperature Na/S8 and Na/NiCl2 batteries suggest that a rechargeable battery based on sodium is feasible on a large scale. Moreover, the natural abundance of sodium is an attractive benefit for the development of batteries based on low cost components. This review provides a summary of the state-of-the-art knowledge on lithium–sulfur and lithium–oxygen batteries and a direct comparison with the analogous sodium systems. The general properties, major benefits and challenges, recent strategies for performance improvements and general guidelines for further development are summarized and critically discussed. In general, the substitution of lithium for sodium has a strong impact on the overall properties of the cell reaction and differences in ion transport, phase stability, electrode potential, energy density, etc. can be thus expected. Whether these differences will benefit a more reversible cell chemistry is still an open question, but some of the first reports on room temperature Na/S8 and Na/O2 cells already show some exciting differences as compared to the established Li/S8 and Li/O2 systems.

  3. Low temperature growth and optical properties of ZnO nanowires using an aqueous solution method.

    Science.gov (United States)

    Chu, Manh-Hung; Lee, Joon-Hyung; Kim, Jeong-Joo; Kim, Kyeong-Won; Norton, D P; Heo, Young-Woo

    2012-02-01

    ZnO nanowires were grown on indium tin oxide (ITO) coated glass substrates at a low temperature of 90 degrees C using an aqueous solution method. The ZnO seeds were coated on the ITO thin films by using a spin coater. ZnO nanowires were formed in an aqueous solution containing zinc nitrate hexahydrate (Zn(NO3)2 x 6H2O) and hexamethylenetetramine (C6H12N4). The pH value and concentration of the solution play an important role in the growth and morphologies of ZnO nanowires. The size of ZnO naonowires increased as the concentration of the solution increased. It was formed with a top surface of hexagonal and tapered shape at low and high pH values respectively. Additionally, the single crystalline structure and optical property of the ZnO nanowires were investigated using high-resolution transmission electron microscopy and photoluminescence spectroscopy.

  4. The effect of temperature on radiolysis of iodide ion diluted aqueous solutions

    International Nuclear Information System (INIS)

    Gorbovitskaya, T.; Tiliks, J.

    1996-01-01

    In order to investigate the radiolysis of iodine containing aqueous solutions a flow type facility - Iodine Thermoradiation Facility (ITF) has been designed. It has a possibility to irradiate aqueous solutions in the steel vessel with 60 Co γ-rays and continuously (on line) to analyze the products of radiolysis both in liquid and in gaseous phases. By means of ITF the formation of I ox (I 2 + I 3 - + HOI), IO 3 - , H 2 O 2 was studied in 10 -5 - 10 -3 mol/dm 3 CsI aqueous solutions by their radiolysis at dose rate 4.5 kGv/h for six hours in region of temperatures from 313 to 404 K. Under similar conditions, some experiments in glass ampoules were also performed. The steady-state concentrations of I ox and IO 3 - decreased with increasing temperature as linear function of inverted temperature. The effect decreased with decreasing concentration of iodide ion. As the result, at high temperatures (T≥380 K) the steady-state concentration of I ox does not depend essentially on the iodide ion initial concentration. Molecular iodine (I 2 ) released from the solution was the main radiolysis product in gaseous phase. Its steady-state concentration increased with increasing temperature because of iodine solubility in the water and decreased at the same time because the radiolytic iodine concentrations decreased. Therefore the most volatility of irradiated 10 -3 and 10 -4 M CsI solutions was observed at the temperature about 350 K. The volatility of 10 -5 M solutions gradually decreased with increasing temperature. The experimental data were explained on the base of the hypothesis that the reaction between I 2 and radiolytic H 2 O 2 was the limit one determining the temperature dependence of I ox and IO 3 - steady-state concentrations. Its activation energy was estimated to be 27,5 kcal.mol -1 . The temperature dependence for reaction (IO - + H 2 O 2 ) was also estimated. (author) 8 figs., 1 tab., 17 refs

  5. Low temperature sulfur and sodium metal battery for grid-scale energy storage application

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Gao; Wang, Dongdong

    2018-03-27

    A re-chargeable battery comprising a non-dendrite forming sodium (Na)/potassium (K) liquid metal alloy anode, a sulfur and polyacrylonitrile (PAN) conductive polymer composite cathode, a polyethyleneoxide (PEO) solid electrolyte, a solid electrolyte interface (SEI) formed on the PEO solid electrolyte; and a cell housing, wherein the anode, cathode, and electrolyte are assembled into the cell housing with the PEO solid electrolyte disposed between the cathode and anode.

  6. Effects of Temperature on Aggregation Kinetics of Graphene Oxide in Aqueous Solutions

    Science.gov (United States)

    Wang, M.; Gao, B.; Tang, D.; Sun, H.; Yin, X.; Yu, C.

    2017-12-01

    Temperature may play an important role in controlling graphene oxide (GO) stability in aqueous solutions, but it has been overlooked in the literature. In this work, laboratory experiments were conducted to determine the effects of temperature (6, 25, and 40 °C) on GO aggregation kinetics under different combinations of ionic strength, cation type, humic acid (HA) concentration by monitoring GO hydrodynamic radii and attachment efficiencies. The results showed that, without HA, temperature increase promoted GO aggregation in both monovalent (Na+ and K+) and divalent (Ca2+) solutions. This phenomenon might be caused by multiple processes including enhanced collision frequency, enhanced cation dehydration, and reduced electrostatic repulsion. The presence of HA introduced steric repulsion forces that enhanced GO stability and temperature showed different effects GO aggregation kinetics in monovalent and divalent electrolytes. In monovalent electrolytes, cold temperature diminished the steric repulsion of HA-coated GO. As a result, the fastest increasing rate of GO hydrodynamic radius and the smallest critical coagulation concentration value appeared at the lowest temperature (6 °C). Conversely, in divalent electrolyte solutions with HA, high temperate favored GO aggregation, probably because the interactions between Ca2+ and HA increased with temperature resulting in lower HA coating on GO. Findings of this work emphasized the importance of temperature as well as solution chemistry on the stability and fate of GO nanoparticles in aquatic environment.

  7. Sulfur Mustard

    Science.gov (United States)

    ... Poisoning Methyl isocyanate Case Definition: Methyl Isocyanate Poisoning Mustard gas (H) (sulfur mustard) Facts About Sulfur Mustard Case ... About Strychnine Case Definition: Strychnine Sulfur mustard (H) (mustard gas) Facts About Sulfur Mustard Case Definition: Vesicant (Mustards, ...

  8. Surface properties of W-implanted TiN coatings post-treated by low temperature ion sulfurization

    International Nuclear Information System (INIS)

    Tian, Bin; Yue, Wen; Wang, Chengbiao; Liu, Jiajun

    2015-01-01

    Highlights: • PVD TiN coatings are implanted with W ions at dose of 9 × 10 17 ions/cm 2 . • Low temperature ion sulfurization (LTIS) is adopted on W-implanted TiN coatings. • W content and depth in the W-implanted coatings reduce after LTIS. • LTIS cannot well improve friction and wear of W-implanted TiN under dry sliding. - Abstract: TiN coatings were implanted with W ions by metal vapor vacuum arc (MEVVA) source at dose of 9 × 10 17 ions/cm 2 , and then they were post-treated by low temperature ion sulfurization (LTIS) at 160 °C. The W-implanted TiN samples were characterized before and after post-treatment of LTIS, using Scanning Electron Microscopy (SEM), Scanning Auger Microprobe (SAM), X-ray diffraction (XRD), and Nano Indenter System. Friction and wear properties were evaluated using a ball-on-disc tribometer under dry sliding in air. After post-treatment of LTIS, XRD results showed no diffraction peaks of tungsten sulfides on surfaces of W-implanted TiN coatings; W-implanted TiN coatings were sputtered by the sulfur plasma with about 36% reducing of W depth. Further, the nano-hardness decreased mainly due to the amount decreasing of Ti 2 N and the formation of more metal oxides on surfaces of W-implanted TiN coatings after LTIS. As a result, LTIS treatment could not well improve tribological properties of W-implanted TiN coatings.

  9. Large-Scale Synthesis of Silver Nanoparticles by Aqueous Reduction for Low-Temperature Sintering Bonding

    Directory of Open Access Journals (Sweden)

    Qiu Xiliang

    2014-01-01

    Full Text Available Silver nanoparticles with average diameter of 22.4 nm were prepared by aqueous reduction method for low-temperature sintering bonding application. The reaction temperature and PVP concentration, which are the influential factors of nanoparticle characteristics, were investigated during reduction process. In our research, monodispersity of nanoparticles was remarkably improved while unfavorable agglomeration was avoided with the AgNO3/PVP mass ratio of 1 : 4 at the reaction temperature 30°C. Besides, copper pads were successfully bonded using sintering paste employing fresh silver nanoparticles with diameter of 20~35 nm at 200°C. In addition, after morphology of the bonding joint was analysed by scanning electron microscope (SEM, the porous sintering characteristics were confirmed.

  10. Corrosion behaviour of Alloy 800 in high temperature aqueous solutions: Electrochemical studies

    International Nuclear Information System (INIS)

    Olmedo, A.M.; Villegas, M.; Alvarez, M.G.

    1996-01-01

    The anodic behaviour and passivity breakdown of Alloy 800 in aqueous solutions of sodium chloride, sodium sulphate and sodium bicarbonate were studied by electrochemical techniques in the temperature range from 60 C to 280 C. The pitting resistance and pitting morphology of the alloy in chloride plus sulphate and chloride plus bicarbonate mixtures, at 60 C and 280 C, were also examined. Increasing bicarbonate or sulphate additions to chloride solutions shift the characteristic pitting potential of Alloy 800 to higher values, both at low and high temperatures. Changes in pitting morphology were observed in sulphate containing solutions while the morphology of the attack found in bicarbonate containing solutions was similar to that in pure chloride solutions. Finally, no localized or substantial generalized corrosion was detected in pure sulphate or bicarbonate solutions at any temperature. (orig.)

  11. Hybrid temperature effect on a quartz crystal microbalance resonator in aqueous solutions

    International Nuclear Information System (INIS)

    Li Qiang; Gu Yu; Xie Bin

    2017-01-01

    The quartz crystal microbalance (QCM) is an important tool that can sense nanogram changes in mass. The hybrid temperature effect on a QCM resonator in aqueous solutions leads to unconvincing detection results. Control of the temperature effect is one of the keys when using the QCM for high precision measurements. Based on the Sauerbrey’s and Kanazawa’s theories, we proposed a method for enhancing the accuracy of the QCM measurement, which takes into account not only the thermal variations of viscosity and density but also the thermal behavior of the QCM resonator. We presented an improved Sauerbrey equation that can be used to effectively compensate the drift of the QCM resonator. These results will play a significant role when applying the QCM at the room temperature. (paper)

  12. Chemistry in high temperature aqueous solutions application to the power industry

    International Nuclear Information System (INIS)

    Cohen, P.

    1990-01-01

    The power industry utilizes water (aqueous solutions) for two main functions: as a medium for heat transfer and transport and as a thermodynamic working fluid. These functions are performed in systems fabricated from a wide variety of materials, over a wide range of thermal and hydraulic conditions, and at medium temperatures and densities which determine the significant chemical properties. The major chemical interest is in the concentrated solutions derived from the dilute working fluid at selected sites defined by the physical arrangement and temperature and in their consequential effects on heat transfer and corrosion. Examples of these sites for typical fossil fired and nuclear steam generating equipment are described, as well as the extent and limit of the concentration process. The history of steam power plant water chemistry is discussed from the point of view of the chemical processes involved. The period covered is from the 1920s to the present state of the art, which is a major application of the subject of this symposium--chemistry in high temperature aqueous solution

  13. Solvation behaviour of biologically active compounds in aqueous solutions of antibacterial drug amoxicillin at different temperatures

    International Nuclear Information System (INIS)

    Singla, Meenu; Kumar, Harsh; Jindal, Rajeev

    2014-01-01

    Highlights: • Densities and speeds of sound of amino acids in aqueous amoxicillin solutions. • Partial molar volumes and compressibility of transfer. • Group contribution have been calculated. • (Ion + hydrophilic) and (hydrophilic + hydrophilic) interactions are present. • Pair-wise interactions are dominant in the mixtures. - Abstract: The interactions of glycine (Gly), L-alanine (Ala), L-valine (Val) and L-Leucine (Leu) with drug amoxicillin (AMX) as a function of temperature have been investigated by combination of volumetric and acoustic measurements. Densities and speeds of sound of amino acids in aqueous solutions of amoxicillin have been measured at T = (305.15, 310.15 and 315.15) K and atmospheric pressure. The apparent molar volume (V ϕ ), the partial molar volume (V ϕ 0 ) and standard partial molar volumes of transfer (ΔV ϕ 0 ) for amino acids from water to aqueous amoxicillin solutions have been calculated from density data. Group contributions of amino acids to partial molar volume were determined. Partial molar isentropic compression (κ ϕ,s ) and partial molar isentropic compression of transfer (Δκ ϕ,S 0 ) have been calculated from speed of sound data. The pair and triplet interaction coefficient have been calculated from both the properties. The results have been explained based on competing patterns of interactions of co-solvents and the solute

  14. Structural flexibility of the sulfur mustard molecule at finite temperature from Car-Parrinello molecular dynamics simulations.

    Science.gov (United States)

    Lach, Joanna; Goclon, Jakub; Rodziewicz, Pawel

    2016-04-05

    Sulfur mustard (SM) is one of the most dangerous chemical compounds used against humans, mostly at war conditions but also in terrorist attacks. Even though the sulfur mustard has been synthesized over a hundred years ago, some of its molecular properties are not yet resolved. We investigate the structural flexibility of the SM molecule in the gas phase by Car-Parrinello molecular dynamics simulations. Thorough conformation analysis of 81 different SM configurations using density functional theory is performed to analyze the behavior of the system at finite temperature. The conformational diversity is analyzed with respect to the formation of intramolecular blue-shifting CH⋯S and CH⋯Cl hydrogen bonds. Molecular dynamics simulations indicate that all structural rearrangements between SM local minima are realized either in direct or non-direct way, including the intermediate structure in the last case. We study the lifetime of the SM conformers and perform the population analysis. Additionally, we provide the anharmonic dynamical finite temperature IR spectrum from the Fourier Transform of the dipole moment autocorrelation function to mimic the missing experimental IR spectrum. Copyright © 2015 Elsevier B.V. All rights reserved.

  15. Probing Ionic Liquid Aqueous Solutions Using Temperature of Maximum Density Isotope Effects

    Directory of Open Access Journals (Sweden)

    Mohammad Tariq

    2013-03-01

    Full Text Available This work is a new development of an extensive research program that is investigating for the first time shifts in the temperature of maximum density (TMD of aqueous solutions caused by ionic liquid solutes. In the present case we have compared the shifts caused by three ionic liquid solutes with a common cation—1-ethyl-3-methylimidazolium coupled with acetate, ethylsulfate and tetracyanoborate anions—in normal and deuterated water solutions. The observed differences are discussed in terms of the nature of the corresponding anion-water interactions.

  16. Temperature dependence of the surface enhanced raman spectroelectrochemistry of iron in aqueous solutions.

    Energy Technology Data Exchange (ETDEWEB)

    Simpson, L. J.; Melendres, C. A.; Chemical Engineering

    1996-06-01

    The effect of temperature on the composition of the corrosion film on iron in aqueous sodium hydroxide and borate solutions was investigated using surface enhanced Raman spectroelectrochemistry (SERS). Fe(OH){sub 2} and Fe{sub 3}O{sub 4} were observed in the prepassivation region, while Fe{sub 3}O{sub 4} and FeOOH accounted for most of the passivated film at 25, 60 and 95 C. Fe(OH){sub 2} was found to be a stable component of the corrosion film on iron at 95 C, which is contrary to recently published theoretical calculations.

  17. Aluminum speciation in aqueous fluids at deep crustal pressure and temperature

    Science.gov (United States)

    Mookherjee, Mainak; Keppler, Hans; Manning, Craig E.

    2014-05-01

    We investigated aluminum speciation in aqueous fluids in equilibrium with corundum using in situ Raman spectroscopy in hydrothermal diamond anvil cells to 20 kbar and 1000 °C. We have studied aluminum species in (a) pure H2O, (b) 5.3 m KOH solution, and (c) 1 m KOH solution. In order to better understand the spectral features of the aqueous fluids, we used ab initio simulations based on density functional theory to calculate and predict the energetics and vibrational spectra for various aluminum species that are likely to be present in aqueous solutions. The Raman spectra of pure water in equilibrium with Al2O3 are devoid of any characteristic spectral features. In contrast, aqueous fluids with 5.3 m and 1 m KOH solution in equilibrium with Al2O3 show a sharp band at ˜620 cm-1 which could be attributed to the [ species. The band grows in intensity with temperature along an isochore. A shoulder on the high-frequency side of this band may be due to a hydrated, charge neutral Al(OH)3·H2O species. In the limited pressure, temperature and density explored in the present study, we do not find any evidence for the polymerization of the [ species to dimers [(OH)2-Al-(OH)2-Al(OH)2] or [(OH)3-Al-O-Al(OH)3]2-. This is likely due to the relatively low concentration of Al in the solutions and does not rule out significant polymerization at higher pressures and temperatures. Upon cooling of Al-bearing solutions to room temperatures, Raman bands indicating the precipitation of diaspore (AlOOH) were observed in some experiments. The Raman spectra of the KOH solutions (with or without dissolved alumina) showed a sharp OH stretching band at ˜3614 cm-1 and an in-plane OH bending vibration at ˜1068 cm-1, likely related to an OH- ion with the oxygen atom attached to a water molecule by hydrogen bonding. A weak feature at ˜935 cm-1 may be related to the out-of-plane bending vibration of the same species or to an OH species with a different environment.

  18. Improved AIOMFAC model parameterisation of the temperature dependence of activity coefficients for aqueous organic mixtures

    Science.gov (United States)

    Ganbavale, G.; Zuend, A.; Marcolli, C.; Peter, T.

    2015-01-01

    This study presents a new, improved parameterisation of the temperature dependence of activity coefficients in the AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) model applicable for aqueous as well as water-free organic solutions. For electrolyte-free organic and organic-water mixtures the AIOMFAC model uses a group-contribution approach based on UNIFAC (UNIversal quasi-chemical Functional-group Activity Coefficients). This group-contribution approach explicitly accounts for interactions among organic functional groups and between organic functional groups and water. The previous AIOMFAC version uses a simple parameterisation of the temperature dependence of activity coefficients, aimed to be applicable in the temperature range from ~ 275 to ~ 400 K. With the goal to improve the description of a wide variety of organic compounds found in atmospheric aerosols, we extend the AIOMFAC parameterisation for the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon to atmospherically relevant low temperatures. To this end we introduce a new parameterisation for the temperature dependence. The improved temperature dependence parameterisation is derived from classical thermodynamic theory by describing effects from changes in molar enthalpy and heat capacity of a multi-component system. Thermodynamic equilibrium data of aqueous organic and water-free organic mixtures from the literature are carefully assessed and complemented with new measurements to establish a comprehensive database, covering a wide temperature range (~ 190 to ~ 440 K) for many of the functional group combinations considered. Different experimental data types and their processing for the estimation of AIOMFAC model parameters are discussed. The new AIOMFAC parameterisation for the temperature dependence of activity coefficients from low to high temperatures shows an overall improvement of 28% in

  19. Solubility of Sulfur Dioxide in Sulfuric Acid

    Science.gov (United States)

    Chang, K. K.; Compton, L. E.; Lawson, D. D.

    1982-01-01

    The solubility of sulfur dioxide in 50% (wt./wt.) sulfuric acid was evaluated by regular solution theory, and the results verified by experimental measurements in the temperature range of 25 C to 70 C at pressures of 60 to 200 PSIA. The percent (wt./wt.) of sulfur dioxide in 50% (wt./wt.) sulfuric acid is given by the equation %SO2 = 2.2350 + 0.0903P - 0.00026P 10 to the 2nd power with P in PSIA.

  20. Dissolution kinetics of soil clays in sulfuric acid solutions: Ionic strength and temperature effects

    International Nuclear Information System (INIS)

    Bibi, Irshad; Singh, Balwant; Silvester, Ewen

    2014-01-01

    Highlights: • Acid sulfate dissolution of clay-rich sediments from inland acid sulfate site in flow-through reactor experiments at pH 1–4. • Enhanced Al and K release at the higher ionic strength of solutions compared to the lower ionic strength. • Acid neutralization capacity (ANC) of 1.11 kg H 2 SO 4 /tonne clay-rich sediment/day was provided at pH 1, 25 °C. • ANC provided at 45 °C by the same amount of clay-rich sediment was more than three times higher than the ANC at 25 °C. - Abstract: Significant amounts of sulfuric acid (H 2 SO 4 ) rich saline water can be produced by the oxidation of sulfide minerals contained in inland acid sulfate soils (IASS). In the absence of carbonate minerals, the dissolution of phyllosilicate minerals is one of very few processes that can provide long-term acid neutralisation. It is therefore important to understand the acid dissolution behavior of naturally occurring clay minerals from IASS under saline–acidic solutions. The objective of this study was to investigate the dissolution of a natural clay-rich sample under saline–acidic conditions (pH 1–4; ionic strengths = 0.01 and 0.25 M; 25 °C) and over a range of temperatures (25–45 °C; pH 1 and pH 4). The clay-rich sample referred to as Bottle Bend clay (BB clay) used was from an IASS (Bottle Bend lagoon) in south-western New South Wales (Australia) and contained smectite (40%), illite (27%), kaolinite (26%) and quartz (6%). Acid dissolution of the BB clay was initially rapid, as indicated by the fast release of cations (Si, Al, K, Fe, Mg). Relatively higher Al (pH 4) and K (pH 2–4) release was obtained from BB clay dissolution in higher ionic strength solutions compared to the lower ionic strength solutions. The steady state dissolution rate (as determined from Si, Al and Fe release rates; R Si , R Al , R Fe ) increased with decreasing solution pH and increasing temperature. For example, the highest log R Si value was obtained at pH 1 and 45 °C (−9

  1. OSMOTIC COEFFICIENTS, SOLUBILITIES, AND DELIQUESCENCE RELATIONS IN MIXED AQUEOUS SALT SOLUTIONS AT ELEVATED TEMPERATURE

    International Nuclear Information System (INIS)

    M.S. Gruszkiewicz; D.A. Palmer

    2006-01-01

    While thermodynamic properties of pure aqueous electrolytes are relatively well known at ambient temperature, there are far fewer data for binary systems extending to elevated temperatures and high concentrations. There is no general theoretically sound basis for prediction of the temperature dependence of ionic activities, and consequently temperature extrapolations based on ambient temperature data and empirical equations are uncertain and require empirical verification. Thermodynamic properties of mixed brines in a wide range of concentrations would enhance the understanding and precise modeling of the effects of deliquescence of initially dry solids in humid air in geological environments and in modeling the composition of waters during heating, cooling, evaporation or condensation processes. These conditions are of interest in the analysis of waters on metal surfaces at the proposed radioactive waste repository at Yucca Mountain, Nevada. The results obtained in this project will be useful for modeling the long-term evolution of the chemical environment, and this in turn is useful for the analysis of the corrosion of waste packages. In particular, there are few reliable experimental data available on the relationship between relative humidity and composition that reveals the eutonic points of the mixtures and the mixture deliquescence RH. The deliquescence RH for multicomponent mixtures is lower than that of pure component or binary solutions, but is not easy to predict quantitatively since the solutions are highly nonideal. In this work we used the ORNL low-temperature and high-temperature isopiestic facilities, capable of precise measurements of vapor pressure between ambient temperature and 250 C for determination of not only osmotic coefficients, but also solubilities and deliquescence points of aqueous mixed solutions in a range of temperatures. In addition to standard solutions of CaCl 2 , LiCl, and NaCl used as references, precise direct

  2. Temperature dependent absorption spectra of Br(-), Br2(•-), and Br3(-) in aqueous solutions.

    Science.gov (United States)

    Lin, Mingzhang; Archirel, Pierre; Van-Oanh, Nguyen Thi; Muroya, Yusa; Fu, Haiying; Yan, Yu; Nagaishi, Ryuji; Kumagai, Yuta; Katsumura, Yosuke; Mostafavi, Mehran

    2011-05-05

    The absorption spectra of Br(2)(•-) and Br(3)(-) in aqueous solutions are investigated by pulse radiolysis techniques from room temperature to 380 and 350 °C, respectively. Br(2)(•-) can be observed even in supercritical conditions, showing that this species could be used as a probe in pulse radiolysis at high temperature and even under supercritical conditions. The weak temperature effect on the absorption spectra of Br(2)(•-) and Br(3)(-) is because, in these two systems, the transition occurs between two valence states; for example, for Br(2)(-) we have (2)Σ(u) → (2)Σ(g) transition. These valence transitions involve no diffuse final state. However, the absorption band of Br(-) undergoes an important red shift to longer wavelengths. We performed classical dynamics of hydrated Br(-) system at 20 and 300 °C under pressure of 25 MPa. The radial distribution functions (rdf's) show that the strong temperature increase (from 20 to 300 °C) does not change the radius of the solvent first shell. On the other hand, it shifts dramatically (by 1 Å) the second maximum of the Br-O rdf and introduces much disorder. This shows that the first water shell is strongly bound to the anion whatever the temperature. The first two water shells form a cavity of a roughly spherical shape around the anion. By TDDFT method, we calculated the absorption spectra of hydrated Br(-) at two temperatures and we compared the results with the experimental data.

  3. Cr(III) solubility in aqueous fluids at high pressures and temperatures

    Science.gov (United States)

    Watenphul, Anke; Schmidt, Christian; Jahn, Sandro

    2014-02-01

    Trivalent chromium is generally considered relatively insoluble in aqueous fluids and melts. However, numerous counterexamples in nature indicate Cr(III) mobilization by aqueous fluids during metamorphism or hydrothermal alteration of chromite-bearing rocks, or by pegmatite melts. So far, very little is known about the chromium concentrations and speciation in such fluids. In this study, the solubility of eskolaite (Cr2O3) in 1.6-4.2 m aqueous HCl solutions was determined in situ at elevated pressures up to 1 GPa and temperatures ranging between 400 and 700 °C using synchrotron micro-X-ray fluorescence spectroscopy (μ-XRF). Determined concentrations of dissolved Cr ranged between about 900-18,000 ppm, with the highest concentrations found at 500 °C and 861 MPa. The Cr(III) solubility in aqueous HCl fluids is retrograde in the studied temperature range and increases with pressure. In addition, Cr(III) complexation in these fluids was explored by Raman spectroscopy on a 12.3 mass% HCl fluid in equilibrium with eskolaite at 400 and 600 °C, 0.3-1.6 GPa. All spectra show two prominent Cr-Cl stretching bands at about 275 and 325 cm-1, which display some fine structure, and in some spectra weak bands in the region between 380 and 500 cm-1. The sum of the integrated intensities of the two dominant bands reveals qualitatively the same changes with temperature along an isochore, with pressure at constant temperature, and with the time required for equilibration as the Cr(III) concentrations in the fluid determined by μ-XRF. Complementary ab initio molecular dynamics simulations of a 4 m HCl solution at two different densities (0.8 and 0.97 g/cm3) and temperatures (427 and 727 °C) were performed to investigate the vibrational properties of various(O)y3-x and (O)y(OH)z3-x-z complexes with 3⩽x+z⩽4 and 0⩽y⩽2. Quasi-normal mode analysis reveals that both the tetrahedral symmetric and antisymmetric Cr-Cl stretching vibrations of CrCl4(H2O)0-2- have characteristic

  4. Green corrosion inhibition of mild steel to aqueous sulfuric acid by the extract of Corchorus olitorius stems

    Science.gov (United States)

    Gobara, Mohamed; Zaghloul, Basem; Baraka, Ahmad; Elsayed, Mohamed; Zorainy, Mahmoud; Mokhtar Kotb, Mohamed; Elnabarawy, Hany

    2017-04-01

    Extract of Corchorus olitorius stems (ECS) was used as a green inhibitor for the inhibition of mild steel corrosion in 0.5 M H2SO4 solution. GC/MS was used for both qualitative and quantitative analysis of the extract. The corrosion performance of the extract was evaluated using electrochemical impedance spectroscopy, potentiodynamic polarization and weight loss. The results showed that ECS is a mixed-type inhibitor which reduces both anodic and cathodic reactions and the inhibition efficiency was reached up to 93%. Adsorption isotherm data was recorded at different temperatures and analyzed by selected adsorption isotherm models to reveal characteristics of inhibition. Thermodynamic calculations showed that the inhibition efficiency increases with increasing inhibitor concentration, and decreases with increasing temperature. Adsorption of ECS on the mild steel surface was found to be spontaneous and exothermic. Adsorption is suggested to be physisorption according to El-Awady isotherm model. Also, the scanning electron microscopy (SEM) was used to investigate the surface morphology to confirm the corrosion results.

  5. Catalytic Palladium Film Deposited by Scalable Low-Temperature Aqueous Combustion.

    Science.gov (United States)

    Voskanyan, Albert A; Li, Chi-Ying Vanessa; Chan, Kwong-Yu

    2017-09-27

    This article describes a novel method for depositing a dense, high quality palladium thin film via a one-step aqueous combustion process which can be easily scaled up. Film deposition of Pd from aqueous solutions by conventional chemical or electrochemical methods is inhibited by hydrogen embrittlement, thus resulting in a brittle palladium film. The method outlined in this work allows a direct aqueous solution deposition of a mirror-bright, durable Pd film on substrates including glass and glassy carbon. This simple procedure has many advantages including a very high deposition rate (>10 cm 2 min -1 ) and a relatively low deposition temperature (250 °C), which makes it suitable for large-scale industrial applications. Although preparation of various high-quality oxide films has been successfully accomplished via solution combustion synthesis (SCS) before, this article presents the first report on direct SCS production of a metallic film. The mechanism of Pd film formation is discussed with the identification of a complex formed between palladium nitrate and glycine at low temperature. The catalytic properties and stability of films are successfully tested in alcohol electrooxidation and electrochemical oxygen reduction reaction. It was observed that combustion deposited Pd film on a glassy carbon electrode showed excellent catalytic activity in ethanol oxidation without using any binder or additive. We also report for the first time the concept of a reusable "catalytic flask" as illustrated by the Suzuki-Miyaura cross-coupling reaction. The Pd film uniformly covers the inner walls of the flask and eliminates the catalyst separation step. We believe the innovative concept of a reusable catalytic flask is very promising and has the required features to become a commercial product in the future.

  6. Influence of temperature, time, liquid/solid ratio and sulfuric acid concentration on the hydrolysis of palm empty fruit bunches.

    Science.gov (United States)

    Ferrer, Ana; Requejo, Ana; Rodríguez, Alejandro; Jiménez, Luis

    2013-02-01

    The influence of temperature (150-190 °C), time (0-20 min), liquid/solid ratio (6-8) and sulfuric acid concentration (0.1-0.5%), on the hydrolysis of palm empty fruit bunches (EFBs) was studied and the liquid and solid fractions were analyzed. Polynomial models were found to reproduce the experimental results with errors less than 15% in most of the cases (except for xylose concentration). Operating conditions of 190 °C for 15 min at a liquid/solid ratio of 6 and a sulfuric acid concentration of 0.1% resulted in the production of 3.12, 4.0, 2.35 and 2.28 g/L of glucose, xylose, arabinose and acetic acid, respectively, starting with 1000 g of EFBs. The yield was 67.96%. Soda-anthraquinone, ethanol and ethanolamine pulping of the solid fraction provided pulps with brightness values (63.24%, 28.78%, 48.76%), but with poor resistance properties (6.57-8.54 Nm/g for tensile index, 0.38-0.44 k N/g for burst index and 0.96-1.02 mN m2/g for tear index). Therefore it is advisable to use the pulps for speciality papers or for bioethanol-production. Copyright © 2012 Elsevier Ltd. All rights reserved.

  7. Sulfur crosslinks from thermal degradation of chitosan dithiocarbamate derivatives and thermodynamic study for sorption of copper and cadmium from aqueous system.

    Science.gov (United States)

    Yong, Soon Kong; Skinner, William M; Bolan, Nanthi S; Lombi, Enzo; Kunhikrishnan, Anitha; Ok, Yong Sik

    2016-01-01

    Pristine chitosan beads were modified with sulfur (S)-containing functional groups to produce thiolated chitosan beads (ETB), thereby increasing S donor ligands and crosslinks. The effect of temperature, heating time, carbon disulfide (CS2)/chitosan ratio, and pH on total S content of ETB was examined using Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. The total S content of ETB increased with increasing CS2/chitosan ratio and decreased with decreasing pH and increasing temperature (>60 °C) and heating time (at 60 °C). Spectroscopic analyses revealed the presence of thiol (-SH)/thione, disulfide (-S-S-), and sulfonate groups in ETB. The thiolation mechanism involves decomposition of dithiocarbamate groups, thereby forming thiourea crosslinks and trithiocarbonate, resulting in -SH oxidation to produce -S-S- crosslinks. The partially formed ETB crosslinks contribute to its acid stability and are thermodynamically feasible in adsorbing Cd and Cu. The S-containing functional groups added to chitinous wastes act as sorbents for metal remediation from acidic environments.

  8. Effect of High Temperature on the Electrochemical and Optical Properties of Emeraldine Salt Doped with DBSA and Sulfuric Acid

    Directory of Open Access Journals (Sweden)

    Salma Gul

    2015-01-01

    Full Text Available A comprehensive study of thermally treated polyaniline in its emeraldine salt form is presented here. It offers an understanding of the thermal stability of the polymer. Emeraldine salt was prepared by a novel emulsion polymerization pathway using dodecylbenzene sulfonic acid and sulfuric acid together as dopants. The effect of temperature and heating rate on the degradation of this emeraldine salt was studied via thermogravimetric analysis. The thermally analyzed sample was collected at various temperatures, that is, 250, 490, 500, and 1000°C. The gradual changes in the structure of the emeraldine salt were followed through cyclic voltammetry, Fourier transform infrared spectroscopy, and ultraviolet-visible spectroscopy. Results demonstrate that emeraldine salt shows high thermal stability up to 500°C. This is much higher working temperature for the use of emeraldine salt in higher temperature applications. Further heat treatment seems to induce deprotonation in emeraldine salt. Cyclic voltammetry and ultraviolet-visible spectroscopy revealed that complete deprotonation takes place at 1000°C where it loses its electrical conductivity. It is interesting to note that after the elimination of the dopants, the basic backbone of emeraldine salt was not destroyed. The results reveal that the dopants employed have a stability effect on the skeleton of emeraldine salt.

  9. Temperature dependence of the internal dynamics of a protein in an aqueous solvent: Decoupling from the solvent viscosity

    International Nuclear Information System (INIS)

    Mamontov, E.; O’Neill, H.; Zhang, Q.; Chathoth, S.M.

    2013-01-01

    Highlights: ► LiCl enables low-temperature proteins studies in aqueous solutions without freezing. ► Glass transition temperature of aqueous solvent is unaffected by lithium chloride. ► Solvent viscosity governs global dynamics of lysozyme down to glass transition arrest. ► Lysozyme internal dynamics is decoupled showing dynamic arrest at higher temperatures. - Abstract: We have recently observed decoupling of the dynamics of a protein from its aqueous solvent [Chu et al., JPCL 3 (2012) 380]; here we report the more detailed studies. We analyzed quasielastic neutron scattering data from a 40 mg/ml solution of lysozyme in (D 2 O) 8 (LiCl) and (H 2 O) 8 (LiCl). The internal dynamics of lysozyme exhibited super-Arrhenius temperature dependence with no crossover to a different regime down to at least 200 K. The decoupling of the internal protein dynamics from the viscosity of its aqueous solvent is evident. The temperature dependence of the protein dynamics indicates an apparent dynamic arrest at a temperature above 190 K, whereas the glass transition temperature for the solvent is around 135–140 K. The internal dynamics of the solvated protein is coupled to the dynamics of its hydration shell, not of the bulk solvent, which is qualitatively altered by the salt to defer the dynamic arrest to 135–140 K

  10. Low-temperature aqueous-phase methanol dehydrogenation to hydrogen and carbon dioxide.

    Science.gov (United States)

    Nielsen, Martin; Alberico, Elisabetta; Baumann, Wolfgang; Drexler, Hans-Joachim; Junge, Henrik; Gladiali, Serafino; Beller, Matthias

    2013-03-07

    Hydrogen produced from renewable resources is a promising potential source of clean energy. With the help of low-temperature proton-exchange membrane fuel cells, molecular hydrogen can be converted efficiently to produce electricity. The implementation of sustainable hydrogen production and subsequent hydrogen conversion to energy is called "hydrogen economy". Unfortunately, its physical properties make the transport and handling of hydrogen gas difficult. To overcome this, methanol can be used as a material for the storage of hydrogen, because it is a liquid at room temperature and contains 12.6 per cent hydrogen. However, the state-of-the-art method for the production of hydrogen from methanol (methanol reforming) is conducted at high temperatures (over 200 degrees Celsius) and high pressures (25-50 bar), which limits its potential applications. Here we describe an efficient low-temperature aqueous-phase methanol dehydrogenation process, which is facilitated by ruthenium complexes. Hydrogen generation by this method proceeds at 65-95 degrees Celsius and ambient pressure with excellent catalyst turnover frequencies (4,700 per hour) and turnover numbers (exceeding 350,000). This would make the delivery of hydrogen on mobile devices--and hence the use of methanol as a practical hydrogen carrier--feasible.

  11. Kinetics of hydrogen evolution at tantalum electrode in sulfuric acid media: effects of pH and solution temperature

    International Nuclear Information System (INIS)

    Sherstobitova, I.N.; Stepanova, M.L.; Kichigin, V.I.

    1997-01-01

    The influence of temperature in the range of 20-80 deg C and sulfuric acid and potassium sulfate solution pH in the range of pH=1.81-3.0 on kinetics of electrochemical reaction of hydrogen evolution on tantalum, which is characterized by Ta-H high binding energy, has been studied. It has been ascertained that the reaction occurs on the surface of electrode covered by a thin film of tantalum oxide. The oxide is preserved during cathode polarization, only its electrophysical and adsorption al properties change at the expense of hydrogen atoms penetration to the oxide film volume and appearance of low-valency; tantalum cations in the oxide

  12. SOLUBILITIES AND PHYSICAL PROPERTIES OF SATURATED SOLUTIONS IN THE COPPER SULFATE + SULFURIC ACID + SEAWATER SYSTEM AT DIFFERENT TEMPERATURES

    Directory of Open Access Journals (Sweden)

    F. J. Justel

    2015-09-01

    Full Text Available AbstractIn Chile, the most important economic activity is mining, concentrated in the north of the country. This is a desert region with limited water resources; therefore, the mining sector requires research and identification of alternative sources of water. One alternative is seawater, which can be a substitute of the limited fresh water resources in the region. This work determines the influence of seawater on the solid-liquid equilibrium for acid solutions of copper sulfate at different temperatures (293.15 to 318.15 K, and its effect on physical properties (density, viscosity, and solubility. Knowledge of these properties and solubility data are useful in the leaching process and in the design of copper sulfate pentahydrate crystallization plants from the leaching process using seawater by means of the addition of sulfuric acid.

  13. Soft cutting of single-wall carbon nanotubes by low temperature ultrasonication in a mixture of sulfuric and nitric acids.

    Science.gov (United States)

    Shuba, M V; Paddubskaya, A G; Kuzhir, P P; Maksimenko, S A; Ksenevich, V K; Niaura, G; Seliuta, D; Kasalynas, I; Valusis, G

    2012-12-14

    To decrease single-wall carbon nanotube (SWCNT) lengths to a value of 100-200 nm, aggressive cutting methods, accompanied by a high loss of starting material, are frequently used. We propose a cutting approach based on low temperature intensive ultrasonication in a mixture of sulfuric and nitric acids. The method is nondestructive with a yield close to 100%. It was applied to cut nanotubes produced in three different ways: gas-phase catalysis, chemical vapor deposition, and electric-arc-discharge methods. Raman and Fourier transform infrared spectroscopy were used to demonstrate that the cut carbon nanotubes have a low extent of sidewall degradation and their electronic properties are close to those of the untreated tubes. It was proposed to use the spectral position of the far-infrared absorption peak as a simple criterion for the estimation of SWCNT length distribution in the samples.

  14. Synthesis and characterization of sulfur functionalized graphene oxide nanosheets as efficient sorbent for removal of Pb2+, Cd2+, Ni2+ and Zn2+ ions from aqueous solution: A combined thermodynamic and kinetic studies

    Science.gov (United States)

    Pirveysian, Mahtab; Ghiaci, Mehran

    2018-01-01

    A very simple, one pot method was used for preparation of sulfur functionalized graphene oxide (GO-SOxR) with sodium sulfide and water in reflux condition. The elemental analysis data showed high sulfur content up to 15%. EDS and XPS analysis also proved introduction of sulfur element. To make the sorbent more efficient operationally, the GO-SOxR was coated with a mesoporous shell of TiO2 or SiO2. The prepared sorbents were characterized by SEM, TEM, TGA, XPS, XRD, IR and EDS. GO-SOxR@TiO2 and GO-SOxR@SiO2 composites were tested for removal of Pb(II), Cd(II), Ni(II) and Zn(II) as heavy metal ions from aqueous solution in batch method. Adsorption of the heavy metal ions was studied kinetically, and the adsorption capacities of GO-SOxR, GO-SOxR@TiO2, and GO-SOxR@SiO2 were evaluated using equilibrium adsorption isotherms, and compared to other adsorbents used for removal of these heavy metals. Kinetic studies showed that the experimental data was fitted with pseudo second order model. The adsorption capacity of GO was significantly improved by sulfur functionalization and TiO2 coating.

  15. Experimental studies in high temperature aqueous chemistry at Oak Ridge National Laboratory

    Energy Technology Data Exchange (ETDEWEB)

    Mesmer, R.E.; Palmer, D.A.; Simonson, J.M.; Holmes, H.F.; Ho, P.C.; Wesolowski, D.J.; Gruszkiewicz, M.S.

    1996-01-01

    Experimental research is conducted and models developed in a long- standing program at Oak Ridge on aqueous chemistry at high temperatures of broad classes of electrolytes emphasizing thermodynamics of reaction equilibria and excess thermodynamic properties of electrolytes. Experimental methods, their capabilities, data analysis, and results are summarized. Relevance of the work to problems in power plants, natural and industrial processes as well as basic solution chemistry and geochemistry are given. Progress in potentiometry, electrical conductivity, flow calorimetry, and isopiestic research is described. Future in this field demands greater precision in measurements and significant gains in our understanding of the solvation phenomena especially in the vicinity and beyond the critical point for water. The communities who do research on scattering, spectroscopy, and computer simulations can help guide these efforts through studies at extreme conditions.

  16. High-temperature thermodynamic data for species in aqueous solution. Final report

    International Nuclear Information System (INIS)

    Cobble, J.W.; Murray, R.C. Jr.; Turner, P.J.; Chen, K.

    1982-05-01

    This final report summarizes the results of experimental and theoretical research on the high temperature thermodynamic properties of aqueous species important to nuclear reactor water chemistry. Methods of predicting thermodynamic functions are included for electrolytes up to 300 0 C where experimental data are lacking. Data in the literature are evaluated and tables of important equilibrium constants for 78 reactions encountered in corrosion and precipitation in nuclear reactors are listed up to 300 0 C. Finally, tables of free energy functions from 0 to 300 0 C are given for 56 individual species. These data represented form a major compilation resulting from the most advanced experimental and theoretical methods. Illustrations of the use of the tables are given for problems involving pH control, precipitation, and corrosion. 11 figures, 100 tables

  17. Transients observed in the low temperature photolysis of alkyl radicals and divalent sulfur substrates

    International Nuclear Information System (INIS)

    The 253.7 nm photolysis of the isometric butyl radicals is described. These radicals are produced by electron capture during the γ-radiolysis of the corresponding butyl chlorides diluted in a rigid glass of 3-methylpentane-d14 at 77K. Thus t-butyl gives an equilibrium mixture of i-butyl and methyl radicals. Solvent radicals, M, are also produced and these obscure the former species in 3-MP-h14. Likewise sec-butyl radicals give rise to the ethyl, n-butyl, methyl and small amounts of the i-butyl radicals. Solvent radicals also rearrange and degrade in the photolytic beam, and the mechanism by which these processes occur is discussed. The procedure has also been used to study the formation and photolability of the alkyl thinyl and perthyl radicals occuring in the photolysis of RSH, RSR and RSSR. The thinyl radical is found to be unstable and gives the alkyl radical and atomic sulfur while the perthiyl radical is stable to radiation > 240 nm. (author)

  18. Thermodynamic stability of sulfur dioxide oxidation by Lyapunov function analysis against temperature perturbation

    Science.gov (United States)

    Tangde, V. M.; Bhalekar, A. A.; Venkataramani, B.

    2007-04-01

    The present paper describes the thermodynamic stability study of the industrially important reaction of sulfur trioxide synthesis using a framework of comprehensive thermodynamic theory of stability of irreversible processes (CTTSIP). The mathematical steps involved, use the CTTSIP set-up. We construct an appropriate expression of \\mathcal{L}_s , the excess rate of entropy production, and use the constitutive equations of the perturbation coordinates and then establish the sign of the time rate of \\mathcal{L}_s. In doing so we expand \\mathcal{L}_s, in a Taylor expansion about the given non-equilibrium state (that is a point on the unperturbed trajectory). In the present case \\mathcal{L}_s has been defined using an appropriate irreversible thermodynamic expression for Σs, the rate of entropy production, that includes the entropy production from the existence of heat flux and the chemical conversion occurring at a finite rate. The operative expression of d\\mathcal{L}_s/dt has been derived using the above inputs and then by the help of 'Polymath 5.1' signs of \\mathcal{L}_s and d\\mathcal{L}_s/dt and their profiles are computed. The effect of variation of the overall heat transfer coefficient on the stability of the process has been analysed.

  19. Polyampholyte hydrogel electrolytes for flexible and self-healing aqueous supercapacitor for low temperature applications

    Science.gov (United States)

    Chung, Hyun-Joong; Li, Xinda

    Quenched polyampholytes provide a novel class of tough hydrogel that has self-healing ability, strong adhesion, and mechanical flexibility. In this study, we show that the polyampholyte hydrogels can be utilized as an aqueous gel electrolyte material that is especially useful for low temperature operations; at -30 °C, energy density of 10.5 Wh/kg at a power density of 500 W/kg was achieved. The high performance at the low temperature is associated to the concept of non-freezable water near the hydrophilic polymer chains. A comparison between differential scanning calorimetry (DSC) measurements for polyampholytes that contained KOH and neat KOH solution revealed that increased amount of water molecules become non-freezable when the solution is contained in the hydrogel networks. In addition, the crosslinked network structure of the polyampholyte chains disrupts the crystalline growth of ice, resulting in `slush-like' ice formation. The interplay between the increased amount of unfrozen water and the limited growth of ice crystals leads to the enhanced supercapacitor performance at low temperatures.

  20. Oxyhalogen-sulfur chemistry: kinetics and mechanism of oxidation of chemoprotectant, sodium 2-mercaptoethanesulfonate, MESNA, by acidic bromate and aqueous bromine.

    Science.gov (United States)

    Adigun, Risikat Ajibola; Mhike, Morgen; Mbiya, Wilbes; Jonnalagadda, Sreekanth B; Simoyi, Reuben H

    2014-03-27

    The oxidation of a well-known chemoprotectant in anticancer therapies, sodium 2-mercaptoethanesulfonate, MESNA, by acidic bromate and aqueous bromine was studied in acidic medium. Stoichiometry of the reaction is: BrO3(-) + HSCH2CH2SO3H → Br(-) + HO3SCH2CH2SO3H. In excess bromate conditions the stoichiometry was deduced to be: 6BrO3(-) + 5HSCH2CH2SO3H + 6H(+) → 3Br2 + 5HO3SCH2CH2SO3H + 3H2O. The direct reaction of bromine and MESNA gave a stoichiometric ratio of 3:1: 3Br2 + HSCH2CH2SO3H + 3H2O → HO3SCH2CH2SO3H + 6Br(-) + 6H(+). This direct reaction is very fast; within limits of the mixing time of the stopped-flow spectrophotometer and with a bimolecular rate constant of 1.95 ± 0.05 × 10(4) M(-1) s(-1). Despite the strong oxidizing agents utilized, there is no cleavage of the C-S bond and no sulfate production was detected. The ESI-MS data show that the reaction proceeds via a predominantly nonradical pathway of three consecutive 2-electron transfers on the sulfur center to obtain the product 1,2-ethanedisulfonic acid, a well-known medium for the delivery of psychotic drugs. Thiyl radicals were detected but the absence of autocatalytic kinetics indicated that the radical pathway was a minor oxidation route. ESI-MS data showed that the S-oxide, contrary to known behavior of organosulfur compounds, is much more stable than the sulfinic acid. In conditions where the oxidizing equivalents are limited to a 4-electron transfer to only the sulfinic acid, the products obtained are a mixture of the S-oxide and the sulfonic acid with negligible amounts of the sulfinic acid. It appears the S-oxide is the preferred conformation over the sulfenic acid since no sulfenic acids have ever been stabilized without bulky substituent groups. The overall reaction scheme could be described and modeled by a minimal network of 18 reactions in which the major oxidants are HOBr and Br2(aq).

  1. Research and development on is process components for hydrogen production. (2) Corrosion resistance of glass lining in high temperature sulfuric acid

    International Nuclear Information System (INIS)

    Tanaka, Nobuyuki; Iwatsuki, Jin; Kubo, Shinji; Terada, Atsuhiko; Onuki, Kaoru

    2009-01-01

    Japan Atomic Energy Agency has been conducting a research and development on hydrogen production system using High Temperature Gas-Cooled Reactor. As a part of this effort, thermochemical water-splitting cycle featuring iodine- and sulfur-compounds (IS process) is under development considering its potential of large-scale economical hydrogen production. The IS process constitutes very severe environments on the materials of construction because of the corrosive nature of process chemicals, especially of the high temperature acidic solution of sulfuric acid and hydriodic acid dissolving iodine. Therefore, selection of the corrosion-resistant materials and development of the components has been studied as a crucial subject of the process development. This paper discusses corrosion resistance of commercially available glass-lining material in high temperature sulfuric acid. Corrosion resistance of a soda glass used for glass-lining was examined by immersion tests. The experiments were performed in 47-90wt% sulfuric acids at temperatures of up to 400degC and for the maximum immersion time of 100 hours using an autoclave designed for the concerned tests. In every condition tested, no indication of localized corrosion such as defect formation or pitting corrosion was observed. Also, the corrosion rates decreased with the progress of immersion, and were low enough (≅0.1 mm/year) after 60-90 hours of immersion probably due to formation of a silica rich surface. (author)

  2. A facile in situ sulfur deposition route to obtain carbon-wrapped sulfur composite cathodes for lithium–sulfur batteries

    International Nuclear Information System (INIS)

    Su Yusheng; Manthiram, Arumugam

    2012-01-01

    Highlights: ► Carbon-wrapped sulfur composite was obtained via an in situ sulfur deposition route. ► Sulfur–carbon composite suppresses the shuttle effect during charging. ► Sulfur–carbon composite shows enhanced cyclability and rate capability. ► Sulfur–carbon composite retains structural integrity and low impedance during cycling. - Abstract: An in situ sulfur deposition route has been developed for synthesizing sulfur–carbon composites as cathode materials for lithium–sulfur batteries. This facile synthesis method involves the precipitation of elemental sulfur at the interspaces between carbon nanoparticles in aqueous solution at room temperature. The product has been characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, charge–discharge measurements, and electrochemical impedance spectroscopy. The sulfur–carbon composite cathode with 75 wt.% active material thus obtained exhibits a remarkably high first discharge capacity of 1116 mAh g −1 with good cycle performance, maintaining 777 mAh g −1 after 50 cycles. The significantly improved electrochemical performance of the sulfur–carbon composite cathode is attributed to the carbon-wrapped sulfur network structure, which suppresses the loss of active material during charging/discharging and the migration of the polysulfide ions to the anode (i.e., shuttling effect). The integrity of the cathode structure during cycling is reflected in low impedance values observed after cycling. This facile in situ sulfur deposition route represents a low-cost approach to obtain high-performance sulfur–carbon composite cathodes for rechargeable Li–S batteries.

  3. Effects of pressure on aqueous chemical equilibria at subzero temperatures with applications to Europa

    Science.gov (United States)

    Marion, G.M.; Kargel, J.S.; Catling, D.C.; Jakubowski, S.D.

    2005-01-01

    Pressure plays a critical role in controlling aqueous geochemical processes in deep oceans and deep ice. The putative ocean of Europa could have pressures of 1200 bars or higher on the seafloor, a pressure not dissimilar to the deepest ocean basin on Earth (the Mariana Trench at 1100 bars of pressure). At such high pressures, chemical thermodynamic relations need to explicitly consider pressure. A number of papers have addressed the role of pressure on equilibrium constants, activity coefficients, and the activity of water. None of these models deal, however, with processes at subzero temperatures, which may be important in cold environments on Earth and other planetary bodies. The objectives of this work were to (1) incorporate a pressure dependence into an existing geochemical model parameterized for subzero temperatures (FREZCHEM), (2) validate the model, and (3) simulate pressure-dependent processes on Europa. As part of objective 1, we examined two models for quantifying the volumetric properties of liquid water at subzero temperatures: one model is based on the measured properties of supercooled water, and the other model is based on the properties of liquid water in equilibrium with ice. The relative effect of pressure on solution properties falls in the order: equilibrium constants(K) > activity coefficients (??) > activity of water (aw). The errors (%) in our model associated with these properties, however, fall in the order: ?? > K > aw. The transposition between K and ?? is due to a more accurate model for estimating K than for estimating ??. Only activity coefficients are likely to be significantly in error. However, even in this case, the errors are likely to be only in the range of 2 to 5% up to 1000 bars of pressure. Evidence based on the pressure/temperature melting of ice and salt solution densities argue in favor of the equilibrium water model, which depends on extrapolations, for characterizing the properties of liquid water in electrolyte

  4. Sulfur resistance of Ce-Mn/TiO2 catalysts for low-temperature NH3-SCR

    Science.gov (United States)

    Xu, Quan; Yang, Wenjing; Cui, Shitong; Street, Jason; Luo, Yan

    2018-03-01

    Ce-Mn/TiO2 catalyst prepared using a simple impregnation method demonstrated a better low-temperature selective catalytic reduction of NO with NH3 (NH3-SCR) activity in comparison with the sol-gel method. The Ce-Mn/TiO2 catalyst loading with 20% Ce had the best low-temperature activity and achieved a NO conversion rate higher than 90% at 140-260°C with a 99.7% NO conversion rate at 180°C. The Ce-Mn/TiO2 catalyst only had a 6% NO conversion rate decrease after 100 ppm of SO2 was added to the stream. When SO2 was removed from the stream, the catalyst was able to recover completely. The crystal structure, morphology, textural properties and valence state of the metals involving the novel catalysts were investigated using X-ray diffraction, N2 adsorption and desorption analysis, X-ray photoelectron spectroscopy, scanning electron microscopy and energy dispersive spectroscopy, respectively. The decrease of NH3-SCR performance in the presence of 100 ppm SO2 was due to the decrease of the surface area, change of the pore structure, the decrease of Ce4+ and Mn4+ concentration and the formation of the sulfur phase chemicals which blocked the active sites and changed the valence status of the elements.

  5. Impact of pretreatment with dilute sulfuric acid under moderate temperature on hydrolysis of corn stover with two enzyme systems.

    Science.gov (United States)

    Tai, Chao; Keshwani, Deepak

    2014-03-01

    Pretreatment of corn stover with dilute sulfuric acid at moderate temperature was investigated, and glucan digestibility by Cellic CTec2 and Celluclast on the pretreated biomass was compared. Pretreatments were carried out from 60 to 180 min at the temperature from 105 to 135 °C, with acid concentrations ranging from 0.5 to 2% (w/v). Significant portion of xylan was removed during pretreatment, and the glucan digestibility by CTec2 was significantly better than that by Celluclast in all cases. Analysis showed that glucan digestibility by both two enzymes correlated directly with the extent of xylan removal in pretreatment. Confidence interval was built to give a more precise range of glucan conversion and to test the significant difference among pretreatment conditions. Response surface model was built to obtain the optimal pretreatment condition to achieve high glucan conversion after enzymatic hydrolysis. Considering the cost and energy savings, the optimal pretreatment condition of 1.75% acid for 160 min at 135 °C was determined, and glucan conversion can achieve the range from 72.86 to 76.69% at 95% confidence level after enzymatic hydrolysis, making total glucan recovery up to the range from 89.42 to 93.25%.

  6. Temperature of maximum density and excess thermodynamics of aqueous mixtures of methanol

    Energy Technology Data Exchange (ETDEWEB)

    González-Salgado, D.; Zemánková, K. [Departamento de Física Aplicada, Universidad de Vigo, Campus del Agua, Edificio Manuel Martínez-Risco, E-32004 Ourense (Spain); Noya, E. G.; Lomba, E. [Instituto de Química Física Rocasolano, CSIC, Calle Serrano 119, E-28006 Madrid (Spain)

    2016-05-14

    In this work, we present a study of representative excess thermodynamic properties of aqueous mixtures of methanol over the complete concentration range, based on extensive computer simulation calculations. In addition to test various existing united atom model potentials, we have developed a new force-field which accurately reproduces the excess thermodynamics of this system. Moreover, we have paid particular attention to the behavior of the temperature of maximum density (TMD) in dilute methanol mixtures. The presence of a temperature of maximum density is one of the essential anomalies exhibited by water. This anomalous behavior is modified in a non-monotonous fashion by the presence of fully miscible solutes that partly disrupt the hydrogen bond network of water, such as methanol (and other short chain alcohols). In order to obtain a better insight into the phenomenology of the changes in the TMD of water induced by small amounts of methanol, we have performed a new series of experimental measurements and computer simulations using various force fields. We observe that none of the force-fields tested capture the non-monotonous concentration dependence of the TMD for highly diluted methanol solutions.

  7. Ambient temperature aqueous synthesis of ultrasmall copper doped ceria nanocrystals for the water gas shift and carbon monoxide oxidation reactions

    Energy Technology Data Exchange (ETDEWEB)

    Curran, Christopher D. [Department of Chemical and Biomolecular Engineering; Lehigh University; Bethlehem; USA; Lu, Li [Department of Materials Science and Engineering; Lehigh University; Bethlehem; USA; Kiely, Christopher J. [Department of Chemical and Biomolecular Engineering; Lehigh University; Bethlehem; USA; Department of Materials Science and Engineering; McIntosh, Steven [Department of Chemical and Biomolecular Engineering; Lehigh University; Bethlehem; USA

    2018-01-01

    Ultra-small CuxCe1-xO2-δnanocrystals were prepared through a room temperature, aqueous synthesis method, achieving high copper doping and low water gas shift activation energy.

  8. Organic sulfur metabolisms in hydrothermal environments.

    Science.gov (United States)

    Rogers, Karyn L; Schulte, Mitchell D

    2012-07-01

    Sulfur is central to the metabolisms of many organisms that inhabit extreme environments. While biotic and abiotic cycling of organic sulfur compounds has been well documented in low-temperature anaerobic environments, cycling of organic sulfur in hydrothermal environments has received less attention. Recently published thermodynamic data have been used to estimate aqueous alkyl thiol and sulfide activities in deep-sea hydrothermal systems. Here we use geochemical mixing models to predict fluid compositions that result from mixing end-member hydrothermal fluid from the East Pacific Rise with bottom seawater. These fluid compositions are combined with estimates of methanethiol and dimethylsulfide activities to evaluate energy yields for potential organic sulfur-based metabolisms under hydrothermal conditions. Aerobic respiration has the highest energy yields (over -240 kJ/mol e⁻) at lower temperature; however, oxygen is unlikely to persist at high temperatures, restricting aerobic respiration to mesophilic communities. Nitrite reduction to N₂ has the highest energy yields at higher temperatures (greater than ∼40 °C). Nitrate and nitrite reduction to ammonium also yield significant energy (up to -70 kJ/mol e⁻). Much lower, but still feasible energy yields are calculated for sulfate reduction, disproportionation, and reduction with H₂. Organic compound family and the activity of methanethiol and dimethylsulfide were less important than metabolic strategy in determining overall energy yields. All metabolic strategies considered were exergonic within some portion of the mixing regime suggesting that organic sulfur-based metabolisms may be prevalent within deep-sea hydrothermal vent microbial communities. © 2012 Blackwell Publishing Ltd.

  9. Global phenotypic and genomic comparison of two Saccharomyces cerevisiae wine strains reveals a novel role of the sulfur assimilation pathway in adaptation at low temperature fermentations.

    Science.gov (United States)

    García-Ríos, Estéfani; López-Malo, María; Guillamón, José Manuel

    2014-12-03

    The wine industry needs better-adapted yeasts to grow at low temperature because it is interested in fermenting at low temperature to improve wine aroma. Elucidating the response to cold in Saccharomyces cerevisiae is of paramount importance for the selection or genetic improvement of wine strains. We followed a global approach by comparing transcriptomic, proteomic and genomic changes in two commercial wine strains, which showed clear differences in their growth and fermentation capacity at low temperature. These strains were selected according to the maximum growth rate in a synthetic grape must during miniaturized batch cultures at different temperatures. The fitness differences of the selected strains were corroborated by directly competing during fermentations at optimum and low temperatures. The up-regulation of the genes of the sulfur assimilation pathway and glutathione biosynthesis suggested a crucial role in better performance at low temperature. The presence of some metabolites of these pathways, such as S-Adenosilmethionine (SAM) and glutathione, counteracted the differences in growth rate at low temperature in both strains. Generally, the proteomic and genomic changes observed in both strains also supported the importance of these metabolic pathways in adaptation at low temperature. This work reveals a novel role of the sulfur assimilation pathway in adaptation at low temperature. We propose that a greater activation of this metabolic route enhances the synthesis of key metabolites, such as glutathione, whose protective effects can contribute to improve the fermentation process.

  10. Reactions of sulfur fluorides and benzenes in a low temperature plasma

    Science.gov (United States)

    Klampfer, Peter; Skapin, Tomaž; Kralj, Bogdan; Žigon, Dušan; Jesih, Adolf

    2000-10-01

    The introduction of pentafluorosulfanyl, SF_5, group into molecules can substantially change their physical, chemical and biological properties, making them potentially useful for a number of applications: high temperature and oxidation resistant materials, blood substitutes, energetic materials and surface-active agents. With the aim to determine possible formation of pentafluorosulfanylbenzenes, C_6H_5SF_5, in plasma, the gases SF_6, CF_3SF5 and ClSF5 were allowed to react with benzene, chlorobenzene and bromobenzene in an inductively coupled radio-frequency discharge. Reaction products were collected in a cold trap held at 77 K and subsequently analysed by combined GC-MS and GC-FTIR spectroscopy. The main reaction products were different halogenated benzenes along with sulfides, disulfides and biphenyl. The pentafluorosulfanylbenzene was produced in all reactions in very small quantities, which amounted to less than 1 % of all reaction products in favorable cases.

  11. High-temperature phase relations and thermodynamics in the iron-lead-sulfur system

    Science.gov (United States)

    Eric, R. Hurman; Ozok, Hakan

    1994-01-01

    The PbS activities in FeS-PbS liquid mattes were obtained at 1100 °C and 1200 °C by the dew-point method. Negative deviations were observed, and the liquid-matte solutions were modeled by the Krupkowski formalism. The liquid boundaries of the FeS-PbS phase diagram were derived from the model equations yielding a eutectic temperature of 842 °C at X Pbs = 0.46. A phase diagram of the pseudobinary FeS-PbS was also verified experimentally by quenching samples equilibrated in evacuated and sealed silica capsules. No terminal solid solution ranges could be found. Within the Fe-Pb-S ternary system, the boundaries of the immiscibility region together with the tie-line distributions were established at 1200 °C. Activities of Pb were measured by the dew-point technique along the metal-rich boundary of the miscibility gap. Activities of Fe, Pb, and S, along the miscibility gap were also calculated by utilizing the bounding binary thermodynamics, phase equilibria, and tie-lines.

  12. Apparent molal volumes of HMT and TATD in aqueous solutions around the temperature of maximum density of water

    International Nuclear Information System (INIS)

    Clavijo Penagos, J.A.; Blanco, L.H.

    2012-01-01

    Highlights: ►V φ for HMT and TATD in aqueous solutions around the temperature of maximum density of water are reported. ► V φ is linear in m form m = 0.025 for all the aqueous solutions investigated. ► Variation of V ¯ 2 ∞ with T obeys a second grade polynomial trend. ► The solutes are classified as structure breakers according to Hepler’s criterion. - Abstract: Apparent molal volumes V φ have been determined from density measurements for several aqueous solutions of 1,3,5,7-tetraazatricyclo[3.3.1.1(3,7)]decane (HMT) and 1,3,6,8-tetraazatricyclo[4.4.1.1(3,8)]dodecane (TATD) at T = (275.15, 275.65, 276.15, 276.65, 277.15, 277.65 and 278.15) K as function of composition. The infinite dilution partial molar volumes of solutes in aqueous solution are evaluated through extrapolation. Interactions of the solutes with water are discussed in terms of the effect of the temperature on the volumetric properties and the structure of the solutes. The results are interpreted in terms of water structure-breaking or structure forming character of the solutes.

  13. Effect of alkyl chain length and temperature on the thermodynamic properties of ionic liquids 1-alkyl-3-methylimidazolium bromide in aqueous and non-aqueous solutions at different temperatures

    International Nuclear Information System (INIS)

    Sadeghi, Rahmat; Shekaari, Hemayat; Hosseini, Rahim

    2009-01-01

    The alkyl chain length of 1-alkyl-3-methylimidazolium bromide ([Rmim][Br], R = propyl (C 3 ), hexyl (C 6 ), heptyl (C 7 ), and octyl (C 8 )) was varied to prepare a series of room-temperature ionic liquids (RTILs), and experimental measurements of density and speed of sound at different temperatures ranging from (288.15 to 308.15) K for their aqueous and methanolic solutions in the dilute concentration region (0.01 to 0.30) mol . kg -1 were taken. The values of the compressibilities, expansivity and apparent molar properties for [C n mim][Br] in aqueous and methanolic solutions were determined at the investigated temperatures. The obtained apparent molar volumes and apparent molar isentropic compressibilities were fitted to the Redlich-Mayer and the Pitzer's equations from which the corresponding infinite dilution molar properties were obtained. The values of the infinite dilution molar properties were used to obtain some information about solute-solvent and solute-solute interactions. The thermodynamic properties of investigated ionic liquids in aqueous solutions have been compared with those in methanolic solutions. Also, the comparison between thermodynamic properties of investigated solutions and those of electrolyte solutions, polymer solutions, cationic surfactant solutions and tetraalkylammonium salt solutions have been made

  14. High-Performance High-Loading Lithium-Sulfur Batteries by Low Temperature Atomic Layer Deposition of Aluminum Oxide on Nanophase S Cathodes

    Energy Technology Data Exchange (ETDEWEB)

    Meng, Xiangbo [Department of Mechanical Engineering, University of Arkansas, Fayetteville AR 72701 USA; Liu, Yuzi [Center for Nanoscale Materials, Argonne National Laboratory, Argonne IL 60439 USA; Cao, Yanqiang [Energy Systems Division, Argonne National Laboratory, Argonne IL 60439 USA; Ren, Yang [Advanced Photon Source, Argonne National Laboratory, Argonne IL 60439 USA; Lu, Wenquan [Chemical Sciences and Engineering Division, Argonne National Laboratory, Argonne IL 60439 USA; Elam, Jeffrey W. [Energy Systems Division, Argonne National Laboratory, Argonne IL 60439 USA

    2017-05-18

    This study examines the effects of nanophase S and surface coatings via atomic layer deposition (ALD) on high-loading sulfur cathodes for developing high-performance and high-energy lithium-sulfur (Li-S) batteries. It is first verified that ball milling is an effective and facile route for nanoengineering microsized S powders and the resultant nanoscale S particles exhibit better performance. Using these ball milled nanoscale S cathodes, it is found that ALD Al2O3 performed at 50 degrees C yields deposits that evolve with ALD cycles from dispersed nanoparticles, to porous, connected films, and finally to dense and continuous films. Moreover, this low temperature ALD process suppresses S loss by sublimation. The ALD Al2O3 greatly improves sulfur cathode sustainable capacity and Coulombic efficiency. This study postulates two different mechanisms underlying the effects of ALD Al2O3 surface coatings depending on their morphology. ALD Al2O3 nanoparticles dispersed on the sulfur surface mainly function to adsorb polysulfides, thereby inhibiting S shuttling and improving sustainable capacity and Coulombic efficiency. By contrast, ALD Al2O3 films behave as a physical barrier to prevent polysulfides from contacting the liquid electrolyte and dissolving. The dispersed Al2O3 nanoparticles improve both sustainable capacity and Coulombic efficiency while the closed Al2O3 films improve Coulombic efficiency while decreasing the capacity

  15. The Role of Perturbations in the B-X UV Spectrum of S_{2} in a Temperature-Dependent Mechanism for Sulfur Mass Independent Fractionation

    Science.gov (United States)

    Hull, Alexander W.; Field, Robert W.; Ono, Shuhei

    2017-06-01

    Sulfur mass independent fractionation (S-MIF) describes anomalous sulfur isotope ratios commonly found in sedimentary rocks older than 2.45 billion years. These anomalies likely originate from photochemistry of small, sulfur-containing molecules in the atmosphere, and their sudden disappearance from rock samples younger than 2.45 years is thought to be correlated with a sharp rise in atmospheric oxygen levels. The emergence of atmospheric oxygen is an important milestone in the development of life on Earth, but the mechanism for sulfur MIF in an anoxic atmosphere is not well understood. In this context, we present an analysis of the B-X UV spectrum of S_{2}, an extension of work presented last year. The B state of S_{2} is strongly perturbed by the nearby B" state, as originally described by Green and Western (1996). Our analysis suggests that a doorway-mediated transfer mechanism shifts excited state population from the short-lifetime B state to the longer-lifetime B" state. Furthermore, access to the perturbed doorway states is strongly dependent on the population distribution in the ground state. This suggests that the temperature of the Achaean atmosphere may have played a significant role in determining the extent of S-MIF.

  16. Effect of temperature on the dilution enthalpies of α,ω-amino acids in aqueous solutions

    International Nuclear Information System (INIS)

    Romero, C.M.; Cadena, J.C.; Lamprecht, I.

    2011-01-01

    Highlights: → The dilution of 3-amino propanoic acid, 4-amino butanoic acid, 5-amino pentanoic acid, and 6-amino hexanoic acid in water is an exothermic process at T = (293.15, 298.15, 303.15, and 308.15) K. → The limiting experimental slopes of the enthalpies of dilution with respect to the molality change Δm, are negative suggesting that the solutes interact with water primarily through their alkyl groups. → The value of the pairwise coefficient is positive at the temperatures considered, and the magnitude increases linearly with the number of methylene groups. → The comparison between the pairwise interaction coefficients for α,ω-amino acids and α-amino acids shows that the change in the enthalpic interaction coefficient is related to the relative position of the polar groups. - Abstract: Dilution enthalpies of aqueous solutions of 3-amino propanoic acid, 4-amino butanoic acid, 5-amino pentanoic acid, and 6-amino hexanoic acid were determined at T = (293.15, 298.15, 303.15, and 308.15) K using an LKB flow microcalorimeter. The homotactic interaction coefficients were obtained according to the McMillan-Mayer theory from the experimental data. For all the systems studied, the dilution of α,ω-amino acids in water is an exothermic process; the pair coefficients have positive values which increases with chain length. The obtained values of the interaction coefficients are interpreted in terms of solute-solvent and solute-solute interactions and are used as indicative of hydrophobic behavior of the amino acid studied.

  17. Removal of the Pesticide Pymetrozine from Aqueous Solution by Biochar Produced from Brewer's Spent Grain at Different Pyrolytic Temperatures

    OpenAIRE

    Xinguo Xi; Jinlong Yan; Guixiang Quan; Liqiang Cui

    2014-01-01

    Biochar (BC) produced from brewer's spent grain (BSG) via slow pyrolysis at 300, 400, 500, 600, and 700 °C was characterized and investigated as an adsorbent for the removal of the pesticide pymetrozine from aqueous solution. Batch BSG BCs adsorption experiments were carried out under various conditions (such as pH, pymetrozine concentration, and BC dosage) to adsorb the pymetrozine. The BSG BCs adsorption pymetrozine capacities were increased by 21.4% to 55.5% under pyrolysis temperatures of...

  18. Degeneration of amyloid-ß fibrils caused by exposure to low-temperature atmospheric-pressure plasma in aqueous solution

    OpenAIRE

    Takai, Eisuke; Ohashi, Gai; Yoshida, Tomonori; Sörgjerd, Karin Margareta; Zako, Tamotsu; Maeda, Mizuo; Kitano, Katsuhisa; Shiraki, Kentaro

    2014-01-01

    Low-temperature atmospheric-pressure plasma was applied to degenerate amyloid-ß (Aß) fibrils, which are a major component of neuritic plaque associated with Alzheimer's disease (AD). We showed that an Aß fibril exposed to a low-frequency (LF) plasma jet in aqueous solution retained its morphology, molecular weight, and cytotoxicity, but, intriguingly, decreased in protease resistance and ß-sheet content. These results suggested that an LF plasma jet could be utilized for the treatment of AD t...

  19. Rechargeable Lithium Sulfur (Li-S) Battery with Specific Energy 400 Wh/kg and Operating Temperature Range -60°C to 60°C, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — Sion Power is developing a rechargeable lithium sulfur (Li-S) battery with a demonstrated specific energy exceeding 350 Wh/kg and the range of operating temperatures...

  20. The oxidation and hydriding of zircaloy fuel cladding in high temperature aqueous solutions

    Science.gov (United States)

    Chen, Yingzi

    at the metal/film interface control the rate of film growth when the potential is displaced in the positive direction, whereas the kinetics of dissolution of the barrier layer at the barrier layer/solution interface control the rate of passive film thinning when the potential is stepped in the negative direction. Both the growth rate and dissolution rate of the passive films formed in the hydrogenated solution are lower than that formed in the dehydrogenated solution. In addition, the effects of second phase particles (SPPs) on the electrochemistry of passive zirconium in the hydrogenated, high temperature aqueous solutions are examined by using different heat-treated Zircaloy-4 samples; i.e., as-received, beta-quenched, and alpha-annealed. Optical microscopy with polarized light and scanning electron microscopy (SEM) were used to characterize the microstructure and determine the size and density of the SPPs. The average size of the second phase particles in the Zircaloy-4 samples was in the sequence of beta-quenched beta-quenched sample has the highest corrosion resistance, while the a-annealed sample has the lowest. It is also evident that the second phase particles play an important role in determining the electronic character of a passive film, as demonstrated by Mott-Schottky analysis. The second phase particles may cause short circuits in the electrical path across the passive film, which would explain the effect of the size and the density of the SPPs, and hence heat treatment, on the corrosion properties of passive Zircaloy-4.

  1. Densities of L-Glutamic Acid HCl Drug in Aqueous NaCl and KCl Solutions at Different Temperatures

    Science.gov (United States)

    Ryshetti, Suresh; Raghuram, Noothi; Rani, Emmadi Jayanthi; Tangeda, Savitha Jyostna

    2016-04-01

    Densities (ρ ) of (0.01 to 0.07) {mol}{\\cdot } {kg}^{-1} L-Glutamic acid HCl (L-HCl) drug in water, and in aqueous NaCl and KCl (0.5 and 1.0) {mol}{\\cdot } {kg}^{-1} solutions have been reported as a function of temperature at T = (298.15, 303.15, 308.15, and 313.15) K and atmospheric pressure. The accurate density (ρ ) values are used to estimate the various parameters such as the apparent molar volume (V_{2,{\\upphi }}), the partial molar volume (V2^{∞}), the isobaric thermal expansion coefficient (α 2), the partial molar expansion (E2^{∞}), and Hepler's constant (partial 2V2^{∞}/partial T2)P. The Cosphere overlap model is used to understand the solute-solvent interactions in a ternary mixture (L-HCl drug + NaCl or KCl + water). Hepler's constant (partial 2V2^{∞}/partial T2)_P is utilized to interpret the structure-making or -breaking ability of L-HCl drug in aqueous NaCl and KCl solutions, and the results are inferred that L-HCl drug acts as a structure maker, i.e., kosmotrope in aqueous NaCl solutions and performs as a structure breaker, i.e., chaotrope in aqueous KCl solutions.

  2. Control of temperature and aqueous Mg2+/Ca2+ ratio on the (trans-)formation of ikaite

    Science.gov (United States)

    Purgstaller, B.; Dietzel, M.; Baldermann, A.; Mavromatis, V.

    2017-11-01

    The calcium carbonate hexahydrate mineral ikaite (CaCO3 ṡ 6 H2O) has been documented in aquatic environments at near-freezing temperatures. An increase of the prevailing temperature in the depositional environment, results in the transformation of natural ikaite into less soluble calcium carbonate phases occasionally leaving calcite pseudomorphs in the sediments, which are considered as an indicator for primary cold water temperatures. Detailed understanding on the physicochemical parameters controlling ikaite (trans-)formation however, such as temperature and reactive solution chemical composition, are still under debate. In order to study the formation of ikaite, we conducted precipitation experiments under controlled physicochemical conditions (pH = 8.3 ± 0.1; T = 6, 12, and 18 ± 0.1 °C) at defined aqueous molar Mg/Ca ratios. The transformation of ikaite into anhydrous calcium carbonate polymorphs was investigated in solution and at air exposure. The obtained results reveal the formation of ikaite at temperatures up to 12 °C, whereas Mg-rich amorphous calcium carbonate precipitated at 18 °C. In contact with the reactive solution ikaite transformed into aragonite at aqueous molar Mg2+/Ca2+ ratios of ≥14. In contrast, ikaite separated from the Mg-rich solution and exposed to air transformed in all cases into calcite/vaterite. The herein obtained temperature limit of ≤12 for ikaite formation is significantly higher than formerly expected and most probably caused by (i) the high saturation degree of the solution with respect to ikaite and (ii) the slow dehydration of the aqueous Ca2+ ion at low temperatures. This result questions the suitability of calcite pseudomorphs (i.e. glendonites) as a proxy for near-freezing temperatures. Moreover, our findings show that the CaCO3 polymorph formed from ikaite is strongly controlled by the physicochemical conditions, such as aqueous molar Mg2+/Ca2+ ratio of the reactive fluid and H2O availability throughout the

  3. Condensation of amino acids to form peptides in aqueous solution induced by the oxidation of sulfur(iv): an oxidative model for prebiotic peptide formation.

    Science.gov (United States)

    Chen, Fei; Yang, Dan

    2007-02-01

    Condensation of amino acids to peptides is an important step during the origin of life. However, up to now, successful explanations for plausible prebiotic peptide formation pathways have been limited. Here we report that the oxidation of sulfur (IV) can induce the condensation reaction of carboxylic acids and amines to form amides, and the condensation reaction of amino acids to form peptides. This might be a general reaction contributing to prebiotic peptide formation.

  4. 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.

  5. Quantitative analysis of the calorimetric parameters associated with the temperature induced aggregation of aqueous solutions of polyoxypropylene

    International Nuclear Information System (INIS)

    Armstrong, Jonathan K.; Chowdhry, Babur Z.; Snowden, Martin J.; Dong, Jingfeng; Leharne, Stephen A.

    2003-01-01

    High sensitivity differential scanning calorimetry (HSDSC)--coupled with the application of a previously outlined thermodynamic model [Patterson et al., Langmuir 13 (1997) 2219]--has been used to the obtain thermodynamic parameters that characterise thermal aggregation in aqueous solutions of polyoxypropylene (POP) of molecular mass 1000 g mol -1 over a range of concentrations (2.5-51.5 g dm -3 ). An important aspect of the derived thermodynamic values, which complements previously reported HSDSC data [Armstrong et al., J. Phys. Chem. 99 (1995) 4590], is the elaboration of heat capacity changes which accompany the aggregation transition. The concentration dependence of the POP thermodynamic data, obtained in this investigation, has been established. These observations provide the means for establishing functional relationships between enthalpy and temperature as well as heat capacity and temperature. The parameters describing the quadratic relationship between enthalpy change associated with aggregation and temperature are in close agreement with those describing the linear relationship between heat capacity change and temperature

  6. Effect of temperature on solvation behaviour of diclofenac sodium salt in aqueous glycine and L-proline solutions

    International Nuclear Information System (INIS)

    Ryshetti, Suresh; Gardas, Ramesh L; Tangeda, Savitha Jyostna

    2015-01-01

    Highlights: • Solvation behaviour of diclofenac drug studied in aqueous solutions. • Density and speed of sound of drug in aq. glycine and L-proline are measured. • Hydrophobic nature of diclofenac sodium salt is studied. • Effect of temperature on solvation of diclofenac sodium salt is analysed. - Abstract: Apparent molar volume (V 2,ϕ ) and apparent molar isentropic compressibility (K s,2,ϕ ) of diclofenac sodium salt (DSS) drug within the concentration range of (0.001 to 0.008) mol · kg −1 in (0.01, 0.03 and 0.05) mol · kg −1 aqueous glycine and L-proline solutions are computed from the experimental density (ρ) and speed of sound (u) values at T = (293.15 to 313.15) K and atmospheric pressure. Derived parameters such as partial molar properties, transfer partial molar properties, hydration numbers and Hepler’s constant are computed from the data of V 2,ϕ and K s,2,ϕ . These parameters have been used to understand the effect of temperature on interactions between DSS drug and aqueous glycine/L-proline solution. Furthermore, the structure making and breaking ability of DSS drug in probed solutions are analysed at experimental conditions

  7. Ultrasonic speed, densities and viscosities of xylitol in water and in aqueous tyrosine and phenylalanine solutions at different temperatures

    Science.gov (United States)

    Ali, A.; Bidhuri, P.; Uzair, S.

    2014-07-01

    Ultrasonic speed u, densities ρ and viscosities η of xylitol in water and in 0.001 m aqueous l-tyrosine (Tyr) and l-phenylalanine (Phe) have been measured at different temperatures. From the density and ultrasonic speed measurements apparent molar isentropic compression κ_{φ}, apparent molar isentropic compressions at infinite dilution κ_{{S,φ}}0 , experimental slope S K , hydration number n H , transfer partial molar isentropic compressibility Δ_{tr} κ_{{S,φ}}0 of xylitol from water to aqueous Tyr and Phe have been obtained. From the viscosity data, B-coefficient and B-coefficient of transfer Δ tr B of xylitol from water to aqueous Phe and Tyr at different temperatures have also been estimated. Gibbs free energies of activation of viscous flow per mole of solvent Δ μ 1 0# and per mole of solute Δ μ 2 0# have been calculated by using Feakins transition state theory for the studied systems. The calculated parameters have been interpreted in terms of solute-solute and solute-solvent interactions and hydration behavior of xylitol.

  8. Influence of temperature on water and aqueous glucose absorption spectra in the near- and mid-infrared regions at physiologically relevant temperatures

    DEFF Research Database (Denmark)

    Jensen, P.S.; Bak, J.; Andersson-Engels, S.

    2003-01-01

    Near- and mid-infrared absorption spectra of pure water and aqueous 1.0 g/dL glucose solutions in the wavenumber range 8000-950 cm(-1) were measured in the temperature range 30-42 C in steps of 2 degreesC. Measurements were carried out with an FT-IR spectrometer and a variable pathlength...... degreesC water spectrum from the spectra measured at other temperatures. The difference spectra reveal that the effect of temperature is highest in the vicinity of the strong absorption bands, with a number of isosbestic points with no temperature dependence and relatively flat plateaus in between....... The change in water absorption associated with the addition of glucose has also been studied. An estimate of these effects is given and is related to the expected level of infrared signals from glucose in humans....

  9. Gaseous byproducts from high-temperature thermal conversion elemental analysis of nitrogen- and sulfur-bearing compounds with considerations for δ2H and δ18O analyses.

    Science.gov (United States)

    Hunsinger, Glendon B; Tipple, Christopher A; Stern, Libby A

    2013-07-30

    High-temperature, conversion-reduction (HTC) systems convert hydrogen and oxygen in materials into H2 and CO for δ(2)H and δ(18)O measurements by isotope ratio mass spectrometry. HTC of nitrogen- and sulfur-bearing materials produces unintended byproduct gases that could affect isotope analyses by: (1) allowing isotope exchange reactions downstream of the HTC reactor, (2) creating isobaric or co-elution interferences, and (3) causing deterioration of the chromatography. This study characterizes these HTC byproducts. A HTC system (ThermoFinnigan TC/EA) was directly connected to a gas chromatograph/quadrupole mass spectrometer in scan mode (m/z 8 to 88) to identify the volatile products generated by HTC at conversion temperatures of 1350 °C and 1450 °C for a range of nitrogen- and sulfur-bearing solids [keratin powder, horse hair, caffeine, ammonium nitrate, potassium nitrate, ammonium sulfate, urea, and three nitrated organic explosives (PETN, RDX, and TNT)]. The prominent HTC byproduct gases include carbon dioxide, hydrogen cyanide, methane, acetylene, and water for all nitrogen-bearing compounds, as well as carbon disulfide, carbonyl sulfide, and hydrogen sulfide for sulfur-bearing compounds. The 1450 °C reactor temperature reduced the abundance of most byproduct gases, but increased the significant byproduct, hydrogen cyanide. Inclusion of a post-reactor chemical trap containing Ascarite II and Sicapent, in series, eliminated the majority of byproducts. This study identified numerous gaseous HTC byproducts. The potential adverse effects of these gases on isotope ratio analyses are unknown but may be mitigated by higher HTC reactor temperatures and purifying the products with a purge-and-trap system or with chemical traps. Published in 2013. This article is a U.S. Government work and is in the public domain in the USA.

  10. NMR investigations of temperature-induced phase transition in aqueous polymer solutions

    Czech Academy of Sciences Publication Activity Database

    Spěváček, Jiří

    2011-01-01

    Roč. 305, č. 1 (2011), s. 18-25 ISSN 1022-1360 R&D Projects: GA ČR GA202/09/1281 Institutional research plan: CEZ:AV0Z40500505 Keywords : aqueous polymer solutions * cooperative effects * NMR Subject RIV: CD - Macromolecular Chemistry

  11. Determination of Optimal Temperature for Biosorption of Heavy Metal Mixture from Aqueous Solution by Pretreated Biomass of Aspergillus niger

    Directory of Open Access Journals (Sweden)

    Javad Yousefi

    2012-01-01

    Full Text Available Biosorption is a novel technology that uses dead and inactive biomass for removal of heavy metals from aqueous solution. Some parameters such as temperature, contact time, solution pH, initial metal concentration, biosorbent dose and also agitating speed of solution and biosorbent mixing can affect the amount of metal sorption by biosorbent. The aim of this study was to investigate the effects of different treatments of temperatures (25, 35, 45 and 55oC on biosorption of metals mixture in order to determine optimal temperature for more metals removal from aqueous solution. This study uses dead and pretreated biomass of Aspergillus niger with 0.5N NaOH for removal of Zn(II, Co(II and Cd(II. In all temperature treatments and in the case of all of heavy metals, maximum amount of metal sorption and concentration decrease was occurred in first 5 minutes and achieved to equilibrium after 20 minute. The percent of metals sorption show growth trend with temperature increase. Between 4 experimental treatments, 55oC treatment was shown maximum sorption and 25oC was shown minimum sorption amount. The percent of Cr(II sorption was increase from 28.5% in 25oC to 44.7% in 55oC. Also, this increase was from 40% to 58% for Cd(II and from 37.7% to 65.6% for Zn(II. About 60% of increase in sorption by A. niger was due to increase in temperature. Therefore the amount of metals sorption can be increase, only with temperature increase and without any biomass addition.

  12. Solubilization of sulfur compounds in the crude oil by nonionic surfactants

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Suk Kyu; Han, Ji Won; Park, Sang Kwon; Lo, Jong Choo [Department of Chemical Engineering, Dongguk University, Seoul (Korea); Kim, Byung Hong; Shin, Pyung Gyun [Korea Institute of Science and Technology (Korea)

    2000-04-01

    In this study, polyoxyethylene(POE) nonionic surfactants were used in order ro enhance the solubilization of sulfur compounds contained in the crude oil and the solubilized sulfur contents in the aqueous surfactant solutions were measured by X-ray sulfur spectrometer. The most hydrophobic surfactant among used during this study showed the maximum solubilization capacity for the sulfur compounds in the crude oil and the solubilization of sulfur compounds was found to be increased with temperature and to be abruptly increased at above 1 wt % surfactant solutions. It was found that Tergitol series surfactants showed higher solubilizing capacity than Neodol series surfactants presumably due to the disruption of the regular packing in the hydrocarbon region of the surfactant aggregates. The addition of a cosurfactant such as alcohol and/or an electrolyte increased the solubilization of sulfur compound in the crude oil. It was found that preheating phenomena were shown to be significant with an hydrophobic surfactant at high temperature and the growth of sulfur reducing microorganisms was not greatly affected by the addition of nonionic surfactants. 21 ref s.,11 fig., 2 tabs.

  13. Low-temperature formation and stabilization of rare allotropes of cyclooctasulfur (β-S8 and γ-S8) in the presence of organic carbon at a sulfur-rich glacial site in the Canadian High Arctic

    Science.gov (United States)

    Lau, Graham E.; Cosmidis, Julie; Grasby, Stephen E.; Trivedi, Christopher B.; Spear, John R.; Templeton, Alexis S.

    2017-03-01

    Large-scale deposits of elemental sulfur form annually on a glacier's surface at Borup Fiord Pass in the Canadian High Arctic. However, the mechanisms of mineralization and stabilization of elemental sulfur at this site are currently unknown. Here we show that X-ray diffraction (XRD) data for fresh sulfur precipitates collected from the surface of a melt pool over sulfide-rich ice reveal the presence of three sulfur allotropes, α-S8, β-S8, and γ-S8 (the three solid forms of cyclooctasulfur (S8)). The detection of the β-S8 allotrope of elemental sulfur is notable, since β-S8 typically only forms in high temperature environments (>96 °C). The γ-S8 allotrope is also rare in natural settings and has previously been implicated as a signature of microbial sulfur cycling. Using combustion and infrared spectroscopy approaches, organic carbon is also detected within the sample bearing the three allotropes of elemental sulfur. Electron microscopy and scanning transmission X-ray microscopy (STXM) at the C K-edge show that the sulfur precipitates are intimately associated with the organic carbon at the submicron scale. The occurrence of β-S8 and γ-S8 in this low-temperature setting indicates that there are unknown pathways for the formation and stabilization of these rare allotropes of elemental sulfur. In particular, we infer that the occurrence of these allotropes is related to their association with organic carbon. The formation of carbon-associated sulfur globules may not be a direct by-product of microbial activity; however, a potential role of direct or indirect microbial mediation in the formation and stabilization of β-S8 and γ-S8 remains to be assessed.

  14. Sulfuric Acid and Water: Paradoxes of Dilution

    Science.gov (United States)

    Leenson, I. A.

    2004-01-01

    On equilibrium properties of aqueous solutions of sulfuric acid, Julius Thomsen has marked that the heat evolved on diluting liquid sulfuric acid with water is a continuous function of the water used, and excluded absolutely the acceptance of definite hydrates as existing in the solution. Information about thermochemical measurement, a discussion…

  15. Comparison of catalytic activity of Ru(3) cloride and Ru(8) oxide in oxidation of 2-methyl cyclohexanol by Ce(4) sulfate in aqueous solutions of sulfuric acid

    International Nuclear Information System (INIS)

    Tondeon, P.K.; Krishna, B.

    1985-01-01

    The catalytic activity of Ru(3) chloride and Ru(8) oxide in the course of 2-methyl cyclohexanol (MCH) oxidation by Ce(4) sulfate in sulfuric acid is compared. In the presepce of RU(3) the reaction kinetics obeys the equation of the first order relative to organic substrate concentration (at its low concentrations) and tends to zero order at its higher concentrations. For ruthenium (3) chloride the first order is observed. In the presence of Ru(8) the reaction rate is proportional to substrate and catalyst concentrations only in the low concentrations region of the latter while at RU(8) high concentrations a decrease of the catalytic effect is observed. In both cases the process rate is inversely proportional to the sulfuric acid concentration square at its great values and directly proportional-at small ones. An assumption is made that cyclic alcohol oxidation occurs through the activated complex formed as a result of alcohol interaction with Ru(3) or ruthenium (8) hydride

  16. Simultaneous determination of nitric acid and uranium concentrations in aqueous solution from measurements of electrical conductivity, density, and temperature

    International Nuclear Information System (INIS)

    Spencer, B.B.

    1991-01-01

    Nuclear fuel reprocessing plants handle aqueous solutions of nitric acid and uranium in large quantities. Automatic control of process operations requires reliable measurements of these solutes concentration, but this is difficult to directly measure. Physical properties such as solution density and electrical conductivity vary with solute concentration and temperature. Conductivity, density and temperature can be measured accurately with relatively simple and inexpensive devices. These properties can be used to determine solute concentrations will good correlations. This paper provides the appropriate correlations for solutions containing 2 to 6 Molar (M) nitric acid and 0 to 300 g/L uranium metal at temperatures from 25--90 degrees C. The equations are most accurate below 5 M nitric acid, due to a broad maximum in the conductivity curve at 6 M. 12 refs., 9 figs., 6 tabs

  17. Influence of pyrolysis temperature on lead immobilization by chemically modified coconut fiber-derived biochars in aqueous environments.

    Science.gov (United States)

    Wu, Weidong; Li, Jianhong; Niazi, Nabeel Khan; Müller, Karin; Chu, Yingchao; Zhang, Lingling; Yuan, Guodong; Lu, Kouping; Song, Zhaoliang; Wang, Hailong

    2016-11-01

    Biochar has received widespread attention as an eco-friendly and efficient material for immobilization of toxic heavy metals in aqueous environments. In the present study, three types of coconut fiber-derived biochars were obtained by pyrolyzing at three temperatures, i.e., 300, 500, and 700 °C. In addition, nine types of biochars were prepared by chemical modification with ammonia, hydrogen peroxide, and nitric acid, respectively, which were used to investigate changes in physico-chemical properties by inter alia, Fourier transformation infrared spectrophotometry (FTIR), scanning electron microscope (SEM), and BET specific surface area analysis. Batch sorption experiments were carried out to determine the sorption capacity of the biochars for lead (Pb) in aqueous solutions. Results showed that the cation exchange capacity of biochar pyrolyzed at 300 °C and modified with nitric acid increased threefold compared to the control. Loosely corrugated carbon surface and uneven carbon surface of the biochar pyrolyzed at 300 °C were produced during ammonia and nitric acid modifications. Removal rate of Pb by the coconut biochar pyrolyzed at 300 °C and modified with ammonia was increased from 71.8 to 99.6 % compared to the untreated biochar in aqueous solutions containing 100 mg L -1 Pb. However, chemical modification did not enhance adsorption of Pb of the biochars pyrolyzed at higher temperatures (e.g., 500 or 700 °C), indicating that resistance of biochars to chemical treatment increased with pyrolysis temperature.

  18. Application of Eh-pH diagram for room temperature precipitation of zinc stannate microcubes in an aqueous media

    International Nuclear Information System (INIS)

    Al-Hinai, Ashraf T.; Al-Hinai, Muna H.; Dutta, Joydeep

    2014-01-01

    Graphical abstract: - Highlights: • One pot aqueous synthesis of zinc stannate (ZnSnO 3 ) particles at low temperature. • Synthesis designed with the assistance of potential-pH diagram. • ZnSnO 3 estimated to be stable between pH 8 and 12 was used for synthesis of the particles. • ZnSnO 3 ·3H 2 O were formed during the precipitation of zinc stannate. - Abstract: Potential-pH diagram assisted-design for controlled precipitation is an attractive method to obtain engineered binary and ternary oxide particles. Aqueous synthesis conditions of zinc stannate (ZnSnO 3 ) particles at low temperature were formulated with the assistance of potential-pH diagram. The pH of a solution containing stoichiometric amounts of Zn 2+ and Sn 4+ was controlled for the precipitation in a one pot synthesis step at room temperature (25 °C). The effect of the concentration of the reactants on the particle size was studied by varying the concentration of the precursor (Zn 2+ + Sn 4+ ) solution. Scanning electron micrographs show that the particles are monodispersed micron sized cubes formed by the self-organization of nano-sized crystallites. The obtained microcubes characterized by X-ray Diffraction and thermo gravimetric analysis (TGA) show that the particles are in ZnSnO 3 ·3H 2 O form

  19. Aqueous singlet oxygen reaction kinetics of furfuryl alcohol: effect of temperature, pH, and salt content.

    Science.gov (United States)

    Appiani, Elena; Ossola, Rachele; Latch, Douglas E; Erickson, Paul R; McNeill, Kristopher

    2017-04-19

    The rate constant for the reaction between furfuryl alcohol (FFA) and singlet oxygen ( 1 O 2 ) in aqueous solution was measured as a function of temperature, pH and salt content employing both steady-state photolysis (β value determination) and time-resolved singlet oxygen phosphorescence methods. The latter provided more precise and reproducible data. The reaction rate constant, k rxn,FFA , had a relatively small temperature dependence, no pH dependence and showed a small increase in the presence of high salt concentrations (+19% with 1 M NaCl). A critical review of the available literature suggested that the widely used value of 1.2 × 10 8 M -1 s -1 is likely overestimated. Therefore, we recommend the use of 1.00 × 10 8 M -1 s -1 for reactions performed in low ionic strength aqueous solutions (freshwater) at 22 °C. Furthermore, corrections are provided that should be applied when working at higher or lower temperatures, and/or at high salt concentrations (seawater).

  20. Hexadecyltrimethylammonium bromide micellization in glycine, diglycine, and triglycine aqueous solutions as a function of surfactant concentration and temperatures

    Science.gov (United States)

    Ali, Anwar; Malik, Nisar Ahmad; Uzair, Sahar; Ali, Maroof; Ahmad, Mohammad Faiz

    2014-06-01

    Micellization behavior of hexadecyltrimethylammonium bromide (HTAB) was investigated conductometrically in aqueous solutions containing 0.02 mol kg-1glycine (Gly), diglycine (Gly-Gly), and triglycine (Gly-Gly-Gly) as a function of surfactant concentration at different temperatures. The critical micelle concentration (CMC) of HTAB exhibits a decreasing trend as the number of carbon atoms increases from Gly to Gly-Gly-Gly, favoring the micelle formation. The values of CMC and the degree of counterion dissociation of the micelles were utilized to evaluate the standard free energy for transferring the surfactant hydrophobic chain out of the solvent to the interior of the micelle, Δ G {HP/○}, free energy associated with the surface contributions, Δ G {S/○}, standard free energy, Δ G {m/○}, enthalpy, Δ H {m/○}, and entropy, Δ S {m/○} of micellization were also calculated. The results show that the micellization of HTAB in aqueous solutions as well as in aqueous Gly/Gly-Gly/Gly-Gly-Gly solutions is primarily governed by the entropy gain due to the transfer of the hydrophobic groups of the surfactant from the solvent to the interior part of the micelle. The CMC obtained by fluorometric method is in close agreement with those obtained conductometrically. Furthermore, decrease in the I 1/ I 3 ratio of pyrene fluorescence intensity suggests the solubilization of the additives by the surfactant micelles and that this solubilization increases as the hydrophobicity increases from Gly to Gly-Gly-Gly.

  1. Experimental and Numerical Study on Effects of Airflow and Aqueous Ammonium Temperature on Ammonia Mass Transfer Coefficient

    DEFF Research Database (Denmark)

    Rong, Li; Nielsen, Peter V.; Zhang, Guoqiang

    2010-01-01

    transfer are investigated by using computational fluid dynamics (CFD) modeling and by a mechanism modeling using dissociation constant and Henry's constant models based on the parameters measured in the experiments performed in a wind tunnel. The validated CFD model by experimental data is used......This paper reports the results of an investigation, based on fundamental fluid dynamics and mass transfer theory, carried out to obtain a general understanding of ammonia mass transfer from an emission surface. The effects of airflow and aqueous ammonium solution temperature on ammonia mass...

  2. Calcium isotope fractionation between aqueous compounds relevant to low-temperature geochemistry, biology and medicine

    OpenAIRE

    Frédéric Moynier; Toshiyuki Fujii

    2017-01-01

    Stable Ca isotopes are fractionated between bones, urine and blood of animals and between soils, roots and leaves of plants by >1000?ppm for the 44Ca/40Ca ratio. These isotopic variations have important implications to understand Ca transport and fluxes in living organisms; however, the mechanisms of isotopic fractionation are unclear. Here we present ab initio calculations for the isotopic fractionation between various aqueous species of Ca and show that this fractionation can be up to 3000?...

  3. Temperature-induced phase transition in aqueous solutions of poly(N-isopropylacrylamide)-based block copolymer

    Czech Academy of Sciences Publication Activity Database

    Spěváček, Jiří; Konefal, Rafal; Dybal, Jiří

    2016-01-01

    Roč. 369, č. 1 (2016), s. 92-96 ISSN 1022-1360. [International IUPAC Conference on Polymer-Solvent Complexes and Intercalates /11./ - POLYSOLVAT-11. Kolkata, 27.01.2016-30.01.2016] R&D Projects: GA ČR(CZ) GA15-13853S Institutional support: RVO:61389013 Keywords : aqueous solutions * block copolymers * micelles Subject RIV: CD - Macromolecular Chemistry

  4. Estimation and application of the thermodynamic properties of aqueous phenanthrene and isomers of methylphenanthrene at high temperature

    Science.gov (United States)

    Dick, Jeffrey M.; Evans, Katy A.; Holman, Alex I.; Jaraula, Caroline M. B.; Grice, Kliti

    2013-12-01

    Estimates of standard molal Gibbs energy (ΔGf°) and enthalpy (ΔHf°) of formation, entropy (S°), heat capacity (CP°) and volume (V°) at 25 °C and 1 bar of aqueous phenanthrene (P) and 1-, 2-, 3-, 4- and 9-methylphenanthrene (1-MP, 2-MP, 3-MP, 4-MP, 9-MP) were made by combining reported standard-state properties of the crystalline compounds, solubilities and enthalpies of phenanthrene and 1-MP, and relative Gibbs energies, enthalpies and entropies of aqueous MP isomers from published quantum chemical simulations. The calculated properties are consistent with greater stabilities of the β isomers (2-MP and 3-MP) relative to the α isomers (1-MP and 9-MP) at 25 °C. However, the metastable equilibrium values of the abundance ratios 2-MP/1-MP (MPR) and (2-MP + 3-MP)/(1-MP + 9-MP) (MPI-3) decrease with temperature, becoming Australia) indicates a likely effect of high-temperature equilibration on reported values of MPR and MPI-3, but this finding is contingent on the location within the deposit. If metastable equilibrium holds, a third aromatic maturity ratio, 1.5 × (2-MP + 3-MP)/(P + 1-MP + 9-MP) (MPI-1), can be used as a proxy for oxidation potential. Values of logaH2aq determined from data reported for HYC and for a sequence of deeply buried source rocks are indicative of more reducing conditions at a given temperature than those inferred from data reported for two sets of samples exposed to contact or regional metamorphism. These results are limiting-case scenarios for the modeled systems that do not account for effects of non-ideal mixing or kinetics, or external sources or transport of the organic matter. Nevertheless, quantifying the temperature dependence of equilibrium constants of organic reactions enables the utilization of organic maturity parameters as relative geothermometers at temperatures higher than the nominal limits of the oil window.

  5. Electrochemistry in aqueous solution at high temperature and under pressure: study of nickel in a highly alkaline environment

    International Nuclear Information System (INIS)

    Forestier, Michel

    1981-01-01

    This research thesis reports the study of the corrosion resistance and anodic behaviour of various metals and alloys used in conventional thermal or nuclear power stations, more particularly the case of nickel in a highly alkaline environment (KOH 5 N) which is widely used for hydrogen production by water electrolysis. The author studied the influence of temperature and pressure on the electrochemical behaviour of nickel, and more particularly the first-oxidation kinetics. The report discusses the physicochemical and thermodynamic properties of aqueous systems at high temperature and under pressure, presents the general techniques of high-temperature electrochemistry, describes the experimental installation, and reports the development of a reference electrode which can operate in those experimental conditions. The author reports the study of the electrochemical behaviour of nickel in alkaline environment and at high temperature, reports a surface analysis performed by Auger spectroscopy, electron spectroscopy for chemical analysis or ESCA, and scanning electronic microscopy, reports the study of the electrochemical behaviour of nickel in a potassium hydroxide solution under normal temperature and pressure, but also in acid environment. Results are interpreted with respect to temperature [fr

  6. Pyrolysis temperature and steam activation effects on sorption of phosphate on pine sawdust biochars in aqueous solutions

    Directory of Open Access Journals (Sweden)

    Kangyi Lou

    2016-10-01

    Full Text Available Biochar can be used as an adsorbent for phosphate removal in aquatic environments to treat eutrophication problems. Designing biochars that have large phosphate adsorption capacity through altering pyrolysis conditions and applying activation techniques will improve phosphate removal efficiency. In this study, four pine sawdust biochars were produced at 300 and 550 °C with and without steam activation. Batch sorption experiments including isotherm and kinetic studies were conducted to understand how phosphate removal capabilities and adsorption mechanisms of biochars were affected by pyrolysis temperature and steam activation. Our results showed that the steam activation and pyrolysis temperature did not affect phosphate adsorption by the biochars. The four biochars removed <4% of phosphate from the aqueous solution, which were not affected by the pH of the solution and biochar application rate. The repulsion forces between biochar surfaces and phosphate ions were likely the cause of the low adsorption.

  7. Studies on the Solute Solvent Interaction of Nimesulide in Aqueous Solutions of Hydrotropic Agents at Different Temperatures

    Directory of Open Access Journals (Sweden)

    Chandravir S. Solanki

    2010-01-01

    Full Text Available The present study deals with experiments so as to highlight the solute (drug nimesulide - solvent(water interactions and related modifications in case of the presence of hydrotropic agents at different temperatures T(=298.15 to 313.15K. Density and viscosity values of nimesulide have been determined in water in (0.1, 0.2, 0.4, 0.6, 0.8, 1 and 2 mol dm-3 aqueous solutions of hydrotropic agents (sodium benzoate, sodium salicylate, sodium bromide and nicotinamide at temperatures 298.15, 303.15, 308.15 and 313.15 K where as the solubility was studied at 308.15 K. From the density values, the limiting partial molar volumes and expansibilities have been calculated. The experimental viscosity values have been analyzed in terms of jones-dole equation and on the basis of transition theory for relative viscosity.

  8. Producing Zirconium Diboride Components with Complex, Near-Net Shape Geometries by Aqueous Room-Temperature Injection Molding

    Science.gov (United States)

    Wiesner, Valerie L.; Youngblood, Jeffrey; Trice, Rodney

    2014-01-01

    Room-temperature injection molding is proposed as a novel, low-cost and more energy efficient manufacturing process capable of forming complex-shaped zirconium diboride (ZrB2) parts. This innovative processing method utilized aqueous suspensions with high powder loading and a minimal amount (5 vol.) of water-soluble polyvinylpyrrolidone (PVP), which was used as a viscosity modifier. Rheological characterization was performed to evaluate the room-temperature flow properties of ZrB2-PVP suspensions. ZrB2 specimens were fabricated with high green body strength and were machinable prior to binder removal despite their low polymer content. After binder burnout and pressureless sintering, the bulk density and microstructure of specimens were characterized using Archimedes technique and scanning electron microscopy. X-Ray Diffraction was used to determine the phase compositions present in sintered specimens. Ultimate strength of sintered specimens will be determined using ASTM C1323-10 compressive C-ring test.

  9. Kinetics of hydrolysis of 1-benzoyl-1,2,4-triazole in aqueous solution as a function of temperature near the temperature of maximum density, and the isochoric controversy

    NARCIS (Netherlands)

    Blandamer, MJ; Buurma, NJ; Engberts, JBFN; Reis, JCR; Buurma, Niklaas J.; Reis, João C.R.

    2003-01-01

    At temperatures above and below the temperature of maximum density, TMD, for water at ambient pressure, pairs of temperatures exist at which the molar volumes of water are equal. First-order rate constants for the pH-independent hydrolysis of 1-benzoyl-1,2,4-triazole in aqueous solution at pairs of

  10. Volumetric behaviour of amino acids and their group contributions in aqueous lactose solutions at different temperatures

    International Nuclear Information System (INIS)

    Pal, Amalendu; Chauhan, Nalin

    2011-01-01

    Densities, ρ, for glycine, L-alanine, L-valine, and L-leucine [(0.05 to 0.30) m] in aqueous lactose solutions ranging from pure water to 6 mass% lactose were determined at T = (293.15, 298.15, 303.15, and 308.15) K. The density was used to compute apparent molar volume, V φ , partial molar volume at infinite dilution, V φ o , and experimental slope, S V were obtained and interpreted in terms of solute-solvent and solute-solute interactions. These data were used to calculate the (∂V φ 0 /∂T) P values. The partial molar volume of transfer, ΔV φ 0 from water to aqueous lactose solutions at infinite dilution has also been calculated. In addition to this, the linear correlation of V φ 0 with number of carbon atoms in the alkyl chain of amino acids was utilized to determine the respective contributions of NH 3 + COO - , and CH 2 groups to V φ 0 .

  11. Volumetric behaviour of amino acids and their group contributions in aqueous lactose solutions at different temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Pal, Amalendu, E-mail: palchem@sify.co [Department of Chemistry, Kurukshetra University, Kurukshetra 136 119 (India); Chauhan, Nalin [Department of Chemistry, Kurukshetra University, Kurukshetra 136 119 (India)

    2011-02-15

    Densities, {rho}, for glycine, L-alanine, L-valine, and L-leucine [(0.05 to 0.30) m] in aqueous lactose solutions ranging from pure water to 6 mass% lactose were determined at T = (293.15, 298.15, 303.15, and 308.15) K. The density was used to compute apparent molar volume, V{sub {phi}}, partial molar volume at infinite dilution, V{sub {phi}}{sup o}, and experimental slope, S{sub V} were obtained and interpreted in terms of solute-solvent and solute-solute interactions. These data were used to calculate the ({partial_derivative}V{sub {phi}}{sup 0}/{partial_derivative}T){sub P} values. The partial molar volume of transfer, {Delta}V{sub {phi}}{sup 0} from water to aqueous lactose solutions at infinite dilution has also been calculated. In addition to this, the linear correlation of V{sub {phi}}{sup 0} with number of carbon atoms in the alkyl chain of amino acids was utilized to determine the respective contributions of NH{sub 3}{sup +}COO{sup -}, and CH{sub 2} groups to V{sub {phi}}{sup 0}.

  12. Low-temperature aqueous alteration on the CR chondrite parent body: Implications from in situ oxygen-isotope analyses

    Science.gov (United States)

    Jilly-Rehak, Christine E.; Huss, Gary R.; Nagashima, Kazu; Schrader, Devin L.

    2018-02-01

    The presence of hydrated minerals in chondrites indicates that water played an important role in the geologic evolution of the early Solar System; however, the process of aqueous alteration is still poorly understood. Renazzo-like carbonaceous (CR) chondrites are particularly well-suited for the study of aqueous alteration. Samples range from being nearly anhydrous to fully altered, essentially representing snapshots of the alteration process through time. We studied oxygen isotopes in secondary-minerals from six CR chondrites of varying hydration states to determine how aqueous fluid conditions (including composition and temperature) evolved on the parent body. Secondary minerals analyzed included calcite, dolomite, and magnetite. The O-isotope composition of calcites ranged from δ18O ≈ 9 to 35‰, dolomites from δ18O ≈ 23 to 27‰, and magnetites from δ18O ≈ -18 to 5‰. Calcite in less-altered samples showed more evidence of fluid evolution compared to heavily altered samples, likely reflecting lower water/rock ratios. Most magnetite plotted on a single trend, with the exception of grains from the extensively hydrated chondrite MIL 090292. The MIL 090292 magnetite diverges from this trend, possibly indicating an anomalous origin for the meteorite. If magnetite and calcite formed in equilibrium, then the relative 18O fractionation between them can be used to extract the temperature of co-precipitation. Isotopic fractionation in Al Rais carbonate-magnetite assemblages revealed low precipitation temperatures (∼60 °C). Assuming that the CR parent body experienced closed-system alteration, a similar exercise for parallel calcite and magnetite O-isotope arrays yields "global" alteration temperatures of ∼55 to 88 °C. These secondary mineral arrays indicate that the O-isotopic composition of the altering fluid evolved upon progressive alteration, beginning near the Al Rais water composition of Δ17O ∼ 1‰ and δ18O ∼ 10‰, and becoming increasingly

  13. A unified theory of the thermodynamic properties of aqueous electrolytes to extreme temperatures and pressures.

    Science.gov (United States)

    Djamali, Essmaiil; Cobble, James W

    2009-02-26

    A new theoretical treatment has been developed for predicting the thermodynamic properties of electrolytes up to and beyond the critical temperature of water (973 K and at pressures up to 1000 MPa). The model is based upon the classical Born equation corrected for non-Born hydration effects. The temperature and pressure behavior of electrolytes can now be accurately predicted from existing low temperature data. Only two constants are needed for each electrolyte at all temperatures and pressures, where data exist to test the theory.

  14. Conductometric and volumetric study of copper sulphate in aqueous ethanol solutions at different temperatures

    Directory of Open Access Journals (Sweden)

    Esam A. Gomaa

    2017-09-01

    Full Text Available An Anton Par Model 55 densimeter was used to measure the densities of copper sulphate solutions in H2O and EtOH–H2O at 298.15 K, 303.15 K, 308.15 K, and 313.15 K. The acquired information was used to ascertain the apparent molar volumes, limiting partial molar volumes, and transfer partial molar volumes of copper sulphate. These computed parameters were utilized to decipher the solute–solute and solute–solvent interactions of copper sulphate in an aqueous ethanol solution. The ion solvation behavior of copper sulphate in water and aqueous ethanol over the range of 298.15–313.15 K was studied using the electrical conductivity principle. The Kraus–Bray and Shedlovsky models of conductivity were used to analyze the obtained conductance data. From the obtained data, the limiting molar conductance λ°m, association constant KA, energy of activation of the rating process (Ea, and related thermodynamic parameters were determined. The Walden product (λ°mη0 was determined. The standard thermodynamic parameters of association (ΔG°A, ΔH°A were calculated and discussed. Increased ion–solvent and solvent–solvent interactions are indicated by limiting molar conductance values with an increasing amount of ethanol. The negative ΔG°A values indicate that the association processes in all of the studied systems are spontaneous processes. The negative estimation of (ΔH°A demonstrates that the association processes is exothermic in nature.

  15. Corrosion Study of Mild Steel in Aqueous Sulfuric Acid Solution Using 4-Methyl-4H-1,2,4-Triazole-3-Thiol and 2-Mercaptonicotinic Acid—An Experimental and Theoretical Study

    Directory of Open Access Journals (Sweden)

    Valbonë V. Mehmeti

    2017-08-01

    Full Text Available The corrosion behavior of mild steel in 0.1 M aqueous sulfuric acid medium has been studied using weight loss, potentiodynamic polarization measurements, quantum chemical calculations, and molecular dynamic simulations in the presence and absence of 4-methyl-4H-1,2,4-triazole-3-thiol and 2-mercaptonicotinic acid. Potentiodynamic measurements indicate that these compounds mostly act as mixed inhibitors due to their adsorption on the mild steel surface. The goal of the study was to use theoretical calculations to better understand the inhibition. Monte Carlo simulation was used to calculate the adsorption behavior of the studied molecules onto Fe (1 1 1 and Fe2O3 (1 1 1 surface. The molecules were also studied with the density functional theory (DFT, using the B3LYP functional in order to determine the relationship between the molecular structure and the corrosion inhibition behavior. More accurate adsorption energies between the studied molecules and iron or iron oxide were calculated by using DFT with periodic boundary conditions. The calculated theoretical parameters gave important assistance into the understanding the corrosion inhibition mechanism expressed by the molecules and are in full agreement with the experimental results.

  16. Electrolytic conductivity and molar heat capacity of two aqueous solutions of ionic liquids at room-temperature: Measurements and correlations

    International Nuclear Information System (INIS)

    Lin Peiyin; Soriano, Allan N.; Leron, Rhoda B.; Li Menghui

    2010-01-01

    As part of our systematic study on physicochemical characterization of ionic liquids, in this work, we report new measurements of electrolytic conductivity and molar heat capacity for aqueous solutions of two 1-ethyl-3-methylimidazolium-based ionic liquids, namely: 1-ethyl-3-methylimidazolium dicyanamide and 1-ethyl-3-methylimidazolium 2-(2-methoxyethoxy) ethylsulfate, at normal atmospheric condition and for temperatures up to 353.2 K. The electrolytic conductivity and molar heat capacity were measured by a commercial conductivity meter and a differential scanning calorimeter (DSC), respectively. The estimated experimental uncertainties for the electrolytic conductivity and molar heat capacity measurements were ±1% and ±2%, respectively. The property data are reported as functions of temperature and composition. A modified empirical equation from another researcher was used to correlate the temperature and composition dependence of the our electrolytic conductivity results. An excess molar heat capacity expression derived using a Redlich-Kister type equation was used to represent the temperature and composition dependence of the measured molar heat capacity and calculated excess molar heat capacity of the solvent systems considered. The correlations applied represent the our measurements satisfactorily as shown by an acceptable overall average deviation of 6.4% and 0.1%, respectively, for electrolytic conductivity and molar heat capacity.

  17. Amino acid behavior in aqueous amide solutions: Temperature dependence of the L-phenylalanine–N,N-dimethylformamide interaction

    International Nuclear Information System (INIS)

    Kustov, Andrey V.

    2013-01-01

    Highlights: • Thermodynamics of amino acid solvation in aqueous DMF solutions was studied at 288–318 K. • The pair interaction parameters were compared with those for urea solutions. • For hydrophobic solutes enthalpies and entropies of interaction reveal strong temperature changes. • The relationship between the temperature dependence of solvation and solute–solute interactions was found. - Abstract: We have studied thermodynamics of the L-phenylalanine (Phe) pair interaction with denaturing agents – urea (U) and dimethylformamide (DMF) at 288–318 K. Our study does indicate that enthalpies and entropies of the Phe–U interaction reveal the anomalous temperature dependence which does not occur for DMF solutions. The anomalous Phe behavior in U solutions appears to be closely related to peculiarities of U hydration. One more result is in the fact that for hydrophobic solutes such as L-phenylalanine and substituted amides it is not justified to use the results obtained at 298 K for predicting the solute behavior at physiological temperatures

  18. An effective route for the room temperature formation of Pd coatings on multiwalled carbon nanotubes in aqueous solutions

    Energy Technology Data Exchange (ETDEWEB)

    Kim, Yeong Joon [Dept. of Chemistry, Chungnam National University, Daejeon (Korea, Republic of); Lee, Im Kyu; Song, Jae Hee [Dept. of Chemistry, Sunc hon National University, Suncheon (Korea, Republic of)

    2016-10-15

    We present an easy one-pot synthesis route for the production of palladium nanoparticles and multiwalled carbon nanotubes (MWCNTs)-supported Pd-nanomaterial composites by a simple proton beam irradiation process in an aqueous solution at room temperature. Pristine and surface-modified MWCNTs were used to prepare MWCNT–Pd hybrids. Pd nanoparticles on the surfaces of MWCNTs were produced in situ in an aqueous solution without the addition of any harsh reducing agent. Pristine and thiolated MWCNTs were both densely decorated with spherical Pd nanoparticles and eventually Pd nanowire formation on MWCNTs was realized when reaction times exceeded 60 min. The thicknesses of Pd coatings on MWCNT surfaces were controlled by varying the concentration of MWCNTs in the reaction mixture. MWCNT-Pd composites were characterized by time-resolved transmission electron microscopy, selected area electron diffraction, and energy dispersive X-ray spectroscopy, and the results obtained showed that Pd coatings were continuous, and resulted in a MWCNT-supported Pd nanowire structure.

  19. Behavior of sulfur during coal pyrolysis

    Science.gov (United States)

    Shao, D.; Hutchinson, E.J.; Heidbrink, J.; Pan, W.-P.; Chou, C.-L.

    1994-01-01

    The behavior of sulfur in Illinois coals during pyrolysis was evaluated by thermogravimetry/ Fourier transform-infrared spectroscopy (TG/FT-IR) techniques. SO2, COS, and H2S were major gaseous sulfur-containing products observed during coal pyrolysis. The release rates of the gaseous sulfur species showed several peaks within the temperature ranges, which were due to the emission of different forms of sulfur in coal. ?? 1994.

  20. Effects of surface nanocrystallization pretreatment on low-temperature ion sulfurization behavior of 1Cr18Ni9Ti stainless steel

    International Nuclear Information System (INIS)

    Ma Guozheng; Xu Binshi; Wang Haidou; Si Hongjuan

    2010-01-01

    A nanocrystalline surface layer of 10 μm thickness was fabricated on 1Cr18Ni9Ti stainless steel by means of supersonic fine particles bombarding (SFPB). The followed low-temperature ion sulfurizing was carried out on the original and the SFPBed (SFPB treated) surface, respectively, forming sulfide layers with certain thickness. X-ray diffraction (XRD) and transmission electron microscopy (TEM) were employed to analyze the phase constituents and grain size of the nanocrystallized surface layer. The surface morphologies and compositions of the sulfide layers were examined by scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS). X-ray photoelectron spectroscope (XPS) was used to detect the valence states of the sulfide layers. Elemental distribution with depth was measured by Auger energy spectroscopy (AES). The results show that the microstructure of the surface layer is refined to nano-grains with the grain size about 30 nm and random crystallographic orientations by SFPB treatment. The surface nanocrystallization pretreatment can significantly improve the thickness, density, and the FeS content ratio of the sulfide layers. The analysis indicates that, the enhancement in efficiency of the ion sulfurization treatment by SFPB surface nanocrystallization treatment is mainly attributed to the high-density crystal defects and the increase of surface chemical activity.

  1. Measurements of liquid film thickness, concentration, and temperature of aqueous urea solution by NIR absorption spectroscopy

    Science.gov (United States)

    Pan, R.; Jeffries, J. B.; Dreier, T.; Schulz, C.

    2016-01-01

    A multi-wavelength near-infrared (NIR) diode laser absorption sensor has been developed and demonstrated for real-time monitoring of the thickness, solute concentration, and temperature of thin films of urea-water solutions. The sensor monitors the transmittance of three near-infrared diode lasers through the thin liquid film. Film thickness, urea mass fraction, and liquid temperature were determined from measured transmittance ratios of suitable combinations of lasers. Available laser wavelengths were selected depending on the variation of the NIR absorption spectrum of the solution with temperature and solute concentration. The spectral database was measured by a Fourier transform infrared spectrometer in the range 5500-8000 cm-1 for urea solutions between 5 and 40 wt% and temperatures between 298 and 338 K. A prototype sensor was constructed, and the sensor concept was first validated with measurements using a calibration cell providing liquid layers of variable thickness (200-1500 µm), urea mass fraction (5-40 wt%) and temperature (298-318 K). Temporal variations of film thickness and urea concentration were captured during the constant-temperature evaporation of a liquid film deposited on an optically polished heated quartz flat.

  2. Optimization of on-line hydrogen stable isotope ratio measurements of halogen- and sulfur-bearing organic compounds using elemental analyzer–chromium/high-temperature conversion isotope ratio mass spectrometry (EA-Cr/HTC-IRMS)

    Science.gov (United States)

    Gehre, Matthias; Renpenning, Julian; Geilmann, Heike; Qi, Haiping; Coplen, Tyler B.; Kümmel, Steffen; Ivdra, Natalija; Brand, Willi A.; Schimmelmann, Arndt

    2017-01-01

    Rationale: Accurate hydrogen isotopic analysis of halogen- and sulfur-bearing organics has not been possible with traditional high-temperature conversion (HTC) because the formation of hydrogen-bearing reaction products other than molecular hydrogen (H2) is responsible for non-quantitative H2 yields and possible hydrogen isotopic fractionation. Our previously introduced, new chromium-based EA-Cr/HTC-IRMS (Elemental Analyzer–Chromium/High-Temperature Conversion Isotope Ratio Mass Spectrometry) technique focused primarily on nitrogen-bearing compounds. Several technical and analytical issues concerning halogen- and sulfur-bearing samples, however, remained unresolved and required further refinement of the reactor systems.

  3. Protein remains stable at unusually high temperatures when solvated in aqueous mixtures of amino acid based ionic liquids

    DEFF Research Database (Denmark)

    Chevrot, Guillaume; Fileti, Eudes Eterno; Chaban, Vitaly V.

    2016-01-01

    Using molecular dynamics simulations, we investigated the thermal stability and real-time denaturation of a model mini-protein in four solvents: (1) water, (2) 1-ethyl-3-methylimidazolium alaninate [EMIM][ALA] (5 mol% in water), (3) methioninate [EMIM][MET] (5 mol% in water), and (4) tryptophanate...... [EMIM][TRP] (5 mol% in water). Upon analyzing the radius of gyration, the solvent-accessible surface area, root-mean-squared deviations, and inter- and intramolecular hydrogen bonds, we found that the mini-protein remains stable at 30–40 K higher temperatures in aqueous amino acid based ionic liquids...... (AAILs) than in water. This thermal stability was correlated with the thermodynamics and shear viscosity of the AAIL-containing mixtures. These results suggest that AAILs are generally favorable for protein conservation. [Figure not available: see fulltext.]...

  4. Controllable synthesis of spindle-like ZnO nanostructures by a simple low-temperature aqueous solution route

    Energy Technology Data Exchange (ETDEWEB)

    Lu Hongxia, E-mail: luhx@zzu.edu.cn [School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001 (China); Zhao Yunlong; Yu Xiujun; Chen Deliang [School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001 (China); Zhang Liwei [School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001 (China); Xinxiang University, Xinxiang 453003 (China); Xu Hongliang; Yang Daoyuan; Wang Hailong [School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001 (China); Zhang Rui [School of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001 (China); Zhengzhou Institute of Aeronautical Industry Management, Zhengzhou 450005 (China)

    2011-02-15

    Spindle-like ZnO nanostructures were successfully synthesized through direct precipitation of zinc acetate aqueous solution at 60 deg. C. Phase structure, morphology and microstructure of the products were investigated by X-ray diffraction, TG-DTA, FTIR and field emission scanning electron microscopy (FESEM). Result showed that hexagonal wurtzite structure ZnO nanostructures with about 100 nm in diameter and 100-200 nm in length were obtained. HMTA acted as a soft template in the process and played an important role in the formation of spindle-like ZnO nanostructures. Meanwhile, different morphologies were also obtained by altering synthetic temperature, additional agents and the ratios of Zn{sup 2+}/OH{sup -}. Possible mechanism for the variations of morphology with synthesis parameters was also discussed in this paper.

  5. A Flow-Through High-Pressure Electrical Conductance Cell for Determining of Ion Association of Aqueous Electrolyte Solutions at High Temperature and Pressure

    Energy Technology Data Exchange (ETDEWEB)

    Bianchi, H.; Ho, P.C.; Palmer, D.A.; Wood, R.H.

    1999-09-12

    A flow-through high-pressure electrical conductance cell was designed and constructed to measure limiting molar conductances and ion association constants of dilute aqueous solutions with high precision at high temperatures and pressures. The basic concept of the cell employs the principle developed at the University of Delaware in 1995, but overall targets higher temperatures (to 600 C) and pressures (to 300 MPa). At present the cell has been tested by measuring aqueous NaCl and LiOH solutions (10{sup {minus}3} to 10{sup {minus}5} mol.kg{sup {minus}1}) to 405 C and 33 MPa with good results.

  6. Calcium isotope fractionation between aqueous compounds relevant to low-temperature geochemistry, biology and medicine

    Science.gov (United States)

    Moynier, Frédéric; Fujii, Toshiyuki

    2017-03-01

    Stable Ca isotopes are fractionated between bones, urine and blood of animals and between soils, roots and leaves of plants by >1000 ppm for the 44Ca/40Ca ratio. These isotopic variations have important implications to understand Ca transport and fluxes in living organisms; however, the mechanisms of isotopic fractionation are unclear. Here we present ab initio calculations for the isotopic fractionation between various aqueous species of Ca and show that this fractionation can be up to 3000 ppm. We show that the Ca isotopic fractionation between soil solutions and plant roots can be explained by the difference of isotopic fractionation between the different first shell hydration degree of Ca2+ and that the isotopic fractionation between roots and leaves is controlled by the precipitation of Ca-oxalates. The isotopic fractionation between blood and urine is due to the complexation of heavy Ca with citrate and oxalates in urine. Calculations are presented for additional Ca species that may be useful to interpret future Ca isotopic measurements.

  7. Electrical double layer modulation of hybrid room temperature ionic liquid/aqueous buffer interface for enhanced sweat based biosensing.

    Science.gov (United States)

    Jagannath, Badrinath; Muthukumar, Sriram; Prasad, Shalini

    2018-08-03

    We have investigated the role of kosmotropic anionic moieties and chaotropic cationic moieties of room temperature hydrophilic ionic liquids in enhancing the biosensing performance of affinity based immunochemical biosensors in human sweat. Two ionic liquids, 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM[BF 4 ]) and choline dihydrogen phosphate (Choline[DHP]) were investigated in this study with Choline[DHP] being more kosmotropic in nature having a more protein stabilizing effect based on the hofmeister series. Non-faradaic interfacial charge transfer has been employed as the mechanism for evaluating the formation and the biosensing of capture probe antibodies in room temperature ionic liquids (RTILs)/aqueous human sweat interface. The charge of the ionic moieties were utilized to form compact electrical double layers around the antibodies for enhancing the stability of the antibody capture probes, which was evaluated through zeta potential measurements. The zeta potential measurements indicated stability of antibodies due to electrostatic repulsion of the RTIL charged moieties encompassing the antibodies, thus preventing any aggregation. Here, we report for the first time of non-faradaic electrochemical impedance spectroscopy equivalent circuit model analysis for analyzing and interpreting affinity based biosensing at hybrid electrode/ionic liquid-aqueous sweat buffer interface guided by the choice of the ionic liquid. Interleukin-6 (IL-6) and cortisol two commonly occurring biomarkers in human sweat were evaluated using this method. The limit of detection (LOD) obtained using both ionic liquids for IL-6 was 0.2 pg mL -1 with cross-reactivity studies indicating better performance of IL-6 detection using Choline[DHP] and no response to cross-reactive molecule. The LOD of 0.1 ng/mL was achieved for cortisol and the cross-reactivity studies indicated that cortisol antibody in BMIM[BF 4 ] did not show any signal response to cross-reactive molecules

  8. Effect of temperature on sequestration of Cu (II) from aqueous solution onto turmeric powder

    International Nuclear Information System (INIS)

    Qayoom, A.

    2010-01-01

    In this work effect of temperature on adsorption of Cu(II) onto turmeric powder was investigated in order to understand sequestrating behavior of turmeric powder. Langmuir, Freundlich and D-R equilibrium models were employed and changes in equilibrium parameters with changing temperature have been discussed. Various thermodynamic parameters such as delta H, delta G and delta S have been calculated. It was found that with increase in temperature maximum adsorption capacities of Cu(II) increase which showed that the adsorption of Cu(II) onto turmeric powder is endothermic. delta H and Ea values also confirmed the same trend. Entropy values showed increased in randomness with increasing temperature. Gibbs free energies were non spontaneous at all the temperatures studied. E values were in the range of 2.89-3.53 KJmol /sup -1/, which indicated that adsorption is essentially of physical nature. The value of S is much less than 1 indicating favourable sticking of adsorbate to adsorbent with physiosorption mechanism predominant. (author)

  9. SULFUR POLYMER ENCAPSULATION.

    Energy Technology Data Exchange (ETDEWEB)

    KALB, P.

    2001-08-22

    Sulfur polymer cement (SPC) is a thermoplastic polymer consisting of 95 wt% elemental sulfur and 5 wt% organic modifiers to enhance long-term durability. SPC was originally developed by the U.S. Bureau of Mines as an alternative to hydraulic cement for construction applications. Previous attempts to use elemental sulfur as a construction material in the chemical industry failed due to premature degradation. These failures were caused by the internal stresses that result from changes in crystalline structure upon cooling of the material. By reacting elemental sulfur with organic polymers, the Bureau of Mines developed a product that successfully suppresses the solid phase transition and significantly improves the stability of the product. SPC, originally named modified sulfur cement, is produced from readily available, inexpensive waste sulfur derived from desulfurization of both flue gases and petroleum. The commercial production of SPC is licensed in the United States by Martin Resources (Odessa, Texas) and is marketed under the trade name Chement 2000. It is sold in granular form and is relatively inexpensive ({approx}$0.10 to 0.12/lb). Application of SPC for the treatment of radioactive, hazardous, and mixed wastes was initially developed and patented by Brookhaven National Laboratory (BNL) in the mid-1980s (Kalb and Colombo, 1985; Colombo et al., 1997). The process was subsequently investigated by the Commission of the European Communities (Van Dalen and Rijpkema, 1989), Idaho National Engineering Laboratory (Darnell, 1991), and Oak Ridge National Laboratory (Mattus and Mattus, 1994). SPC has been used primarily in microencapsulation applications but can also be used for macroencapsulation of waste. SPC microencapsulation has been demonstrated to be an effective treatment for a wide variety of wastes, including incinerator hearth and fly ash; aqueous concentrates such as sulfates, borates, and chlorides; blowdown solutions; soils; and sludges. It is not

  10. Aqueous solutions of calcium ions: hydration numbers and the effect of temperature.

    Science.gov (United States)

    Zavitsas, Andreas A

    2005-11-03

    Hydration numbers of calcium ions are determined from extensive measurements of colligative properties of water solutions of calcium salts. The hydration numbers reported refer to the average number of water molecules that are bound sufficiently strongly to calcium ions so as to be removed from the solvent and become part of the solute. Contrary to common descriptions of deviations from ideal behavior for concentrated solutions, ideal behavior is demonstrated when mole fractions are calculated by taking account of such bound water. Measurements over wide concentration and temperature ranges are used to obtain the effect of temperature on the average hydration number of Ca(2+). Freezing point depression measurements yield a hydration number of 12.0 +/- 0.8. Boiling point elevations yield 6.7 +/- 0.6. Consistent with this, vapor pressure measurements from 0 to 200 degrees C show a gradual decrease in hydration number with increasing temperature, with a value of 5.0 at 200 degrees C.

  11. Ion pair formation in copper sulfate aqueous solutions at high temperatures

    International Nuclear Information System (INIS)

    Mendez De Leo, Lucila P.; Bianchi, Hugo L.; Fernandez-Prini, Roberto

    2005-01-01

    Ionic association between Cu 2+ (aq) and SO42-(aq) has been studied in the temperature range (298 to 473) K using a spectrophotometric technique. Experiments were designed to minimize the contribution of other protolytic equilibria in solution. The values of the ionic association equilibrium constant at different temperatures and pressures were fitted to an appropriate equation that allows the calculation of the thermodynamic quantities for states close to the saturation line. Using Bjerrum's model for ionic association evidence for two ion pair populations was obtained. The process of ion pairing is discussed and a possibility to reconcile the continuum model (Bjerrum) with molecular simulation results is suggested

  12. Low temperature aqueous living/controlled (RAFT) polymerization of carboxybetaine methacrylamide up to high molecular weights

    Czech Academy of Sciences Publication Activity Database

    Rodriguez-Emmenegger, Cesar Adolfo; Schmidt, B. V. K. J.; Sedláková, Zdeňka; Šubr, Vladimír; Bologna Alles, A.; Brynda, Eduard; Barner-Kowollik, C.

    2011-01-01

    Roč. 32, č. 13 (2011), s. 958-965 ISSN 1022-1336 R&D Projects: GA AV ČR KAN200670701; GA AV ČR IAAX00500803 Institutional research plan: CEZ:AV0Z40500505 Keywords : biofouling * carboxybetaine methacrylamide * low temperature polymerization Subject RIV: CD - Macromolecular Chemistry Impact factor: 4.596, year: 2011

  13. On-line monitoring of resistance of aqueous solutions at high temperature

    International Nuclear Information System (INIS)

    Hu Shilin; Zhang Pingzhu; Shang Weiguo

    1999-01-01

    The coulostatic measurement is a fast speed electrochemical test method. By this technology, analyzing Δ E(t)- T curves recorded under coulostatic perturbation, the solution resistance R l , resistance of coated film R f , capacity of coated film C f , Polarization resistance R p and double layer capacity C d are obtained. The resistance variety of 0.05N KCl is measured from room temperature up to 255 deg. C under saturation steam pressure. (author)

  14. Corrosion rate of copper in aqueous lithium bromide concentrated solutions at room temperature by immersion tests

    Energy Technology Data Exchange (ETDEWEB)

    Munoz-Portero, M.J.; Garcia-Anton, J.; Guinon-Segura, J.L.; Perez-Herranz, V. [Departamento de Ingenieria Quimica y Nuclear, E.T.S.I. Industriales, Universidad Politecnica de Valencia, P.O. Box 22012, E-46071 Valencia (Spain)

    2004-07-01

    Concentrated solutions of lithium bromide (LiBr) are widely used in absorption refrigeration and heating systems. However, LiBr solutions can cause serious corrosion problems in structural materials (copper, steels, and other metals) in an absorption plant. The aim of the present work was the study of the corrosion rate of copper in 400 and 700 g/L (4.61 and 8.06 M) LiBr solutions pre-nitrogenous or pre-oxygenated at room temperature by immersion tests. The corroded copper concentration was determined with two techniques: weight-loss method and polarographic method. The corrosion curves of copper in LiBr solutions at room temperature as a function of the exposure time showed a similar tendency, and were fitted to a power function such as: C = kt{sup b}, where C was the corroded copper quantity per unit area (mg/cm{sup 2}), t was the exposure time (h), k was the corrosion coefficient, and b was the time exponent. From the corrosion coefficient values (k) it was deduced that the corrosion rate of copper in LiBr solutions at room temperature followed the order: 400 g/L (bubble of O{sub 2}) > 400 g/L (bubble of N{sub 2}) > 700 g/L (bubble of O{sub 2}) > 700 g/L (bubble of N{sub 2}). (authors)

  15. Structural and interactional behaviour of aqueous mixture of room temperature ionic liquid; 2-hydroxyethyl-trimethylammonium L-lactate

    International Nuclear Information System (INIS)

    Chaudhary, Ganga Ram; Bansal, Shafila; Mehta, S.K.; Ahluwalia, A.S.

    2014-01-01

    Highlights: • Thermophysical and spectroscopic properties of aqueous mixtures 2-[HE3MA]LAC have been measured. • Effect of temperature on thermophysical properties has also been studied. • Stronger intermolecular have been observed between [HE3MA]LAC and H 2 O. • Magnitude of interactions decreases with the rise in temperature. • Spectroscopic studies shows interactions between -N + -(CH 3 ) 3 with -OH - group and COO − with -H + of IL and H 2 O. - Abstract: In order to understand the molecular interactions between the green solvent system, (water + lactate based ionic liquid); 2-hydroxyethyl-trimethylammonium L-lactate ([(C 2 H 4 OH)(CH 3 ) 3 N][Lactate]), the thermophysical properties viz. density ρ, speed of sound u, specific conductivity κ, refractive index n D and spectroscopic properties viz. IR, 1 H and 13 C NMR have been investigated over the whole composition range at atmospheric pressure with temperature varied from (293.15 to 323.15) K. To gain more insight of intermolecular interactions occurring in the aqueous mixture of [(C 2 H 4 OH)(CH 3 ) 3 N][Lactate], intermolecular free length L f , acoustic impedance Z, relative association R A , excess molar volume V E , deviations in isentropic compressibility ΔK S , partial molar excess volume V i E , partial molar deviations in isentropic compressibility ΔK S,i , deviation in specific conductivity Δκ and deviation in refractive index Δn D have been predicted as a function of IL concentration over the whole composition range. These results have been fitted to the Redlich–Kister polynomial. A large deviation from ideality has been observed on mixing water and [(C 2 H 4 OH)(CH 3 ) 3 N][Lactate] which are due to the formation of strong intermolecular hydrogen bonding between the two molecules. Also, it has been noticed that the mixture of water and [(C 2 H 4 OH)(CH 3 ) 3 N][Lactate] became warm that indicates mixing of these two components is exothermic. Thermodynamic and spectroscopic data

  16. The role of the temperature in the morphology and properties of zinc oxide structures obtained by electrosynthesis in aqueous solution

    Energy Technology Data Exchange (ETDEWEB)

    Jaffry, U.; Mazario, E. [Universidad Autónoma de Madrid, Facultad de Ciencias, Departamento de Química Física Aplicada, 28049 Madrid (Spain); Lemus, J. [CICECO – Aveiro Institute of Materials, Chemistry Department, University of Aveiro, 3810-193 Aveiro (Portugal); Rivero, M.; Muñoz-Bonilla, A. [Universidad Autónoma de Madrid, Facultad de Ciencias, Departamento de Química Física Aplicada, 28049 Madrid (Spain); Herrasti, P., E-mail: pilar.herrasti@uam.es [Universidad Autónoma de Madrid, Facultad de Ciencias, Departamento de Química Física Aplicada, 28049 Madrid (Spain)

    2016-09-15

    Herein, ZnO micro and nanostructures were synthesized by an electrochemical method in aqueous solution employing NaCl as the electrolyte. Different parameters influencing the synthesis process, i.e. current intensity, reaction time and temperature, were investigated. From this, it was concluded that the productivity of the reaction increases with longer reaction time, whereas the use of higher current intensity augments the specific energy consumption. On the other hand, the increase in temperature seems to exert a negative effect. The characterization of the resulting materials by scanning electron microscopy, X-ray diffraction and thermogravimetric analysis demonstrated that a mixture of Zn(OH){sub 2} and ZnO crystalline structures is formed directly from the synthesis procedure. The content of Zn(OH){sub 2} phase in the sample decreases as the temperature of the synthesis increases, this fact indicates that the low productivity obtained at higher temperatures is related to the nature of the resulting material. Thermal annealing of the samples containing both phases prepared following synthesis allows the phase transformation from Zn(OH){sub 2} to pure ZnO structures. The band gap energies of the ZnO materials were determined by diffuse reflectance measurements according to the Kubelka Munk theory, revealing low values in all the cases which were highly dependent on the size of crystals within the materials. The photocatalytic properties of the pure ZnO samples post calcination were investigated by the decomposition of an organic dye under UV light irradiation. The results show the beneficial photocatalytic properties of the samples that had undergone calcination, these were superior in comparison to those prepared at room temperature which mainly consisted of Zn(OH){sub 2}. - Highlights: • ZnO micro and nanostructures were synthesized by an electrochemical method. • Increasing the applied current and synthesis temperature augments the specific energy

  17. Solution properties and taste behavior of lactose monohydrate in aqueous ascorbic acid solutions at different temperatures: Volumetric and rheological approach.

    Science.gov (United States)

    Sarkar, Abhijit; Sinha, Biswajit

    2016-11-15

    The densities and viscosities of lactose monohydrate in aqueous ascorbic acid solutions with several molal concentrations m=(0.00-0.08)molkg(-1) of ascorbic acid were determined at T=(298.15-318.15)K and pressure p=101kPa. Using experimental data apparent molar volume (ϕV), standard partial molar volume (ϕV(0)), the slope (SV(∗)), apparent specific volumes (ϕVsp), standard isobaric partial molar expansibility (ϕE(0)) and its temperature dependence [Formula: see text] the viscosity B-coefficient and solvation number (Sn) were determined. Viscosity B-coefficients were further employed to obtain the free energies of activation of viscous flow per mole of the solvents (Δμ1(0≠)) and of the solute (Δμ2(0≠)). Effects of molality, solute structure and temperature and taste behavior were analyzed in terms of solute-solute and solute-solvent interactions; results revealed that the solutions are characterized predominantly by solute-solvent interactions and lactose monohydrate behaves as a long-range structure maker. Copyright © 2016 Elsevier Ltd. All rights reserved.

  18. Calcium and strontium isotope fractionation during precipitation from aqueous solutions as a function of temperature and reaction rate; II. Aragonite

    Science.gov (United States)

    AlKhatib, Mahmoud; Eisenhauer, Anton

    2017-07-01

    In order to study Strontium (Sr) partitioning and isotope fractionation of Sr and Calcium (Ca) in aragonite we performed precipitation experiments decoupling temperature and precipitation rates (R∗, μmol/m2 h) in the interval of about 2.3-4.5 μmol/m2 h. Aragonite is the only pure solid phase precipitated from a stirred solutions exposed to an atmosphere of NH3 and CO2 gases throughout the spontaneous decomposition of (NH4)2CO3. The order of reaction with respect to Ca ions is one and independent of temperature. However, the order of reaction with respect to the dissolved inorganic carbon (DIC) is temperature dependent and decreases from three via two to one as temperature increases from 12.5 and 25.0 to 37.5 °C, respectively. Strontium distribution coefficient (DSr) increases with decreasing temperature. However, R∗ responds differently depending on the initial Sr/Ca concentration and temperature: at 37.5 °C DSr increase as a function of increasing R∗ but decrease for 12.5 and 25 °C. Not seen at 12.5 and 37.5 °C but at 25 °C the DSr-R∗ gradient is also changing sign depending on the initial Sr/Ca ratio. Magnesium (Mg) adsorption coefficient between aragonite and aqueous solution (DMg) decreases with temperature but increases with R∗ in the range of 2.4-3.8 μmol/m2 h. Strontium isotope fractionation (Δ88/86Sraragonite-aq) follows the kinetic type of fractionation and become increasingly negative as a function of R∗ for all temperatures. In contrast Ca isotope fractionation (Δ44/40Caaragonite-aq) shows a different behavior than the Sr isotopes. At low temperatures (12.5 and 25 °C) Ca isotope fractionation (Δ44/40Caaragonite-aq) becomes positive as a function of R∗. In contrast, at 37.5 °C and as a function of increasing R∗ the Δ44/40Caaragonite-aq show a Sr type like behavior and becomes increasingly negative. Concerning both the discrepant behavior of DSr as a function of temperature as well as for the Ca isotope fractionation as a

  19. Sulfur cycle

    Digital Repository Service at National Institute of Oceanography (India)

    LokaBharathi, P.A.

    energy. At the end of the anaerobic food chain in bacteria they serve to purify the system of sulfide and other metabolic end products. In the process sulfur is returned to the system as sulfate. In transition zones from anaerobic to aerobic...

  20. Combined Effect of Temperature and pKa on the Kinetics of Absorption of Carbon Dioxide in Aqueous Alkanolamine and Carbonate Solutions with Carbonic Anhydrase

    NARCIS (Netherlands)

    Penders-Van Elk, Nathalie J M C; Oversteegen, S. Martijn; Versteeg, Geert F.

    2016-01-01

    In present work the absorption of carbon dioxide in aqueous N-methyldiethanolamine, N,N-dimethylethanolamine, and triisopropanolamine solutions with and without the enzyme carbonic anhydrase has been studied in a stirred cell reactor at temperatures varying between 278 and 313 K, at an alkanolamine

  1. Numerical investigations of the aperture size effect for maintaining a constant temperature in a novel sulfur-ammonia water splitting cycle application

    Directory of Open Access Journals (Sweden)

    Sarwar Jawad

    2017-01-01

    Full Text Available Solar-driven thermochemical water splitting cycle is a promising, energy efficient and environmentally friendly approach to produce hydrogen. In this paper, numerical work has been undertaken using a cylindrical solar receiver to investigate fixed and variable aperture sizes to maintain constant steady-state temperature over a day for thermochemical part of a novel hybrid photo-thermochemical sulfur-ammonia cycle. A previously developed and validated optical model in commercial software, TracePro® is used to simulate the light sources of 10, 15, and 28 kW. The sunlight intensity variations for the designated reference day for this study is selected as July 1, 2011, at 39.74 N, 105.18 W and at an elevation of 1829 m. A developed and validated finite volume based coupled Monte Carlo, Heat Transfer model is used to calculate the steady-state temperatures in the receiver by utilizing the output of the optical model. The simulations are performed at different aperture diameters from 2 to 14 cm to quantify the effect of fixed aperture size on the steady-state temperatures of the receiver. Furthermore, simulations to maintain steady-state temperatures of 673, 823, and 1123 K for different sub-cycles of the selected cycle via variable aperture has been performed and compared with selected fixed apertures. It is found that the variable apertures can maintain desired constant temperatures over the day for each thermochemical sub-cycle. The comparison of overall power consumption and savings for fixed and variable apertures has also been investigated and reported.

  2. High-performance zno transistors processed via an aqueous carbon-free metal oxide precursor route at temperatures between 80-180 °c

    KAUST Repository

    Lin, Yenhung

    2013-06-25

    An aqueous and carbon-free metal-oxide precursor route is used in combination with a UV irradiation-assisted low-temperature conversion method to fabricate low-voltage ZnO transistors with electron mobilities exceeding 10 cm2/Vs at temperatures <180°C. Because of its low temperature requirements the method allows processing of high-performance transistors onto temperature sensitive substrates such as plastic. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Water and temperature stresses impact canola (Brassica napus L.) fatty acid, protein and yield over nitrogen and sulfur

    Science.gov (United States)

    Interactive effects of weather and soil nutrient status often control crop productivity. An experiment was conducted to determine effects of N and S fertilizer rate, soil water, and atmospheric temperature on canola fatty acid (FA), total oil, protein and grain yield. Nitrogen and S were assessed in...

  4. Sulfur and Water Resistance of Mn-Based Catalysts for Low-Temperature Selective Catalytic Reduction of NOx: A Review

    Directory of Open Access Journals (Sweden)

    Chen Gao

    2018-01-01

    Full Text Available Selective catalytic reduction (SCR with NH3 is the most efficient and economic flue gas denitrification technology developed to date. Due to its high low-temperature catalytic activity, Mn-based catalysts present a great prospect for application in SCR de-NOx at low temperatures. However, overcoming the poor resistance of Mn-based catalysts to H2O and SO2 poison is still a challenge. This paper reviews the recent progress on the H2O and SO2 resistance of Mn-based catalysts for the low-temperature SCR of NOx. Firstly, the poison mechanisms of H2O and SO2 are introduced in detail, respectively. Secondly, Mn-based catalysts are divided into three categories—single MnOx catalysts, Mn-based multi-metal oxide catalysts, and Mn-based supported catalysts—to review the research progress of Mn-based catalysts for H2O and SO2 resistance. Thirdly, several strategies to reduce the poisonous effects of H2O and SO2, such as metal modification, proper support, the combination of metal modification and support, the rational design of structure and morphology, are summarized. Finally, perspectives and future directions of Mn-based catalysts for the low-temperature SCR of NOx are proposed.

  5. Effect of sodium phosphate salts on the thermodynamic properties of aqueous solutions of poly(ethylene oxide) 6000 at different temperatures

    International Nuclear Information System (INIS)

    Sadeghi, Rahmat; Hosseini, Rahim; Jamehbozorg, Bahman

    2008-01-01

    Precise density, sound velocity, water activity, and phase diagram measurements have been carried out on polyethylene oxide (PEO) in aqueous solutions of sodium di-hydrogen phosphate, di-sodium hydrogen phosphate, and tri-sodium phosphate over a range of temperatures at atmospheric pressure. The experimental density and sound velocity data are used to calculate the apparent specific volume and isentropic compressibility as a function of temperature and concentration. It was found that both of the apparent specific volume and isentropic compressibility of PEO in aqueous solutions increase by increasing temperature and charge on the anion of electrolytes. The results show that the slope of constant water activity lines increased with increasing the temperature and charge on the anion of electrolytes and the vapour pressure depression for an aqueous (PEO + sodium phosphate) system is more than the sum of those for the corresponding binary solutions. Furthermore, the effect of temperature and type of anion of salt on the salting-out effect of polyethylene oxide by sodium phosphate salts has been studied

  6. Effect of sodium phosphate salts on the thermodynamic properties of aqueous solutions of poly(ethylene oxide) 6000 at different temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Sadeghi, Rahmat [Department of Chemistry, University of Kurdistan, Sanandaj (Iran, Islamic Republic of)], E-mail: rahsadeghi@yahoo.com; Hosseini, Rahim; Jamehbozorg, Bahman [Department of Chemistry, University of Kurdistan, Sanandaj (Iran, Islamic Republic of)

    2008-09-15

    Precise density, sound velocity, water activity, and phase diagram measurements have been carried out on polyethylene oxide (PEO) in aqueous solutions of sodium di-hydrogen phosphate, di-sodium hydrogen phosphate, and tri-sodium phosphate over a range of temperatures at atmospheric pressure. The experimental density and sound velocity data are used to calculate the apparent specific volume and isentropic compressibility as a function of temperature and concentration. It was found that both of the apparent specific volume and isentropic compressibility of PEO in aqueous solutions increase by increasing temperature and charge on the anion of electrolytes. The results show that the slope of constant water activity lines increased with increasing the temperature and charge on the anion of electrolytes and the vapour pressure depression for an aqueous (PEO + sodium phosphate) system is more than the sum of those for the corresponding binary solutions. Furthermore, the effect of temperature and type of anion of salt on the salting-out effect of polyethylene oxide by sodium phosphate salts has been studied.

  7. Structural Evolution of Molybdenum Carbides in Hot Aqueous Environments and Impact on Low-Temperature Hydroprocessing of Acetic Acid

    Directory of Open Access Journals (Sweden)

    Jae-Soon Choi

    2015-03-01

    Full Text Available We investigated the structural evolution of molybdenum carbides subjected to hot aqueous environments and their catalytic performance in low-temperature hydroprocessing of acetic acid. While bulk structures of Mo carbides were maintained after aging in hot liquid water, a portion of carbidic Mo sites were converted to oxidic sites. Water aging also induced changes to the non-carbidic carbon deposited during carbide synthesis and increased surface roughness, which in turn affected carbide pore volume and surface area. The extent of these structural changes was sensitive to the initial carbide structure and was lower under actual hydroprocessing conditions indicating the possibility of further improving the hydrothermal stability of Mo carbides by optimizing catalyst structure and operating conditions. Mo carbides were active in acetic acid conversion in the presence of liquid water, their activity being comparable to that of Ru/C. The results suggest that effective and inexpensive bio-oil hydroprocessing catalysts could be designed based on Mo carbides, although a more detailed understanding of the structure-performance relationships is needed, especially in upgrading of more complex reaction mixtures or real bio-oils.

  8. Poisson-Fermi modeling of ion activities in aqueous single and mixed electrolyte solutions at variable temperature

    Science.gov (United States)

    Liu, Jinn-Liang; Eisenberg, Bob

    2018-02-01

    The combinatorial explosion of empirical parameters in tens of thousands presents a tremendous challenge for extended Debye-Hückel models to calculate activity coefficients of aqueous mixtures of the most important salts in chemistry. The explosion of parameters originates from the phenomenological extension of the Debye-Hückel theory that does not take steric and correlation effects of ions and water into account. By contrast, the Poisson-Fermi theory developed in recent years treats ions and water molecules as nonuniform hard spheres of any size with interstitial voids and includes ion-water and ion-ion correlations. We present a Poisson-Fermi model and numerical methods for calculating the individual or mean activity coefficient of electrolyte solutions with any arbitrary number of ionic species in a large range of salt concentrations and temperatures. For each activity-concentration curve, we show that the Poisson-Fermi model requires only three unchanging parameters at most to well fit the corresponding experimental data. The three parameters are associated with the Born radius of the solvation energy of an ion in electrolyte solution that changes with salt concentrations in a highly nonlinear manner.

  9. Inverted Organic Solar Cells with Low-Temperature Al-Doped-ZnO Electron Transport Layer Processed from Aqueous Solution

    Directory of Open Access Journals (Sweden)

    Qianni Zhang

    2018-01-01

    Full Text Available The aqueous-based Zn-ammine complex solutions represent one of the most promising routes to obtain the ZnO electron transport layer (ETL at a low temperature in inverted organic solar cells (OSCs. However, to dope the ZnO film processed from the Zn-ammine complex solutions is difficult since the introduction of metal ions into the Zn-ammine complex is a nontrivial process as ammonium hydroxide tends to precipitate metal salts due to acid-base neutralization reactions. In this paper, we investigate the inverted OSCs with Al-doped-ZnO ETL made by immersion of metallic Al into the Zn-ammine precursor solution. The effects of ZnO layer with different immersion time of Al on film properties and solar cell performance have been studied. The results show that, with the Al-doped-ZnO ETL, an improvement of the device performance could be obtained compared with the device with the un-doped ZnO ETL. The improved device performance is attributed to the enhancement of charge carrier mobility leading to a decreased charge carrier recombination and improved charge collection efficiency. The fabricated thin film transistors with the same ZnO or AZO films confirm the improved electrical characteristics of the Al doped ZnO film.

  10. Determination of butyltin species in natural waters using aqueous phase ethylation and off-line room temperature trapping

    Energy Technology Data Exchange (ETDEWEB)

    Bowles, Karl C.; Apte, Simon C.; Hales, Leigh T

    2003-01-27

    Monobutyltin (MBT), dibutyltin (DBT) and tributyltin (TBT) were determined in natural water samples by aqueous phase ethylation with sodium tetraethylborate (STEB), room temperature trapping of the resulting volatile derivatives on Tenax TA[reg], followed by gas chromatography-quartz furnace atomic absorption spectrometry (GC-QFAAS). Recoveries of butyltin spikes from natural water samples were 90-109% at concentrations of {approx}100 ng Sn/l. The method precision at {approx}100 ng Sn/l was {<=}6% RSD for butyltins spiked into natural waters. The detection limits for 1 l water samples were <1 ng Sn/l for all butyltin species. Sample throughput of the method is high (greater than three samples per hour) due to the two-stage nature of the procedure, which allows derivatisation/trapping and GC-QFAAS quantitation to be performed separately. Off-line trapping is also advantageous as it extends the life of the GC column and quartz furnace to at least 12 months due to minimisation of carry-over of co-purged material.

  11. Influence of pH and temperature on the rheological properties of aqueous dispersions of starch-sodium palmitate complexes

    Science.gov (United States)

    Aqueous dispersions of high-amylose corn starch were steam jet cooked and blended with aqueous solutions of sodium palmitate to form amylose inclusion complexes. The rheology of dispersions of these complexes was examined. Acetic acid was added to reduce the pH, converting complexed sodium palmita...

  12. Thermodynamics of aqueous methyldiethanolamine (MDEA) and methyldiethanolammonium chloride (MDEAH+Cl-) over a wide range of temperature and pressure: Apparent molar volumes, heat capacities, and isothermal compressibilities

    International Nuclear Information System (INIS)

    Hawrylak, B.; Palepu, R.; Tremaine, Peter R.

    2006-01-01

    Apparent molar volumes of aqueous methyldiethanolamine and its salt were determined with platinum vibrating tube densitometers over a range of temperatures from 283K= o , heat capacities C p o , and isothermal compressibilities κ T o . The standard partial molar volumes V o for the neutral amine and its salt show increasingly positive and negative values, respectively, at high temperatures and pressures, as predicted by corresponding states and group additivity arguments. The density model and the revised Helgeson-Kirkham-Flowers (HKF) model have been used to represent the temperature and pressure dependence of the standard partial molar properties to yield a full thermodynamic description of the system

  13. Geochemistry of High Temperature Vent Fluids in Yellowstone Lake: Dissolved Carbon and Sulfur Concentrations and Isotopic Data

    Science.gov (United States)

    Cino, C.; Seyfried, W. E., Jr.; Tan, C.; Fu, Q.

    2017-12-01

    Yellowstone National Park is a dynamic environment home to an array of geysers, hot springs, and hydrothermal vents fueled by the underlying continental magmatic intrusion. Yellowstone Lake vent fluids accounts for approximately 10% of the total geothermal flux for all of Yellowstone National Park. Though studying this remote hydrothermal system poses severe challenges, it provides an excellent natural laboratory to research hydrothermal fluids that undergo higher pressure and temperature conditions in an environment largely shielded from atmospheric oxygen. The location of these vents also provides chemistry that is characteristic of fluids deeper in the Yellowstone hydrothermal system. In August 2016, hydrothermal fluids were collected from the Stevenson Island vents in collaboration with the Hydrothermal Dynamics of Yellowstone Lake (HD-YLAKE) project using novel sampling techniques and monitoring instrumentation. The newly built ROV Yogi was deployed to reach the vents in-situ with temperatures in excess of 151oC at 100-120 m depth, equipped with a 12-cylinder isobaric sampler to collect the hydrothermal fluids. Results from geochemical analyses indicate the fluids are rich in gases such as CO2, CH4, and H2S, with sample concentrations of approximately 12 mM, 161 μm, and 2.1 mM respectively. However, lake water mixing with the hydrothermal endmember fluid likely diluted these concentrations in the collected samples. Isotopic analyses indicate CO2 has a δ13C of -6 indicating magmatic origins, however the CH4 resulted in a δ13C of -65 which is in the biological range. This biogenic signature is likely due to the pyrolysis of immature organic matter in the lake bottom sediment, since the high temperatures measured for the fluids would not allow the presence of methanogens. H2S concentrations have not been previously measured for the hydrothermal fluids in Yellowstone Lake, and our vent fluid samples indicate significantly higher H2S concentrations than reported

  14. 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

  15. Evaluation of mineral-aqueous chemical equilibria of felsic reservoirs with low-medium temperature: A comparative study in Yangbajing geothermal field and Guangdong geothermal fields

    Science.gov (United States)

    Li, Jiexiang; Sagoe, Gideon; Yang, Guang; Lu, Guoping

    2018-02-01

    Classical geothermometers are useful tools for estimating reservoir temperatures of geothermal systems. However, their application to low-medium temperature reservoirs is limited because large variations of temperatures calculated by different classical geothermometers are usually observed. In order to help choose the most appropriate classical geothermometer for calculating the temperatures of low-medium temperature reservoirs, this study evaluated the mineral-aqueous equilibria of typical low-medium temperature felsic reservoirs in the Yangbajing geothermal field and Guangdong geothermal fields. The findings of this study support that reservoirs in the Guangdong geothermal fields have no direct magma influence. Also, natural reservoirs may represent the intermediate steady state before reaching full equilibrium, which rarely occurs. For the low-medium temperature geothermal systems without the influence of magma, even with seawater intrusion, the process of minerals reaching mineral-aqueous equilibrium is sequential: chlorite and chalcedony are the first, then followed by K-feldspar, kaolinite and K-mica. Chlorite may reach equilibrium at varying activity values, and the equilibrium between K-feldspar and kaolinite or K-feldspar and K-mica can fix the contents of K and Al in the solutions. Although the SiO2 and Al attain equilibrium state, albite and laumontite remain unsaturated and thus may affect low-medium temperature calculations. In this study, the chalcedony geothermometer was found to be the most suitable geothermometer for low-medium temperature reservoirs. The results of K-Mg geothermometer may be useful to complement that of the chalcedony geothermometer in low-medium temperature reservoir systems. Na-K geothermometer will give unreliable results at low-medium temperatures; and Na-K-Ca will also be unsuitable to calculate reservoir temperatures lower than 180 °C, probably caused by the chemical imbalance of laumontite.

  16. Sulfuric acid leaching of high iron-bearing zinc calcine

    Science.gov (United States)

    Yang, Jin-lin; Liu, Ji-guang; Xiao, Han-xin; Ma, Shao-jian

    2017-11-01

    Sulfuric acid leaching of high iron-bearing zinc calcine was investigated to assess the effects of sulfuric acid concentration, liquid- to-solid ratio, leaching time, leaching temperature, and the stirring speed on the leaching rates of zinc and iron. The results showed that the sulfuric acid concentration, liquid-to-solid ratio, leaching time, and leaching temperature strongly influenced the leaching of zinc and iron, whereas stirring speed had little influence. Zinc was mainly leached and the leaching rate of iron was low when the sulfuric acid concentration was less than 100 g/L. At sulfuric acid concentrations higher than 100 g/L, the leaching rate of iron increased quickly with increasing sulfuric acid concentration. This behavior is attributed to iron-bearing minerals such as zinc ferrite in zinc calcine dissolving at high temperatures and high sulfuric acid concentrations but not at low temperatures and low sulfuric acid concentrations.

  17. Determination of Three-Dimensional Morphology and Inner Structure of Second-Phase Inclusions in Metals by Non-Aqueous Solution Electrolytic and Room Temperature Organic Methods

    OpenAIRE

    Jing Guo; Keming Fang; Hanjie Guo; Yiwa Luo; Shengchao Duan; Xiao Shi; Wensheng Yang

    2018-01-01

    The secondary-phase particles in metals, particularly those composed of non-metallic materials, are often detrimental to the mechanical properties of metals; thus, it is crucial to control inclusion formation and growth. One of the challenges is determining the three-dimensional morphology and inner structures of such inclusions. In this study, a non-aqueous solution electrolytic method and a room-temperature organic technique were developed based on the principle of electrochemistry to deter...

  18. Corrosion resistance of materials of construction for high temperature sulfuric acid service in thermochemical IS process. Alloy 800, Alloy 600, SUSXM15J1 and SiC

    International Nuclear Information System (INIS)

    Tanaka, Nobuyuki; Onuki, Kaoru; Shimizu, Saburo; Yamaguchi, Akihisa

    2006-01-01

    Exposure tests of candidate materials were carried out up to 1000 hr in the sulfuric acid environments of thermochemical hydrogen production IS process, focusing on the corrosion of welded portion and of crevice area. In the gas phase sulfuric acid decomposition condition at 850degC, welded samples of Alloy 800 and of Alloy 600 showed the same good corrosion resistance as the base materials. In the boiling condition of 95 wt% sulfuric acid solution, test sample of SiC showed the same good corrosion resistance. Also negligible corrosion was observed in crevice corrosion. (author)

  19. Rate constants and temperature effects for reactions of Cl2sm-bullet- with unsaturated alcohols and hydrocarbons in aqueous and acetonitrile/water solutions

    International Nuclear Information System (INIS)

    Padmaja, S.; Neta, P.; Huie, R.E.

    1992-01-01

    Absolute rate constants for reactions of the dichlorine radical anion, Cl 2 sm-bullet- , with unsaturated alcohols and hydrocarbons have been measured at various temperatures. The alcohol reactions were measured in aqueous solutions and the hydrocarbon reactions in 1:1 aqueous acetonitirle (ACN) solutions. The rate constants for two alcohols and one hydrocarbon were also examined as a function of solvent composition. The room temperature rate constants varied between 10 6 and 10 9 M -1 s -1 . The pre-exponential factors, A, were about (1-5) x 10 9 M -1 s -1 for the alcohols in aqueous solutions and about (0.1-1) x 10 9 M -1 s -1 for the hydrocarbons in aqueous ACN solutions. The activation energies, E a , varied considerably, between 4 and 12 kJ mol -1 for the alcohols and between 2 and 8 kJ mol -1 for the hydrocarbons. The rate constants, k 298 , decrease with increasing ionization potential (IP) of the unsaturated compound, in agreement with an electrophilic addition mechanism. The activation energies for the unsaturated alcohols decrease when the IP decreases from 9.7 to 9.1 eV but appear to level off at lower IP. Most alkenes studied had IP a . Upon addition of ACN to the aqueous solution, the values of log k 298 decreased linearly by more than 1 order of magnitude with increasing ACN mole fraction. This decrease appears to result from a combination of changes in the activation energy and in the pre-exponential factor. The reason for these changes may lie in changes in the solvation shell of the Cl 2 sm-bullet- radical, which will affect the A factor, in combination with changes in solvation of Cl - , which will affect the energetics of the reactions as well. 20 refs., 7 figs., 6 tabs

  20. Room temperature synthesis of PbSe quantum dots in aqueous solution: Stabilization by interactions with ligands

    Science.gov (United States)

    Primera-Pedrozo, Oliva M.; Arslan, Zikri; Rasulev, Bakhtiyor; Leszczynski, Jerzy

    2011-01-01

    An aqueous route of synthesis is described for rapid synthesis of lead selenide quantum dots (PbSe QDs) at room temperature in an attempt to produce water-soluble and stable nanocrystals. Several thiol-ligands, including thioglycolic acid (TGA), thioglycerol (TGC), 3-mercaptopropionic acid (MPA), 2-mercaptoethyleamine hydrochloride (MEA), 6-mercaptohexanoic acid (MHA), and L-cysteine (L-cys), were used for capping/stabilization of PbSe QDs. The effects of the ligands on the stability of PbSe QDs were evaluated for a period of two months at room temperature under normal light conditions and at 4 °C in dark. The TGA- and MEA-capped QDs exhibited the highest stability prior to purification, almost two months when kept in dark at 4 °C. However, the stability of TGA-capped QDs was reduced substantially after purification to about 5 days under same conditions, while MEA-capped QDs did not show any significant instability. The stabilization energies of Pb-thiolate complexes determined by theoretical DFT simulations supported the experimental results. The PbSe QDs capped with TGA, MPA and MEA were successfully purified and re-dispersed in water, while those stabilized with TGC, MHA and L-cys aggregated during purification attempts. The purified PbSe QDs possess very susceptible surface resulting in poor stability for about 30 – 45 min after re-dispersion in water. In the presence of an excess of free ligand, the stability increased up to 5 days for TGA-capped QDs at pH 7.19, 9 –12 days for MPA-capped QDs at pH 7.3–7.5 and 45–47 days for MEA-capped QDs at pH 7.35. X-Ray Diffraction (XRD) results showed that the QDs possess a cubic rock salt structure with the most intense peaks located at 2θ = 25.3° (200) and 2θ = 29.2° (100). TEM images showed that the size of the QDs ranges between 5 and 10 nm. ICP-MS results revealed that Pb:Se ratio was 1.26, 1.28, 3.85, 1.18, and 1.31 for the QDs capped with TGA, MPA, MEA, L-Cys, and TGC, respectively. The proposed method

  1. 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.

  2. Sulfur metabolism in phototrophic sulfur bacteria

    DEFF Research Database (Denmark)

    Frigaard, Niels-Ulrik; Dahl, Christiane

    2008-01-01

    Phototrophic sulfur bacteria are characterized by oxidizing various inorganic sulfur compounds for use as electron donors in carbon dioxide fixation during anoxygenic photosynthetic growth. These bacteria are divided into the purple sulfur bacteria (PSB) and the green sulfur bacteria (GSB......). They utilize various combinations of sulfide, elemental sulfur, and thiosulfate and sometimes also ferrous iron and hydrogen as electron donors. This review focuses on the dissimilatory and assimilatory metabolism of inorganic sulfur compounds in these bacteria and also briefly discusses these metabolisms...... in other types of anoxygenic phototrophic bacteria. The biochemistry and genetics of sulfur compound oxidation in PSB and GSB are described in detail. A variety of enzymes catalyzing sulfur oxidation reactions have been isolated from GSB and PSB (especially Allochromatium vinosum, a representative...

  3. Sulfuric acid thermoelectrochemical system and method

    Science.gov (United States)

    Ludwig, Frank A.

    1989-01-01

    A thermoelectrochemical system in which an electrical current is generated between a cathode immersed in a concentrated sulfuric acid solution and an anode immersed in an aqueous buffer solution of sodium bisulfate and sodium sulfate. Reactants consumed at the electrodes during the electrochemical reaction are thermochemically regenerated and recycled to the electrodes to provide continuous operation of the system.

  4. The effects of sulfur on carbon partitioning and solubility in high pressure-temperature alloy-silicate systems: Implications for fractionation of carbon and sulfur during accretion and core formation of Earth and Mars

    Science.gov (United States)

    Tsuno, K.; Dasgupta, R.; Grewal, D. S.

    2017-12-01

    Constraining the carbon (C) fractionation between the silicate magma ocean (MO) and core-forming alloy liquid is required to determine the origin and evolution of C between reservoirs such as atmosphere, crust, mantle, and core of terrestrial planets. [1]. Alloy-silicate partitioning experiments of C have shown that preferential fractionation of C into the alloy liquid would have left the bulk silicate Earth (BSE) devoid of C [2-4]. Merger of a sulfur (S)-rich differentiated planetary embryo into the proto-Earth could have supplied almost the entire C budget of the present-day BSE [5], however, experimental data on the systematic effect of S on C solubility in Fe-Ni alloy liquid and its partitioning between the alloy liquid and silicate melt are lacking. We have performed multi anvil experiments with alloy-silicate±glassy carbon mixtures at 6-13 GPa and 1800-2000 °C, fO2 of ΔIW of -0.4 to -2.3, using graphite or MgO capsules and varying alloy S content from 10 to 36 wt.%. We find that C content of the alloy liquid decreases from 4.6 to 0.2 wt.% with increasing alloy S content of 10 to 36 wt.%. Temperature has a small positive effect and pressure has little effect on alloy C solubility. Alloy-silicate partition coefficient of C also decreases with increasing alloy S content at a given P-T-fO2. We used the data to quantify the distribution of C between the silicate MO and core-forming alloy liquid of an S-rich planetary embryo. The model calculations using our data suggest that the addition of a relatively oxidized, C-poor ( 0.3 wt.%) and S-rich ( 3 wt.%) large embryo (6-20% of the present-day Earth mass) to a volatile-poor growing Earth can establish the C and S contents [6, 7] and C/S ratio [8] in BSE. The resulting core composition after the accretion and core formation process is estimated to be C- and S-poor ( 0.05 wt.% and 0.6 wt.%, respectively). On the other hand, a single stage core formation on Mars that results in a core with 8-10 wt.% S can yield a

  5. Changes in the structure of water in aqueous solutions of acetic acid, depending on concentration and temperature according to densitometry, viscosimetry, and IR spectroscopy data

    Science.gov (United States)

    Masimov, E. A.; Khasanov, G. Sh.; Pashaev, B. G.

    2013-06-01

    The structural features of aqueous solutions of acetic acid are studied by means of viscosimetry, densimetry, and IR spectroscopy within the temperature range of 283.15-333.15 K and a concentration range of 0-80%. The results from our experiments are used to calculate the parameters of viscous flow activation, the structural temperature, the partial molar volume of acetic acid in the solution, the thermal expansion coefficient, and the energies and lengths of the hydrogen bonds between water molecules. The concentration dependences of these parameters are analyzed. Based on the obtained results, we conclude that acetic acid disrupts the structure of water.

  6. Sulfuric acid-sulfur heat storage cycle

    Science.gov (United States)

    Norman, John H.

    1983-12-20

    A method of storing heat is provided utilizing a chemical cycle which interconverts sulfuric acid and sulfur. The method can be used to levelize the energy obtained from intermittent heat sources, such as solar collectors. Dilute sulfuric acid is concentrated by evaporation of water, and the concentrated sulfuric acid is boiled and decomposed using intense heat from the heat source, forming sulfur dioxide and oxygen. The sulfur dioxide is reacted with water in a disproportionation reaction yielding dilute sulfuric acid, which is recycled, and elemental sulfur. The sulfur has substantial potential chemical energy and represents the storage of a significant portion of the energy obtained from the heat source. The sulfur is burned whenever required to release the stored energy. A particularly advantageous use of the heat storage method is in conjunction with a solar-powered facility which uses the Bunsen reaction in a water-splitting process. The energy storage method is used to levelize the availability of solar energy while some of the sulfur dioxide produced in the heat storage reactions is converted to sulfuric acid in the Bunsen reaction.

  7. The adsorption of sulfur by microporous materials

    NARCIS (Netherlands)

    Steijns, M.; Mars, P.

    1976-01-01

    The sorption of sulfur by the zeolites NaX (= 13X) and CaA (= 5A) and an activated charcoal prepared from sugar was investigated at temperatures between 150 and 350°C and relative sulfur pressures between 10−4 and 10−1. The adsorbate-adsorbate interaction indicated by the S-shaped isotherm for the

  8. Isobaric specific heat capacity of water and aqueous cesium chloride solutions for temperatures between 298 K and 370 K at p = 0.1 MPa

    International Nuclear Information System (INIS)

    Lourenco, M.J.V.; Santos, F.J.V.; Ramires, M.L.V.; Nieto de Castro, C.A.

    2006-01-01

    There has been some controversy regarding the uncertainty of measurements of thermal properties using differential scanning calorimeters, namely heat capacity of liquids. A differential scanning calorimeter calibrated in enthalpy and temperature was used to measure the isobaric specific heat capacity of water and aqueous solutions of cesium chloride, in the temperature range 298 K to 370 K, for molalities up 3.2 mol . kg -1 , at p = 0.1 MPa, with an estimated uncertainty (ISO definition) better than 1.1%, at a 95% confidence level. The measurements are completely traceable to SI units of energy and temperature. The results obtained were correlated as a function of temperature and molality and compared with other authors, obtained by different methods and permit to conclude that a DSC calibrated by Joule effect is capable of very accurate measurements of the isobaric heat capacity of liquids, traceable to SI units of measurement

  9. 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.

  10. Model description of the equivalent electroconductivity of aqueous solutions of alkali metal hydroxides over a wide range of concentrations and temperatures

    Science.gov (United States)

    Kuznetsova, E. M.; Volkov, D. S.

    2011-09-01

    The possibility of a quantitative theoretical description of the λ( c) dependence for aqueous solutions of alkali metal hydroxides in a wide concentration (from 0.0001 to 12 M) and temperature (from 0 to 100°C) was considered on the basis of concept suggested earlier. Effectiveness of the description of characteristics analyzed was illustrated on the examples of the calculation of electroconductivity values for aqueous LiOH, NaOH, KOH, RbOH, and CsOH solutions and comparison of them with experimental values taken from published data. The suggestion on different H+ and OH- ion migration mechanism was made on the basis of the model used for description of λ( c).

  11. Thiophenic Sulfur Compounds Released During Coal Pyrolysis.

    Science.gov (United States)

    Xing, Mengwen; Kong, Jiao; Dong, Jie; Jiao, Haili; Li, Fan

    2013-06-01

    Thiophenic sulfur compounds are released during coal gasification, carbonization, and combustion. Previous studies indicate that thiophenic sulfur compounds degrade very slowly in the environment, and are more carcinogenic than polycyclic aromatic hydrocarbons and nitrogenous compounds. Therefore, it is very important to study the principle of thiophenic sulfur compounds during coal conversion, in order to control their emission and promote clean coal utilization. To realize this goal and understand the formation mechanism of thiophenic sulfur compounds, this study focused on the release behavior of thiophenic sulfur compounds during coal pyrolysis, which is an important phase for all coal thermal conversion processes. The pyrolyzer (CDS-5250) and gas chromatography-mass spectrometry (Focus GC-DSQII) were used to analyze thiophenic sulfur compounds in situ . Several coals with different coal ranks and sulfur contents were chosen as experimental samples, and thiophenic sulfur compounds of the gas produced during pyrolysis under different temperatures and heating rates were investigated. Levels of benzothiophene and dibenzothiophene were obtained during pyrolysis at temperatures ranging from 200°C to 1300°C, and heating rates ranging from 6°C/ms to 14°C/ms and 6°C/s to 14°C/s. Moreover, the relationship between the total amount of benzothiophene and dibenzothiophene released during coal pyrolysis and the organic sulfur content in coal was also discussed. This study is beneficial for understanding the formation and control of thiophenic sulfur compounds, since it provides a series of significant results that show the impact that operation conditions and organic sulfur content in coal have on the amount and species of thiophenic sulfur compounds produced during coal pyrolysis.

  12. Thiophenic Sulfur Compounds Released During Coal Pyrolysis

    Science.gov (United States)

    Xing, Mengwen; Kong, Jiao; Dong, Jie; Jiao, Haili; Li, Fan

    2013-01-01

    Abstract Thiophenic sulfur compounds are released during coal gasification, carbonization, and combustion. Previous studies indicate that thiophenic sulfur compounds degrade very slowly in the environment, and are more carcinogenic than polycyclic aromatic hydrocarbons and nitrogenous compounds. Therefore, it is very important to study the principle of thiophenic sulfur compounds during coal conversion, in order to control their emission and promote clean coal utilization. To realize this goal and understand the formation mechanism of thiophenic sulfur compounds, this study focused on the release behavior of thiophenic sulfur compounds during coal pyrolysis, which is an important phase for all coal thermal conversion processes. The pyrolyzer (CDS-5250) and gas chromatography–mass spectrometry (Focus GC-DSQII) were used to analyze thiophenic sulfur compounds in situ. Several coals with different coal ranks and sulfur contents were chosen as experimental samples, and thiophenic sulfur compounds of the gas produced during pyrolysis under different temperatures and heating rates were investigated. Levels of benzothiophene and dibenzothiophene were obtained during pyrolysis at temperatures ranging from 200°C to 1300°C, and heating rates ranging from 6°C/ms to 14°C/ms and 6°C/s to 14°C/s. Moreover, the relationship between the total amount of benzothiophene and dibenzothiophene released during coal pyrolysis and the organic sulfur content in coal was also discussed. This study is beneficial for understanding the formation and control of thiophenic sulfur compounds, since it provides a series of significant results that show the impact that operation conditions and organic sulfur content in coal have on the amount and species of thiophenic sulfur compounds produced during coal pyrolysis. PMID:23781126

  13. Phase equilibrium properties of binary aqueous solutions containing ethanediamine, 1,2-diaminopropane, 1,3-diaminopropane, or 1,4-diaminobutane at several temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Ahmed, Nouria Chiali-Baba [LATA2M, Laboratoire de Thermodynamique Appliquee et Modelisation Moleculaire, University AbouBekr Belkaid of Tlemcen, P.O. Box 119, Tlemcen 13000 (Algeria); Negadi, Latifa, E-mail: l_negadi@mail.univ-tlemcen.d [LATA2M, Laboratoire de Thermodynamique Appliquee et Modelisation Moleculaire, University AbouBekr Belkaid of Tlemcen, P.O. Box 119, Tlemcen 13000 (Algeria); Mokbel, Ilham; Jose, Jacques [LSA, Laboratoire des Sciences Analytiques, CNRS-UMR 5180, Universite Claude Bernard - Lyon I. 43, Bd du 11 Novembre 1918, Villeurbanne Cedex 69622 (France)

    2011-05-15

    Research highlights: Vapour pressures of ethanediamine (EDA), 1,2-diaminopropane, 1,3-diaminopropane (1,3-DAP), or 1,4-diaminobutane (1,4-DAB) aqueous solutions are reported between (293 and 363) K. The two first mixtures show negative azeotropic behaviour. The aqueous solutions of EDA, 1,2-DAP, or 1,3-DAP exhibit negative G{sup E} whereas the one containing 1,4-DAB shows either negative G{sup E} or sinusoidal shape for G{sup E}. - Abstract: The vapour pressures of {l_brace}ethanediamine (EDA) + water{r_brace}, {l_brace}1,2-diaminopropane (1,2-DAP) + water{r_brace}, {l_brace}1,3-diaminopropane (1,3-DAP) + water{r_brace} or {l_brace}1,4-diaminobutane (1,4-DAB) + water{r_brace} binary mixtures, and of pure EDA, 1,2-DAP, 1,3-DAP, 1,4-DAB, and water components were measured by means of two static devices at temperatures between (293 and 363) K. The data were correlated with the Antoine equation. From these data, the excess Gibbs function (G{sup E}) was calculated for several constant temperatures and fitted to a fourth-order Redlich-Kister equation using the Barker's method. The {l_brace}ethanediamine (EDA) + water{r_brace}, and {l_brace}1,2-diaminopropane (1,2-DAP) + water{r_brace} binary systems show negative azeotropic behaviour. The aqueous solutions of EDA, 1,2-DAP, or 1,3-DAP exhibit negative deviations in G{sup E} for all investigated temperatures over the whole composition range whereas the (1,4-DAB + water) binary mixture shows negative G{sup E} for temperatures (293.15 < T/K < 353.15) and a sinusoidal shape for G{sup E} at T = 363.15 K.

  14. Shear-Induced Phase Separation in Aqueous Polymer Solutions: Temperature-Sensitive Microgels and Linear Polymer Chains

    NARCIS (Netherlands)

    Stieger, M.A.; Richtering, W.

    2003-01-01

    The influence of shear flow on the phase separation of aqueous poly(N-isopropylacrylamide) (PNiPAM) microgel suspensions was investigated by means of rheo-turbidity and rheo-small angle neutron scattering (rheo-SANS) and compared to the behavior of linear PNiPAM macromolecules. The rheological

  15. Mercury chemisorption by sulfur adsorbed in porous materials

    NARCIS (Netherlands)

    Steijns, M.; Peppelenbos, A.; Mars, P.

    1976-01-01

    The sorption of mercury vapor by adsorbed sulfur in the zeolites CaA (= 5A) and NaX (=13X) and two types of active carbon has been measured at a temperature of 50°C. With increasing degree of micropore filling by sulfur the fraction of sulfur accessible to mercury atoms decreased for CaA and NaX.

  16. Kinetics of uncatalyzed thermochemical sulfate reduction by sulfur-free paraffin

    Science.gov (United States)

    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

  17. Ternary (liquid + liquid) equilibria for the extraction of ethanol, or 2-propanol from aqueous solutions with 1,1′-oxybis(butane) at different temperatures

    International Nuclear Information System (INIS)

    Wang, Cui; Guo, Jitai; Cheng, Kai; Chen, Yao

    2016-01-01

    Highlights: • LLE data of [water + ethanol or 2-propanol + 1,1′-oxybis(butane)] were measured at four temperatures. • Tie-line data were correlated by using the extended and modified UNIQUAC models. • The temperature influence on liquid-phase regions was analyzed. • The ability of DBE to extract ethanol or 2-propanol from aqueous solutions was discussed. - Abstract: (Liquid + liquid) equilibrium data for the ternary systems of {water + ethanol + 1,1′-oxybis(butane)} and {water + 2-propanol + 1,1′-oxybis(butane)} at T = (293.15, 298.15, 303.15, 308.15) K have been measured under atmospheric pressure. The experimental results were correlated by using the modified and extended UNIQUAC models. Distribution coefficients and separation factors of ethanol and 2-propanol were calculated and discussed in detail. The temperature influence on liquid-phase regions was analysed.

  18. Thermally induced degradation of sulfur-containing aliphatic glucosinolates in broccoli sprouts (Brassica oleracea var. italica) and model systems.

    Science.gov (United States)

    Hanschen, Franziska S; Platz, Stefanie; Mewis, Inga; Schreiner, Monika; Rohn, Sascha; Kroh, Lothar W

    2012-03-07

    Processing reduces the glucosinolate (GSL) content of plant food, among other aspects due to thermally induced degradation. Since there is little information about the thermal stability of GSL and formation of corresponding breakdown products, the thermally induced degradation of sulfur-containing aliphatic GSL was studied in broccoli sprouts and with isolated GSL in dry medium at different temperatures as well as in aqueous medium at different pH values. Desulfo-GSL have been analyzed with HPLC-DAD, while breakdown products were estimated using GC-FID. Whereas in the broccoli sprouts structural differences of the GSL with regard to thermal stability exist, the various isolated sulfur-containing aliphatic GSL degraded nearly equally and were in general more stable. In broccoli sprouts, methylsulfanylalkyl GSL were more susceptible to degradation at high temperatures, whereas methylsulfinylalkyl GSL were revealed to be more affected in aqueous medium under alkaline conditions. Besides small amounts of isothiocyanates, the main thermally induced breakdown products of sulfur-containing aliphatic GSL were nitriles. Although they were most rapidly formed at comparatively high temperatures under dry heat conditions, their highest concentrations were found after cooking in acidic medium, conditions being typical for domestic processing.

  19. Properties of L-ascorbic acid in water and binary aqueous mixtures of D-glucose and D-fructose at different temperatures

    Science.gov (United States)

    Sharma, Ravi; Thakur, R. C.; Sani, Balwinder; Kumar, Harsh

    2017-12-01

    Using density and sound velocity partial molar volumes, partial molar adiabatic compressibilities, partial molar expansibilities and structure of L-ascorbic acid have been determined in water and aqueous mixtures of D-glucose and D-fructose at different concentrations and temperatures. Masson's equation was used to analyze the measured data. The obtained parameters have been interpreted in terms of solute-solute and solute-solvent interactions. It is found that the L-ascorbic acid acts as structure breaker in water as well in binary studied mixtures.

  20. EFFECT OF TEMPERATURE AND CONCENTRATION ON THE VISCOSITY OF AQUEOUS SOLUTIONS OF 3-AMINOPROPANOIC ACID, 4-AMINOBUTANOIC ACID, 5-AMINOPENTANOIC ACID, 6-AMINOHEXANOIC ACID

    Directory of Open Access Journals (Sweden)

    Carmen María Romero

    2011-12-01

    Full Text Available In this work we present the effect of temperatureon the viscosities of aqueous solutionsof 3-aminopropanoic acid, 4-aminobutanoicacid, 5-aminopentanoic acidand 6-aminohexanoic acid as a functionof concentration. The experimental measurementswere done from 293.15 K to308.15 K. At each temperature the experimentaldata were fi tted to the Tsangaris-Martin equation and the B viscosity coefficient was determined. The dependenceof the B coeffi cients on the number ofcarbon atoms of the amino acids is linear,so the contribution of polar and apolargroups was established. The results areinterpreted in terms of amino acid hydration.

  1. Influence of Sulfur Fertilization on the Antioxidant Activities of Onion Juices Prepared by Thermal Treatment

    Science.gov (United States)

    Koh, Eunmi; Surh, Jeonghee

    2016-01-01

    Two onions (Sulfur-1 and Sulfur-4) cultivated with different sulfur applications were thermally processed to elucidate the effects of heat treatment on browning index and antioxidant activity. Sulfur-4 onion had higher sulfur content compared with the Sulfur-1 onion. After thermal processing, browning intensity was different between the two onions juices, with lower values observed for Sulfur-4 onion juice. This suggests that sulfur inhibits the Maillard browning reaction. The total reducing capacity of the juices increased at higher thermal processing temperatures; however, it was also lower in the Sulfur-4 onion juice. This suggests that the heat treatment of onions enhanced their antioxidant activity, but the effect was offset in the Sulfur-4 onion juice presumably due to higher sulfur content. This study indicates that sulfur, a core element for the functionality of onions, can decrease the antioxidant activity of thermally processed onions because of its potential as a Maillard reaction inhibitor. PMID:27390734

  2. Elimination of active species crossover in a room temperature, neutral pH, aqueous flow battery using a ceramic NaSICON membrane

    Science.gov (United States)

    Allcorn, Eric; Nagasubramanian, Ganesan; Pratt, Harry D.; Spoerke, Erik; Ingersoll, David

    2018-02-01

    Flow batteries are an attractive technology for energy storage of grid-scale renewables. However, performance issues related to ion-exchange membrane (IEM) fouling and crossover of species have limited the success of flow batteries. In this work we propose the use of the solid-state sodium-ion conductor NaSICON as an IEM to fully eliminate active species crossover in room temperature, aqueous, neutral pH flow batteries. We measure the room temperature conductivity of NaSICON at 2.83-4.67 mS cm-1 and demonstrate stability of NaSICON in an aqueous electrolyte with conductivity values remaining near 2.5 mS cm-1 after 66 days of exposure. Charge and discharge of a full H-cell battery as well as symmetric cycling in a flow battery configuration using NaSICON as an IEM in both cases demonstrates the capability of the solid-state IEM. Extensive analysis of aged cells through electrochemical impedance spectroscopy (EIS) and UV-vis spectroscopy show no contaminant species having crossed over the NaSICON membrane after 83 days of exposure, yielding an upper limit to the permeability of NaSICON of 4 × 10-10 cm2 min-1. The demonstration of NaSICON as an IEM enables a wide new range of chemistries for application to flow batteries that would previously be impeded by species crossover and associated degradation.

  3. 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.

  4. 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.

  5. Sulfuric acid poisoning

    Science.gov (United States)

    Sulfuric acid is a very strong chemical that is corrosive. Corrosive means it can cause severe burns and ... or mucous membranes. This article discusses poisoning from sulfuric acid. This article is for information only. Do NOT ...

  6. Internal Nanoparticle Structure of Temperature-Responsive Self-Assembled PNIPAM-b-PEG-b-PNIPAM Triblock Copolymers in Aqueous Solutions: NMR, SANS, and Light Scattering Studies.

    Science.gov (United States)

    Filippov, Sergey K; Bogomolova, Anna; Kaberov, Leonid; Velychkivska, Nadiia; Starovoytova, Larisa; Cernochova, Zulfiya; Rogers, Sarah E; Lau, Wing Man; Khutoryanskiy, Vitaliy V; Cook, Michael T

    2016-05-31

    In this study, we report detailed information on the internal structure of PNIPAM-b-PEG-b-PNIPAM nanoparticles formed from self-assembly in aqueous solutions upon increase in temperature. NMR spectroscopy, light scattering, and small-angle neutron scattering (SANS) were used to monitor different stages of nanoparticle formation as a function of temperature, providing insight into the fundamental processes involved. The presence of PEG in a copolymer structure significantly affects the formation of nanoparticles, making their transition to occur over a broader temperature range. The crucial parameter that controls the transition is the ratio of PEG/PNIPAM. For pure PNIPAM, the transition is sharp; the higher the PEG/PNIPAM ratio results in a broader transition. This behavior is explained by different mechanisms of PNIPAM block incorporation during nanoparticle formation at different PEG/PNIPAM ratios. Contrast variation experiments using SANS show that the structure of nanoparticles above cloud point temperatures for PNIPAM-b-PEG-b-PNIPAM copolymers is drastically different from the structure of PNIPAM mesoglobules. In contrast with pure PNIPAM mesoglobules, where solidlike particles and chain network with a mesh size of 1-3 nm are present, nanoparticles formed from PNIPAM-b-PEG-b-PNIPAM copolymers have nonuniform structure with "frozen" areas interconnected by single chains in Gaussian conformation. SANS data with deuterated "invisible" PEG blocks imply that PEG is uniformly distributed inside of a nanoparticle. It is kinetically flexible PEG blocks which affect the nanoparticle formation by prevention of PNIPAM microphase separation.

  7. Aqueous chemical route synthesis and the effect of calcination temperature on the structural and optical properties of ZnO nanoparticles

    Directory of Open Access Journals (Sweden)

    Mohammad Ramzan Parra

    2014-10-01

    Full Text Available This article reports the controlled size of ZnO nanoparticles synthesized via simple aqueous chemical route without the involvement of any capping agent. The effect of different calcination temperatures on the size of the ZnO nanoparticles was investigated. X-ray diffraction (XRD results indicated that all the samples have crystalline wurtzite phase, and peak broadening analysis was used to evaluate the average crystallite size and lattice strain using Scherrer's equation and Williamson–Hall (W–H method. Morphology and elemental compositions were investigated using atomic force microscopy (AFM and scanning electron microscopy (SEM with energy-dispersive X-ray (EDX spectroscopy. The average crystallite size of ZnO nanoparticles estimated from Scherrer's formula and W–H analysis was found to increase with the increase in calcination temperature. These results were in good agreement with AFM results. Optical properties were investigated using UV–vis spectroscopy in diffused reflectance (DR mode, with a sharp increase in reflectivity at 375 nm and the material has a strong reflective characteristic after 420 nm at 500 °C calcination temperature. Furthermore, photoluminescence spectroscopic results revealed intensive ultraviolet (UV emission with reduced defect concentrations and a slight shifting in band gap energies with increased calcination temperature from 200 °C to 500 °C. This study suggests that the as-prepared ZnO nanoparticles with bandgap tunability might be utilized as window layer in optoelectronic devices.

  8. In-situ, high pressure and temperature experimental determination of hydrogen isotope fractionation between coexisting hydrous melt and silicate-saturated aqueous fluid

    Science.gov (United States)

    Mysen, B. O.

    2012-12-01

    Hydrogen isotope fractionation between water-saturated silicate melt and silicate-saturated aqueous fluid has been determined experimentally, in-situ with the samples in the 450-800C and 101-1567 MPa temperature and pressure range, respectively. The temperatures are, therefore higher than those where hydrogen bonding in fluids and melts is important [1]. The experiments were conducted with a hydrothermal diamond anvil cell (HDAC) as the high-temperature/-pressure tool and vibrational spectroscopy to determine D/H fractionation. Compositions were along the haploandesite join, Na2Si4O9 - Na2(NaAl)4O9 [Al/(Al+Si)=0-0.1], and a 50:50 (by volume) H2O:D2O fluid mixture as starting material. Platinum metal was used to enhance equilibration rate. Isotopic equilibrium was ascertained by using variable experimental duration at given temperature and pressure. In the Al-free Na-silicate system, the enthalpy change of the (D/H) equilibrium of fluid is 3.1±0.7 kJ/mol, whereas for coexisting melt, ΔH=0 kJ/mol within error. With Al/(Al+Si)=0.1, ΔH=5.2±0.9 kJ/mol for fluid and near 0 within error for coexisting melt melt. For the exchange equilibrium between melt and fluid, H2O(melt)+D2O(fluid)=H2O(fluid)+D2O(melt), the ΔH=4.6±0.7 and 6.5±0.7 kJ/mol for the two Al-free and Al-bearing compositions, respectively, respectively. The D/H equilibration within fluids and melts and, therefore, D/H partitioning between coexisting fluid and melt reflect the influence of dissolved H2O(D2O) in melts and dissolved silicate components in H2O(D2O) fluid on their structure. The positive temperature- and pressure-dependence of silicate solubility and on silicate structure in silicate-saturated aqueous fluid governs the D/H fractionation in the fluid because increasing silicate solute concentration in fluid results in silicate polymerization [2]. These structural effects may be analogous to observed solute-dependent oxygen isotope fractionation between brine and CO2 [3]. In the temperature

  9. 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.

  10. Studies on the conformational transformations of L-arginine molecule in aqueous solution with temperature changing by circular dichroism spectroscopy and optical rotations

    Science.gov (United States)

    Wang, Luning; Zhang, Guanghui; Wang, Xinqiang; Wang, Lei; Liu, Xitao; Jin, Lutong; Xu, Dong

    2012-10-01

    Experimental measurements, including circular dichroism (CD) spectroscopy and optical rotations have been employed to characterize the changing tendency of molecular conformations of the full protonated L-arginine (LA2+) in aqueous solution with the rising of temperature. Calculating methods, including conformational search, molecular structural optimization, CD responses as well as specific rotation calculations have been performed to interpret experimental results. Calculated results, no matter in CD spectra or specific rotations, are consistent with experiments, which strongly certify the transformation of molecular conformations. This successful reproduction of experimental results with molecular simulations in both areas of CD responses and optical rotations is of great significance. More detailed analysis about the relationship between LA2+ molecular structure and the optical activity has been conducted.

  11. Thermodynamics of aqueous solutes at high temperatures and pressures: Application of the hydration theory and implications for fluid-mediated mass transfer

    Science.gov (United States)

    Sulak, M.; Dolejs, D.

    2012-04-01

    Magmatic activity and prograde devolatilization of subducting or underplating lithologies release large quantities of aqueous fluids that act as mass and heat transfer agents in the planetary interiors. Understanding of mineral-melt-fluid interactions is essential for evaluating the effects of fluid-mediated mass transport in subduction zones, collisional orogens as well as in igneous provinces. The thermodynamic properties of aqueous species were frequently described by the Helgeson-Kirkham-Flowers equation of state [1] but its utility is limited by inavailability of the solvent dielectric properties at high pressures and temperatures, and by decoupling of species-solvent mechanical and electrostatic interactions that cannot be separated within the Born theory. Systematic description of the hydration process in a Born-Haber cycle leads to the following thermochemical contributions: (i) thermodynamic properties of an unhydrated species, (ii) the pressure-volume work required to create a cavity within the solvent to accommodate the species, described by the scaled particle theory, (iii) entropic contribution related to changes in the solute's and the solvent's kinetic degrees of freedom, and (iv) contribution from the solute-solvent molecular interactions and corresponding rearrangement of the solvent molecules to form the hydration shell. Application of the spatial correlation functions [2, 3] results in apparent Gibbs energy of aqueous species, ΔaGi = a + bT + cTlnT + dP + eTlnρ + fTρlnρ, where athrough f represent constants related to standard thermodynamic properties of aqueous species (ΔfH, S, V, cP) and to solvent volumetric properties at 298.15 K and 1 bar (ρ, α, β etc.). In phase equilibrium calculations, the number of required parameters often reduces to four (c = f = 0) while noting that H2O density as the only solvent-related property is accurately known to extreme temperatures and pressures. The equation of state parameters were calibrated for 30

  12. Extraction of mercury(II) with sulfurized jojoba oil

    Energy Technology Data Exchange (ETDEWEB)

    Wisniak, J.; Schorr, G.; Zacovsky, D.; Belfer, S. (Ben-Gurion Univ. of the Negev, Beersheba (Israel). Dept. of Chemical Engineering)

    1990-09-01

    Sulfurized jojoba oil containing 12% by weight S has been tested as an extractant for Hg(II) from aqueous solutions. This paper reports on experiments performed with the extractant dissolved in a solvent (liquid--liquid extraction) or adsorbed in an appropriate resin matrix (solid--liquid extraction). The extraction characteristics of both systems have been measured and show that sulfurized jojoba oil exhibits very good possibilities as an extractant. The performance of several resins treated with sulfurized jojoba oil for adsorbing mercury(II) was studied. The morphology of the different resins was examined by using scanning electron microscopy. The sulfurized oil is attached to the resin sites through the sulfur atoms; it is estimated that there are about 2 mol of S active sites per kilogram of resin.

  13. Study of thermodynamic and transport properties of glycine, diglycine, and triglycine in aqueous tartrazine at different temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Ali, Anwar; Patel, Rajan; Khan, Shahjahan; Bhushan, Vidiksha [Dept. of Chemistry, Jamia Millia Islamia (Central Univ.), New Delhi (India)

    2009-11-15

    The densities ({rho}), viscosities ({eta}), and refractive indices (n{sub D}) of (0.01, 0.05, 0.10, 0.15, and 0.20 m) amino acid, glycine, and peptides, diglycine and triglycine in 0.01 m aqueous tartrazine solution were determined at 288.15, 293.15, 298.15, 303.15, 308.15, and 313.15 K. The density data were utilized to evaluate apparent molar volumes ({phi}{sub v}) which, in turn, were used to determine partial molar volumes ({phi}{sub v} ) using Masson's equation. The transfer volumes were also calculated. The viscosity data were analyzed using the Jones-Dole equation to determine the viscosity coefficients and the activation parameters. The activation parameters of viscous flow were obtained to throw light on the mechanism of viscous flow. The molar refraction was calculated using the refractive index data. The results were interpreted in the light of ion-ion, ion-nonpolar, and nonpolar-nonpolar interactions and the effect of increasing hydrophobicity as we move from glycine to triglycine on these interactions in presence of the dye tartrazine was also investigated. (orig.)

  14. Study of Thermodynamic and Transport Properties of Glycine, Diglycine, and Triglycine in Aqueous Tartrazine at Different Temperatures

    Science.gov (United States)

    Ali, Anwar; Patel, Rajan; Khan, Shahjahan; Bhushan, Vidiksha

    2009-11-01

    The densities (ρ), viscosities (η), and refractive indices (nD) of (0.01, 0.05, 0.10, 0.15, and 0.20 m) amino acid, glycine, and peptides, diglycine and triglycine in 0.01 m aqueous tartrazine solution were determined at 288.15, 293.15, 298.15, 303.15, 308.15, and 313.15 K. The density data were utilized to evaluate apparent molar volumes (φv) which, in turn, were used to determine partial molar volumes (φv ◦) using Masson's equation. The transfer volumes were also calculated. The viscosity data were analyzed using the Jones-Dole equation to determine the viscosity coefficients and the activation parameters. The activation parameters of viscous flow were obtained to throw light on the mechanism of viscous flow. The molar refraction was calculated using the refractive index data. The results were interpreted in the light of ion-ion, ion-nonpolar, and nonpolar-nonpolar interactions and the effect of increasing hydrophobicity as we move from glycine to triglycine on these interactions in presence of the dye tartrazine was also investigated.

  15. Influence of temperature on the kinetics absorption of carbon dioxide in aqueous of enzyme catalysed MDEA solutions

    NARCIS (Netherlands)

    Penders-van Elk, Nathalie J. M. C.; van Aken, Coen; Versteeg, Geert F.

    In the present work the absorption of carbon dioxide in 1000 mol m(-3) N-methyldiethanolamine (MDEA) solutions with and without enzyme has been studied in a stirred cell reactor in the temperature range 278-343 K and enzyme concentrations ranging from 0 to 1600 gm(-3). During this study a new type

  16. Organic solvent modifier and temperature effects in non-aqueous size-exclusion chromatography on reversed-phase columns.

    Science.gov (United States)

    Caltabiano, Anna M; Foley, Joe P; Striegel, André M

    2018-01-05

    Common reversed-phase columns (C 18 , C 4 , phenyl, and cyano) offer inert surfaces suitable for the analysis of polymers by size-exclusion chromatography (SEC). The effect of tetrahydrofuran (THF) solvent and the mixtures of THF with a variety of common solvents used in high performance liquid chromatography (acetonitrile, methanol, dimethylformamide, 2-propanol, ethanol, acetone and chloroform) on reversed-phase stationary phase characteristics relevant to size exclusion were studied. The effect of solvent on the elution of polystyrene (PS) and poly(methyl methacrylate) (PMMA) and the effect of column temperature (within a relatively narrow range corresponding to typical chromatographic conditions, i.e., 10°C-60°C) on the SEC partition coefficients K SEC of PS and PMMA polymers, were also investigated. The bonded phases show remarkable differences in size separations when binary mixtures of THF with other solvents are used as the mobile phase. The solvent impact can be two-fold: (i) change of the polymeric coil size, and possible shape, and (ii) change of the stationary phase pore volume. If the effect of this impact is properly moderated, then the greatest benefit of optimized solute resolution can be achieved. Additionally, this work provides an insight on solvent-stationary phase interactions and their effects on column pore volume. The only effect of temperature observed in our studies was a decreased elution volume of the polymers with increasing temperature. SEC partition coefficients were temperature-independent in the range of 10°C-60°C and therefore, over this temperature range elution of PS and PMMA polymers is by near-ideal SEC on reversed-phase columns. Non-ideal SEC appears to occur for high molar mass PMMA polymers on a cyano column when alcohols are used as mobile phase modifiers. Copyright © 2017 Elsevier B.V. All rights reserved.

  17. A study on carbothermal reduction of sulfur dioxide to elemental sulfur using oilsands fluid coke

    Energy Technology Data Exchange (ETDEWEB)

    Bejarano, C.A.; Jia, C.Q.; Chung, K.H. [University of Toronto, Toronto, ON (Canada). Dept. of Chemical Engineering and Applied Chemistry

    2001-02-15

    Experiments and reaction equilibrium calculations were carried out for the SO{sub 2} gas and oilsands fluid coke system. The goal was to develop a coke-based sulfur-producing flue gas desulfurization (SP-FGD) process that removes SO{sub 2} from flue gases and converts it into elemental sulfur. The conversion of SO{sub 2} to elemental sulfur proceeded efficiently at temperatures higher than 600{degree}C, and the sulfur yield reached a maximum ({lt} 95%) at about 700{degree}C. An increase of temperature beyond 700{degree}C enhanced the reduction of product elemental sulfur, resulting in the formation of reduced sulfur species (COS and CS{sub 2}), which lowered the sulfur yield at 900{degree}C to 90%. Although equilibrium calculations suggest that a lower temperature favors the conversion of SO{sub 2} as well as the yield of elemental sulfur, experiments showed no formation of elemental sulfur at 600{degree}C and below, likely due to hindered kinetics. Faster reduction of SO{sub 2} was observed at a higher temperature in the range of 700-1000{degree}C. A complete conversion of SO{sub 2} was achieved in about 8 s at 700{degree}C. Prolonging the product gas-coke contact, the yield of elemental sulfur decreased due to the formation of COS and CS{sub 2} while the SO{sub 2} conversion remained complete. Equilibrium calculations suggest that the ultimate yield of elemental sulfur maximizes at the C/SO{sub 2} ratio of 1, which represents the stoichiometry of SO{sub 2} + C {yields} CO{sub 2} + S. For the C/SO{sub 2} ratio {lt} 1, equilibrium calculations predict elemental sulfur and CO{sub 2} being major products, suggesting that SO{sub 2} + C {yields} CO{sub 2} + S is the predominant reaction if SO{sub 2} is in excess. Experiments revealed that elemental sulfur and CO{sub 2} were the only major products if the conversion of SO{sub 2} was incomplete, which is in agreement with the result of the equilibrium modeling. 18 refs., 12 figs.

  18. Global approach for the selection of high temperature comprehensive two-dimensional gas chromatography experimental conditions and quantitative analysis in regards to sulfur-containing compounds in heavy petroleum cuts.

    Science.gov (United States)

    Mahé, Laure; Dutriez, Thomas; Courtiade, Marion; Thiébaut, Didier; Dulot, Hugues; Bertoncini, Fabrice

    2011-01-21

    Extending the knowledge on sulfur-containing compounds is crucial for the petroleum industry because they contribute to atmospheric pollution by combustion. Most of them are concentrated in heavy petroleum cuts, such as vacuum gas oils (VGOs). However, the resolution of the existing analytical methods does not allow a quantitative speciation of S-compounds contained in VGOs. Therefore, a high temperature GC×GC chromatograph hyphenated to a SCD was implemented in this study to obtain a quantitative S-compounds speciation. Firstly, various thermally stable stationary phases, in particular the new ionic liquid IL59 and Mega Wax-HT, were investigated in 1D-GC as a way to reduce the number of columns sets to be used in GC×GC. Consequently, several normal and reversed configurations of these columns were selected and tested in GC×GC. Then, a decision method was applied to facilitate the choice of the best combination of columns. Finally, the most adapted methods led to an innovative group type quantification and to a quantitative distribution of heavy sulfur species contained in a VGO sample. These results represent a major step towards the study of S-compounds in heavy petroleum cuts. Copyright © 2010 Elsevier B.V. All rights reserved.

  19. 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

  20. Radiolysis of Sulfuric Acid, Sulfuric Acid Monohydrate, and Sulfuric Acid Tetrahydrate and Its Relevance to Europa

    Science.gov (United States)

    Loeffler, M. J.; Hudson, R. L.; Moore, M. H.; Carlson, R. W.

    2011-01-01

    We report laboratory studies on the 0.8 MeV proton irradiation of ices composed of sulfuric acid (H2SO4), sulfuric acid monohydrate (H2SO4 H2O), and sulfuric acid tetrahydrate (H2SO4 4H2O) between 10 and 180 K. Using infrared spectroscopy, we identify the main radiation products as H2O, SO2, (S2O3)x, H3O+, HSO4(exp -), and SO4(exp 2-). At high radiation doses, we find that H2SO4 molecules are destroyed completely and that H2SO4 H2O is formed on subsequent warming. This hydrate is significantly more stable to radiolytic destruction than pure H2SO4, falling to an equilibrium relative abundance of 50% of its original value on prolonged irradiation. Unlike either pure H2SO4 or H2SO4 H2O, the loss of H2SO4 4H2O exhibits a strong temperature dependence, as the tetrahydrate is essentially unchanged at the highest irradiation temperatures and completely destroyed at the lowest ones, which we speculate is due to a combination of radiolytic destruction and amorphization. Furthermore, at the lower temperatures it is clear that irradiation causes the tetrahydrate spectrum to transition to one that closely resembles the monohydrate spectrum. Extrapolating our results to Europa s surface, we speculate that the variations in SO2 concentrations observed in the chaotic terrains are a result of radiation processing of lower hydration states of sulfuric acid and that the monohydrate will remain stable on the surface over geological times, while the tetrahydrate will remain stable in the warmer regions but be destroyed in the colder regions, unless it can be reformed by other processes, such as thermal reactions induced by diurnal cycling.

  1. Evidence of temperature dependent activation barriers for near-threshold aqueous photoionization of 2‧-deoxyguanosine and tryptophan

    Science.gov (United States)

    Papadantonakis, George A.; Stevenson, Kenneth L.; LeBreton, Pierre R.

    2001-09-01

    Alkaline 2‧-deoxyguanosine undergoes one- and two-photon laser photoionization at 266 nm. Similar to tryptophan and indole, the one-photon quantum yield increases five-fold between 296 and 362 K. Earlier Arrhenius analyses of tryptophan and indole photoionization rate constants, yielded unreasonably large pre-exponential factors (1013-1018 s-1). An analysis employing pre-exponential factors for diffusion controlled reactions (1010-1011 s-1) provides evidence of activation barriers that decrease with increasing temperature over a range where water structure undergoes significant changes. In the context of Marcus theory, this analysis suggests that curvatures of the electron-transfer free energy surfaces decrease as temperature increases.

  2. Methanol-Water Aqueous-Phase Reforming with the Assistance of Dehydrogenases at Near-Room Temperature.

    Science.gov (United States)

    Shen, Yangbin; Zhan, Yulu; Li, Shuping; Ning, Fandi; Du, Ying; Huang, Yunjie; He, Ting; Zhou, Xiaochun

    2018-01-11

    As an excellent hydrogen-storage medium, methanol has many advantages, such as high hydrogen content (12.6 wt %), low cost, and availability from biomass or photocatalysis. However, conventional methanol-water reforming usually proceeds at high temperatures. In this research, we successfully designed a new effective strategy to generate hydrogen from methanol at near-room temperature. The strategy involved two main processes: CH 3 OH→HCOOH→H 2 and NADH→HCOOH→H 2 . The first process (CH 3 OH→HCOOH→H 2 ) was performed by an alcohol dehydrogenase (ADH), an aldehyde dehydrogenase (ALDH), and an Ir catalyst. The second procedure (NADH→HCOOH→H 2 ) was performed by formate dehydrogenase (FDH) and the Ir catalyst. The Ir catalyst used was a previously reported polymer complex catalyst [Cp*IrCl 2 (ppy); Cp*=pentamethylcyclopentadienyl, ppy=polypyrrole] with high catalytic activity for the decomposition of formic acid at room temperature and is compatible with enzymes, coenzymes, and poisoning chemicals. Our results revealed that the optimum hydrogen generation rate could reach up to 17.8 μmol h -1  g cat -1 under weak basic conditions at 30 °C. This will have high impact on hydrogen storage, production, and applications and should also provide new inspiration for hydrogen generation from methanol. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Sucrose, glucose, and fructose extraction in aqueous carrot root extracts prepared at different temperatures by means of direct NMR measurements.

    Science.gov (United States)

    Cazor, Anne; Deborde, Catherine; Moing, Annick; Rolin, Dominique; This, Hervé

    2006-06-28

    Solutions obtained by heating carrot roots in water (stocks) are widely used in the food industry, but little information is available regarding the metabolites (intermediates and products of metabolism) found in the stock. The effect of treatment temperature and duration on the sugar composition of stocks was investigated directly by quantitative (1)H NMR spectroscopy, to understand the extraction mechanism when processing at 100 degrees C. Stocks prepared at three different temperatures (50, 75, and 100 degrees C) were investigated for up to 36 h. Three sugars (sucrose, glucose, and fructose) were detected and quantified. The concentrations of these three sugars reached a maximum after 9 h when the temperature of treatment was 50 or 75 degrees C. At 100 degrees C, the sucrose concentration reached a maximum after 3 h, whereas the concentration of glucose and fructose was still increasing at that time. Comparison of the kinetic composition of these carrot stocks with that of model sugar solutions leads to the proposal that the changes in stock composition result from sugar diffusion, sucrose hydrolysis, and hydroxymethylfurfural (HMF) formation.

  4. Use of polysulfides of alkali and alkaline-earth metals to obtain highly dispersed sulfur

    International Nuclear Information System (INIS)

    Massalimov, I.A.; Vikhareva, I.N.; Kireeva, M.S.

    2008-01-01

    Possibilities of obtaining polysulfides of alkali and alkaline earth metals (M is Na, K, Ca, Sr, Ba) in aqueous solutions were considered. The composition of the polysulfides and their concentration in solutions were found. The efficiencies of application of highly dispersed sulfur, produced from calcium polysulfide, and colloid sulfur as a fungicide were compared [ru

  5. A new approach of the understanding of sulfur dioxide reduction in non-aqueous solvent; Une nouvelle approche de la comprehension de la reduction du dioxyde de soufre en solvant non aqueux

    Energy Technology Data Exchange (ETDEWEB)

    Potteau, E.; Levillain, E.; Lelieur, J.P. [Laboratoire de Spectrochimie Infrarouge et Raman (LASIR, UPR 2631 CNRS) Haute Etudes Industrielles (HEI), 59 - Lille (France)

    1996-12-31

    The study of SO{sub 2} reduction in non-aqueous solvent can help to understand the functioning of Li/SO{sub 2} batteries and to find a simpler way for the synthesis of Li{sub 2}S{sub 2}O{sub 4} dithionite. This paper presents the results of electrochemical studies (cycle volt-amperometry in semi-infinite and thin film diffusion conditions, visible spectro-electrochemistry) and spectroscopic studies (UV, visible and RPE) performed on SO{sub 2} solutions. A mechanism of SO{sub 2} reduction is proposed and discussed. (J.S.) 18 refs.

  6. Monte Carlo modelling of non-isothermal degradation of two cyanidin-based anthocyanins in aqueous system at high temperatures and its impact on antioxidant capacities.

    Science.gov (United States)

    Sui, Xiaonan; Zhou, Weibiao

    2014-04-01

    The non-isothermal degradation of two cyanidin-based anthocyanins, cyanidin-3-glucoside and cyanidin-3-rutinoside, was investigated in aqueous system within the temperature range from 100 to 165 °C, and the degradation kinetics was modelled using Monte Carlo simulation. The two anthocyanins showed different stability, with cyanidin-3-glucoside exhibiting a higher degradation rate than cyanidin-3-rutinoside. The derived degradation rate at the reference temperature of 132.5 °C and activation energy of cyanidin-3-glucoside and cyanidin-3-rutinoside were 0.0047 and 0.0023 s(-1), and 87 and 104 kJ/mol, respectively. The antioxidant capacity of the thermally processed anthocyanins solutions was measured by using ABTS and DPPH assays. Results showed that the antioxidant capacity of the samples remained at the same level during the thermal treatment process under various conditions, i.e., there was no significant difference (P>0.05) in the antioxidant capacity amongst the samples despite their significantly different contents of the two anthocyanins. Copyright © 2013 Elsevier Ltd. All rights reserved.

  7. Effect of precursor solutions stirring on deep level defects concentration and spatial distribution in low temperature aqueous chemical synthesis of zinc oxide nanorods

    Energy Technology Data Exchange (ETDEWEB)

    Alnoor, Hatim, E-mail: hatim.alnoor@liu.se; Chey, Chan Oeurn; Pozina, Galia; Willander, Magnus; Nur, Omer [Department of Science and Technology (ITN), Campus Norrköping, Linköping University, SE-601 74 Norrköping (Sweden); Liu, Xianjie; Khranovskyy, Volodymyr [Department of Physics, Chemistry and Biology (IFM), Linköping University, SE-583 81 Linköping (Sweden)

    2015-08-15

    Hexagonal c-axis oriented zinc oxide (ZnO) nanorods (NRs) with 120-300 nm diameters are synthesized via the low temperature aqueous chemical route at 80 °C on silver-coated glass substrates. The influence of varying the precursor solutions stirring durations on the concentration and spatial distributions of deep level defects in ZnO NRs is investigated. Room temperature micro-photoluminesnce (μ-PL) spectra were collected for all samples. Cathodoluminescence (CL) spectra of the as-synthesized NRs reveal a significant change in the intensity ratio of the near band edge emission (NBE) to the deep-level emission (DLE) peaks with increasing stirring durations. This is attributed to the variation in the concentration of the oxygen-deficiency with increasing stirring durations as suggested from the X-ray photoelectron spectroscopy analysis. Spatially resolved CL spectra taken along individual NRs revealed that stirring the precursor solutions for relatively short duration (1-3 h), which likely induced high super saturation under thermodynamic equilibrium during the synthesis process, is observed to favor the formation of point defects moving towards the tip of the NRs. In contrary, stirring for longer duration (5-15 h) will induce low super saturation favoring the formation of point defects located at the bottom of the NRs. These findings demonstrate that it is possible to control the concentration and spatial distribution of deep level defects in ZnO NRs by varying the stirring durations of the precursor solutions.

  8. Corrosion behaviour of sensitized and unsensitized Alloy 900 (UNS 1.4462) in concentrated aqueous lithium bromide solutions at different temperatures

    International Nuclear Information System (INIS)

    Leiva-Garcia, R.; Munoz-Portero, M.J.; Garcia-Anton, J.

    2010-01-01

    Duplex stainless steels can undergo microstructural changes if they are heated improperly. When that happens, duplex stainless steels are sensitized and intermetallic phases appear. The high Chromium and Molybdenum content promotes the formation of secondary phases as a consequence of the heat treatment. These secondary phases, which are rich in alloying elements, such as Cr and Mo, deplete these elements from the neighbouring phases, leading to a reduction in corrosion resistance. In order to study the influence of the secondary phases on the corrosion parameters, samples of duplex stainless steel, Alloy 900 (UNS 1.4462), have been heated in argon atmosphere at 825 deg. C for 1 h. The corrosion behaviour of sensitized and unsensitized Alloy 900 has been analyzed in a concentrated aqueous lithium bromide (LiBr) solution of 992 g/L by means of cyclic potentiodynamic curves. Secondary phase presence reduces the pitting potential value of Alloy 900. Besides, the pitting potential decreases with temperature. On the other hand, the corrosion potential and open circuit potential values increase with temperature and sensitization.

  9. 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).

  10. Isotopic equilibria in aqueous clusters at low temperatures: Insights from the MB-pol many-body potential

    Science.gov (United States)

    Videla, Pablo E.; Rossky, Peter J.; Laria, Daniel

    2018-02-01

    By combining path-integrals molecular dynamics simulations with the accurate MB-pol potential energy surface, we investigate the role of alternative potential models on isotopic fractionation ratios between H and D atoms at dangling positions in water clusters at low temperatures. Our results show clear stabilizations of the lighter isotope at dangling sites, characterized by free energy differences ΔG that become comparable to or larger than kBT for temperatures below ˜75 K. The comparison between these results to those previously reported using the empirical q-TIP4P/F water model [P. E. Videla et al., J. Phys. Chem. Lett. 5, 2375 (2014)] reveals that the latter Hamiltonian overestimates the H stabilization by ˜25%. Moreover, predictions from the MB-pol model are in much better agreement with measured results reported for similar isotope equilibria at ice surfaces. The dissection of the quantum kinetic energies into orthogonal directions shows that the dominant differences between the two models are to be found in the anharmonic characteristics of the potential energy surfaces along OH bond directions involved in hydrogen bonds.

  11. Two cloud-point phenomena in tetrabutylammonium perfluorooctanoate aqueous solutions: anomalous temperature-induced phase and structure transitions.

    Science.gov (United States)

    Yan, Peng; Huang, Jin; Lu, Run-Chao; Jin, Chen; Xiao, Jin-Xin; Chen, Yong-Ming

    2005-03-24

    This paper reported the phase behavior and aggregate structure of tetrabutylammonium perfluorooctanoate (TBPFO), determined by differential scanning calorimeter, electrical conductivity, static/dynamic light scattering, and rheology methods. We found that above a certain concentration the TBPFO solution showed anomalous temperature-dependent phase behavior and structure transitions. Such an ionic surfactant solution exhibits two cloud points. When the temperature was increased, the solution turned from a homogeneous-phase to a liquid-liquid two-phase system, then to another homogeneous-phase, and finally to another liquid-liquid two-phase system. In the first homogeneous-phase region, the aggregates of TBPFO were rodlike micelles and the solution was Newtonian fluid. While in the second homogeneous-phase region, the aggregates of TBPFO were large wormlike micelles, and the solution behaved as pseudoplastic fluid that also exhibited viscoelastic behavior. We thought that the first cloud point might be caused by the "bridge" effect of the tetrabutylammonium counterion between the micelles and the second one by the formation of the micellar network.

  12. Fluorescence lifetime of Rhodamine B in aqueous solutions of polysaccharides and proteins as a function of viscosity and temperature.

    Science.gov (United States)

    Mercadé-Prieto, Ruben; Rodriguez-Rivera, Luis; Chen, Xiao Dong

    2017-11-08

    Rhodamine B (RhB) is a well known dye extensively used in thermometric studies, either considering the decrease in the fluorescence intensity or the lifetime (τ) with temperature. Lifetime measurements are preferred over intensity ones as they are more robust. In order to expand microscopy thermometry to complex food fluids, the effect of solutes on the τ of RhB was studied using fluorescence lifetime imaging microscopy (FLIM) in a two-photon microscope. Polysaccharides of different molecular weights (glucose, lactose, dextran, maltodextrin, and sodium alginate), as well as whey proteins, were considered as typical model food ingredients. A linear increase in τ with the concentration is observed in most polysaccharides, highlighting that it is not due to an increase in the macroscopic viscosity, but in maltodextrins a Langmuir-like concentration dependence is observed. There are extensive interactions between RhB and whey proteins at small concentrations that quickly increase τ up to saturation at >10 wt% proteins, with τ modelled well using an adsorption Langmuir model. Therefore, the effect of solutes on RhB τ is not related to changes in the macroscopic viscosity. The temperature sensitivity of τ, quantified using apparent activation energies, decreases at high solute contents.

  13. Toxicokinetics of sulfur mustard

    NARCIS (Netherlands)

    Langenberg, J.P.; Schans, M.J. van der; Noort, D.

    2016-01-01

    In this chapter an overview is presented on the state of knowledge concerning the toxicokinetics of sulfur mustard. The procedures to analyze intact sulfur mustard in the blood and tissues of laboratory animals at toxicologically relevant levels are discussed. In view of the fact that the reviewed

  14. The viscosity and temperature dependence of X-band ESR lineshapes of Gd(III) aqueous complex.

    Science.gov (United States)

    Zhou, Xiangzhi; Westlund, Per-Olof

    2005-11-01

    X-band ESR spectra of Gd-aqua complex in various weight concentration of glycerol have been recorded at four temperatures. The interpretation of the ESR linewidth is preformed using both the stochastic Liouville approach (SLA) and a perturbation theory. The SLA uses a one dynamic model of the zero-field splitting whereas the perturbation approach uses a two dynamic model. Both models can reproduce the variation of the linewidth with respect to viscosity. In the SLA model, both the zero-field splitting (ZFS) interaction and the correlation time vary with the glycerol content. In the two dynamic perturbation model, only the correlation times are viscosity dependent. The two models give different NMRD profiles.

  15. Enthalpies of solution of methylcalix[4]resorcinarene in non-aqueous solvents as a function of concentration and temperature

    Energy Technology Data Exchange (ETDEWEB)

    Riveros, Diana C. [Laboratorio de Termodinamica de Soluciones, Departamento de Quimica, Facultad de Ciencias, Universidad de los Andes, Bogota D.C. (Colombia); Martinez, Fleming [Grupo de Investigaciones Farmaceutico-Fisicoquimicas, Departamento de Farmacia, Facultad de Ciencias, Universidad Nacional de Colombia, Bogota D.C. (Colombia); Vargas, Edgar F., E-mail: edvargas@uniandes.edu.co [Laboratorio de Termodinamica de Soluciones, Departamento de Quimica, Facultad de Ciencias, Universidad de los Andes, Bogota D.C. (Colombia)

    2012-11-20

    Highlights: Black-Right-Pointing-Pointer The solution enthalpies of methylcalix[4]resorcinarene in alcohols have been measured. Black-Right-Pointing-Pointer The solution enthalpies of methylcalix[4]resorcinarene in alcohols are endothermic. Black-Right-Pointing-Pointer Enthalpies of transference are interpreted in terms of proton donor capacity of alcohols. - Abstract: Enthalpies of solution of 2,8,14,20-tetramethyl-4,6,10,12,16,18,22,24-octahydroxyresorci[4]arene in methanol, ethanol and propanol as a function of molal concentration at (288.15, 298.15 and 308.15) K were measured calorimetrically. The enthalpies of solvation were estimated. Using propanol as the referent solvent, transfer properties to other alcohols were also calculated. In addition, temperature dependence of the enthalpy of solution at infinite dilution was also obtained. The data were interpreted in terms of solute-solvent interactions.

  16. Enthalpies of solution of methylcalix[4]resorcinarene in non-aqueous solvents as a function of concentration and temperature

    International Nuclear Information System (INIS)

    Riveros, Diana C.; Martínez, Fleming; Vargas, Edgar F.

    2012-01-01

    Highlights: ► The solution enthalpies of methylcalix[4]resorcinarene in alcohols have been measured. ► The solution enthalpies of methylcalix[4]resorcinarene in alcohols are endothermic. ► Enthalpies of transference are interpreted in terms of proton donor capacity of alcohols. - Abstract: Enthalpies of solution of 2,8,14,20-tetramethyl-4,6,10,12,16,18,22,24-octahydroxyresorci[4]arene in methanol, ethanol and propanol as a function of molal concentration at (288.15, 298.15 and 308.15) K were measured calorimetrically. The enthalpies of solvation were estimated. Using propanol as the referent solvent, transfer properties to other alcohols were also calculated. In addition, temperature dependence of the enthalpy of solution at infinite dilution was also obtained. The data were interpreted in terms of solute–solvent interactions.

  17. 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.

  18. Detoxification of sulfur mustard by enzyme-catalyzed oxidation using chloroperoxidase.

    Science.gov (United States)

    Popiel, S; Nawała, J

    2013-10-10

    One of the most interesting methods for the detoxification of sulfur mustard is enzyme-catalyzed oxidation. This study examined the oxidative destruction of a sulfur mustard by the enzyme chloroperoxidase (EC 1.11.1.10). Chloroperoxidase (CPO) belongs to a group of enzymes that catalyze the oxidation of various organic compounds by peroxide in the presence of a halide ion. The enzymatic oxidation reaction is affected by several factors: pH, presence or absence of chloride ion, temperature, the concentrations of hydrogen peroxide and enzyme and aqueous solubility of the substrate. The optimum reaction conditions were determined by analyzing the effects of all factors, and the following conditions were selected: solvent, Britton-Robinson buffer (pH=3) with tert-butanol (70:30 v/v); CPO concentration, 16U/mL; hydrogen peroxide concentration, 40mmol/L; sodium chloride concentration, 20mmol/L. Under these reaction conditions, the rate constant for the reaction is 0.006s(-1). The Michaelis constant, a measure of the affinity of an enzyme for a particular substrate, is 1.87×10(-3)M for this system. The Michaelis constant for enzymes with a high affinity for their substrate is in the range of 10(-5) to 10(-4)M, so this value indicates that CPO does not have a very high affinity for sulfur mustard. Copyright © 2013 Elsevier Inc. All rights reserved.

  19. Apparent molar volumes and apparent molar heat capacities of aqueous D-lactose · H2O at temperatures from (278.15 to 393.15) K and at the pressure 0.35 MPa

    International Nuclear Information System (INIS)

    Sargent, J.D.; Niederhauser, T.L.; Woolley, E.M.

    2004-01-01

    Apparent molar volumes V phi and apparent molar heat capacities C p,phi were determined for aqueous solutions of D-lactose · H 2 O at molalities (0.01 to 0.34) mol · kg -1 at temperatures (278.15 to 393.15) K, and at the pressure 0.35 MPa. Our V phi values were calculated from densities obtained using a vibrating tube densimeter, and our C p,phi values were obtained using a twin fixed-cell, power-compensation, differential-output, temperature-scanning calorimeter. Our results for D-lactose(aq) and for D-lactcose · H 2 O were fitted to functions of m and T and compared with the literature results for aqueous D-glucose and D-galactose solutions. Infinite dilution partial molar volumes V 2 compfn and heat capacities C p,2 compfn are given over the range of temperatures

  20. Sulfuric Acid on Europa

    Science.gov (United States)

    1999-01-01

    Frozen sulfuric acid on Jupiter's moon Europa is depicted in this image produced from data gathered by NASA's Galileo spacecraft. The brightest areas, where the yellow is most intense, represent regions of high frozen sulfuric acid concentration. Sulfuric acid is found in battery acid and in Earth's acid rain. This image is based on data gathered by Galileo's near infrared mapping spectrometer.Europa's leading hemisphere is toward the bottom right, and there are enhanced concentrations of sulfuric acid in the trailing side of Europa (the upper left side of the image). This is the face of Europa that is struck by sulfur ions coming from Jupiter's innermost moon, Io. The long, narrow features that crisscross Europa also show sulfuric acid that may be from sulfurous material extruded in cracks. Galileo, launched in 1989, has been orbiting Jupiter and its moons since December 1995. JPL manages the Galileo mission for NASA's Office of Space Science, Washington DC. JPL is a division of the California Institute of Technology, Pasadena, CA.

  1. Synthesis of LaCoO{sub 3} nano-powders by aqueous gel-casting for intermediate temperature solid oxide fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Cheng, Chia Siang; Zhang, Lan; Jiang, San Ping [School of Mechanical and Aerospace Engineering, Nanyang Technological University (Singapore); Zhang, Yu.Jun [Key Lab for Liquid Structure and Heredity of Ministry of Education, School of Materials Science and Engineering, Shandong University, Jinan (China)

    2008-04-15

    LaCoO{sub 3} (LC) perovskite powders for intermediate temperature solid oxide fuel cells (IT-SOFCs) are synthesized by a simple and cost-effective aqueous gel-casting technique using metal nitrates as raw materials. Effect of the ratio of organic precursors (acrylamide (AM) monomer and N,N'-Methylenebisacrylamide (MBAM) crosslinker) to metal nitrates (lanthanum nitrate, cobalt nitrate) and the ratio of AM to MBAM on the particle size are investigated in detail. TEM results indicate that the particle size of LC nano-powders is in the range of 31-60 nm and decreases with increasing ratio of organic precursor to metal nitrates but is not affected by the ratio of AM to MBAM. Preliminary results show that the nano-structured electrode approach based on wet impregnation is effective to combine the high electrocatalytic activity of LC nano-powders and the structural stability of La{sub 0.72}Sr{sub 0.18}MnO{sub 3} {sub -} {sub {delta}} (LSM) electrodes for the development of IT-SOFC cathodes. (author)

  2. Comparison of iso-eluotropic mobile phases at different temperatures for the separation of triacylglycerols in Non-Aqueous Reversed Phase Liquid Chromatography.

    Science.gov (United States)

    Hmida, Dorra; Abderrabba, Manef; Tchapla, Alain; Héron, Sylvie; Moussa, Fathi

    2015-05-15

    Triacylglycerols (TAGs) are a large class of neutral lipids that naturally occur in both plant and animal oils and fats. Their analyses in Non-Aqueous Reversed Phase Liquid Chromatography (NARP) require a mixture of weak solvent (mostly acetonitrile) and strong solvent. In the present work, we have established eluotropic solvent strength scale of several binary mobile phases on C18 bonded silica at different temperatures (acetonitrile/methylene chloride, acetonitrile/acetone, acetonitrile/ethyl acetate, acetonitrile/propan-2-ol, and acetonitrile/butan-1-ol at 25°C, 43°C, 63°C and 85°C); it is based on the methylene selectivity and the use of homologous series. We show that this scale is well suited to the TAGs analysis. The analysis of nine seed oils (Aleurites fordii, Calophyllum inophyllum, Glycina max, Olea europea, Orbignya olifeira, Pinus koraiensis, Pistacia lentiscus, Punica granatum and Ribes nigrum) in iso-eluotropic conditions leads to propose unambiguously the couple MeCN/BuOH at 25°C as the best system to separate TAGs. The use of butanol, as strong solvent, provides very good TAGs congeners separations and avoids the use of chlorinated solvents which gave to this day the best separations. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. 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.

  4. Aqueous phase oxidation of sulphur dioxide by ozone in cloud droplets

    Science.gov (United States)

    Hoyle, C. R.; Fuchs, C.; Järvinen, E.; Saathoff, H.; Dias, A.; El Haddad, I.; Gysel, M.; Coburn, S. C.; Tröstl, J.; Bernhammer, A.-K.; Bianchi, F.; Breitenlechner, M.; Corbin, J. C.; Craven, J.; Donahue, N. M.; Duplissy, J.; Ehrhart, S.; Frege, C.; Gordon, H.; Höppel, N.; Heinritzi, M.; Kristensen, T. B.; Molteni, U.; Nichman, L.; Pinterich, T.; Prévôt, A. S. H.; Simon, M.; Slowik, J. G.; Steiner, G.; Tomé, A.; Vogel, A. L.; Volkamer, R.; Wagner, A. C.; Wagner, R.; Wexler, A. S.; Williamson, C.; Winkler, P. M.; Yan, C.; Amorim, A.; Dommen, J.; Curtius, J.; Gallagher, M. W.; Flagan, R. C.; Hansel, A.; Kirkby, J.; Kulmala, M.; Möhler, O.; Stratmann, F.; Worsnop, D. R.; Baltensperger, U.

    2016-02-01

    The growth of aerosol due to the aqueous phase oxidation of sulfur dioxide by ozone was measured in laboratory-generated clouds created in the Cosmics Leaving OUtdoor Droplets (CLOUD) chamber at the European Organization for Nuclear Research (CERN). Experiments were performed at 10 and -10 °C, on acidic (sulfuric acid) and on partially to fully neutralised (ammonium sulfate) seed aerosol. Clouds were generated by performing an adiabatic expansion - pressurising the chamber to 220 hPa above atmospheric pressure, and then rapidly releasing the excess pressure, resulting in a cooling, condensation of water on the aerosol and a cloud lifetime of approximately 6 min. A model was developed to compare the observed aerosol growth with that predicted using oxidation rate constants previously measured in bulk solutions. The model captured the measured aerosol growth very well for experiments performed at 10 and -10 °C, indicating that, in contrast to some previous studies, the oxidation rates of SO2 in a dispersed aqueous system can be well represented by using accepted rate constants, based on bulk measurements. To the best of our knowledge, these are the first laboratory-based measurements of aqueous phase oxidation in a dispersed, super-cooled population of droplets. The measurements are therefore important in confirming that the extrapolation of currently accepted reaction rate constants to temperatures below 0 °C is correct.

  5. Aqueous phase oxidation of sulphur dioxide by ozone in cloud droplets

    Directory of Open Access Journals (Sweden)

    C. R. Hoyle

    2016-02-01

    Full Text Available The growth of aerosol due to the aqueous phase oxidation of sulfur dioxide by ozone was measured in laboratory-generated clouds created in the Cosmics Leaving OUtdoor Droplets (CLOUD chamber at the European Organization for Nuclear Research (CERN. Experiments were performed at 10 and −10 °C, on acidic (sulfuric acid and on partially to fully neutralised (ammonium sulfate seed aerosol. Clouds were generated by performing an adiabatic expansion – pressurising the chamber to 220 hPa above atmospheric pressure, and then rapidly releasing the excess pressure, resulting in a cooling, condensation of water on the aerosol and a cloud lifetime of approximately 6 min. A model was developed to compare the observed aerosol growth with that predicted using oxidation rate constants previously measured in bulk solutions. The model captured the measured aerosol growth very well for experiments performed at 10 and −10 °C, indicating that, in contrast to some previous studies, the oxidation rates of SO2 in a dispersed aqueous system can be well represented by using accepted rate constants, based on bulk measurements. To the best of our knowledge, these are the first laboratory-based measurements of aqueous phase oxidation in a dispersed, super-cooled population of droplets. The measurements are therefore important in confirming that the extrapolation of currently accepted reaction rate constants to temperatures below 0 °C is correct.

  6. Determination of phosphorus, sulfur and the halogens using high-temperature molecular absorption spectrometry in flames and furnaces-A review

    International Nuclear Information System (INIS)

    Welz, Bernhard; Lepri, Fabio G.; Araujo, Rennan G.O.; Ferreira, Sergio L.C.; Huang Maodong; Okruss, Michael; Becker-Ross, Helmut

    2009-01-01

    The literature about the investigation of molecular spectra of phosphorus, sulfur and the halogens in flames and furnaces, and the use of these spectra for the determination of these non-metals has been reviewed. Most of the investigations were carried out using conventional atomic absorption spectrometers, and there were in essence two different approaches. In the first one, dual-channel spectrometers with a hydrogen or deuterium lamp were used, applying the two-line method for background correction; in the second one, a line source was used that emitted an atomic line, which overlapped with the molecular spectrum. The first approach had the advantage that any spectral interval could be accessed, but it was susceptible to spectral interference; the second one had the advantage that the conventional background correction systems could be used to minimize spectral interferences, but had the problem that an atomic line had to be found, which was overlapping sufficiently well with the maximum of the molecular absorption spectrum. More recently a variety of molecular absorption spectra were investigated using a low-resolution polychromator with a CCD array detector, but no attempt was made to use this approach for quantitative determination of non-metals. The recent introduction and commercial availability of high-resolution continuum source atomic absorption spectrometers is offering completely new possibilities for molecular absorption spectrometry and its use for the determination of non-metals. The use of a high-intensity continuum source together with a high-resolution spectrometer and a CCD array detector makes possible selecting the optimum wavelength for the determination and to exclude most spectral interferences.

  7. Effect of precursor solutions stirring on deep level defects concentration and spatial distribution in low temperature aqueous chemical synthesis of zinc oxide nanorods

    Directory of Open Access Journals (Sweden)

    Hatim Alnoor

    2015-08-01

    Full Text Available Hexagonal c-axis oriented zinc oxide (ZnO nanorods (NRs with 120-300 nm diameters are synthesized via the low temperature aqueous chemical route at 80 °C on silver-coated glass substrates. The influence of varying the precursor solutions stirring durations on the concentration and spatial distributions of deep level defects in ZnO NRs is investigated. Room temperature micro-photoluminesnce (μ-PL spectra were collected for all samples. Cathodoluminescence (CL spectra of the as-synthesized NRs reveal a significant change in the intensity ratio of the near band edge emission (NBE to the deep-level emission (DLE peaks with increasing stirring durations. This is attributed to the variation in the concentration of the oxygen-deficiency with increasing stirring durations as suggested from the X-ray photoelectron spectroscopy analysis. Spatially resolved CL spectra taken along individual NRs revealed that stirring the precursor solutions for relatively short duration (1-3 h, which likely induced high super saturation under thermodynamic equilibrium during the synthesis process, is observed to favor the formation of point defects moving towards the tip of the NRs. In contrary, stirring for longer duration (5-15 h will induce low super saturation favoring the formation of point defects located at the bottom of the NRs. These findings demonstrate that it is possible to control the concentration and spatial distribution of deep level defects in ZnO NRs by varying the stirring durations of the precursor solutions.

  8. Optimizations of packed sorbent and inlet temperature for large volume-direct aqueous injection-gas chromatography to determine high boiling volatile organic compounds in water.

    Science.gov (United States)

    Yu, Bofan; Song, Yonghui; Han, Lu; Yu, Huibin; Liu, Yang; Liu, Hongliang

    2014-08-22

    For the expanded application area, fast trace analysis of certain high boiling point (i.e., 150-250 °C) volatile organic compounds (HVOCs) in water, a large volume-direct aqueous injection-gas chromatography (LV-DAI-GC) method was optimized for the following parameters: packed sorbent for sample on-line pretreatment, inlet temperature and detectors configuration. Using the composite packed sorbent self-prepared with lithium chloride and a type of diatomite, the method enabled safe injection of an approximately 50-100 μL sample at an inlet temperature of 150 °C in the splitless mode and separated HVOCs from water matrix in 2 min. Coupled with a flame ionization detector (FID), an electron capture detector (ECD) and a flame photometric detector (FPD), the method could simultaneously quantify 27 HVOCs that belong to seven subclasses (i.e., halogenated aliphatic hydrocarbons, chlorobenzenes, nitrobenzenes, anilines, phenols, polycyclic aromatic hydrocarbons and organic sulfides) in 26 min. Injecting a 50 μL sample without any enrichment step, such as cryotrap focusing, the limits of quantification (LOQs) for the 27 HVOCs was 0.01-3 μg/L. Replicate analyses of the 27 HVOCs spiked source and river water samples exhibited good precision (relative standard deviations ≤ 11.3%) and accuracy (relative errors ≤ 17.6%). The optimized LV-DAI-GC was robust and applicable for fast determination and automated continuous monitoring of HVOCs in surface water. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. Rheological behaviour of some saccharides in aqueous potassium chloride solutions over temperature range (288.15 to 318.15) K

    Energy Technology Data Exchange (ETDEWEB)

    Banipal, Parampaul K., E-mail: pkbanipal@yahoo.co [Department of Chemistry, Guru Nanak Dev University, Amritsar 143005 (India); Chahal, Amanpreet K.; Singh, Vickramjeet [Department of Chemistry, Guru Nanak Dev University, Amritsar 143005 (India); Banipal, Tarlok S. [Department of Applied Chemistry, Guru Nanak Dev University, Amritsar 143005 (India)

    2010-08-15

    The viscosities, {eta} of mono-, di-, tri-saccharides and methylglycosides, viz., D(+)-xylose (XYL), D(-)-arabinose (ARA), D(-)-ribose (RIB), D(-)-fructose (FRU), D(+)-galactose (GAL), D(+)-mannose (MAN), D(+)-glucose (GLU), D(+)-melibiose (MEL), D(+)-cellobiose (CEL), D(+)-lactose monohydrate (LAC), D(+)-maltose monohydrate (MAL), D(+)-trehalose dihydrate (TRE), sucrose (SUC), D(+)-raffinose pentahydrate (RAF), {alpha}-methyl-D(+)-glucoside ({alpha}-Me-GLU), methyl-{alpha}-D-xylopyranoside (Me-{alpha}-XYL), and methyl-{beta}-D-xylopyranoside (Me-{beta}-XYL) in water and in (0.5, 1.0, 2.0, and 3.0) mol . kg{sup -1} aqueous solutions of potassium chloride (KCl) have been determined at T = (288.15, 298.15, 308.15, and 318.15) K from efflux time measurements by using a capillary viscometer. Densities used to determine viscosities have been reported earlier. The viscosity data have been utilized to determine the viscosity B-coefficients employing the Jones-Dole equation at different temperatures. From these data, the viscosity B-coefficients of transfer, {Delta}{sub t}B have been estimated for the transfer of various saccharides/methylglycosides from water to aqueous potassium chloride solutions. The {Delta}{sub t}B values have been found to be positive, whose magnitude increases with the increase in concentration of potassium chloride in all cases. The dB/dT coefficients, pair, {eta}{sub AB} and triplet, {eta}{sub ABB} viscometric interaction coefficients have also been determined. Gibbs free energies of activation and related thermodynamic parameters of activation of viscous flow have been determined employing Feakin's transition-state theory. The signs and magnitudes of various parameters have been discussed in terms of solute-solute and solute-solvent interactions occurring in these solutions. The effect of substitution of -OH by methoxy group, -OCH{sub 3} has also been discussed.

  10. Studies on volumetric properties of some saccharides in aqueous potassium chloride solutions over temperature range (288.15 to 318.15) K

    Energy Technology Data Exchange (ETDEWEB)

    Banipal, Parampaul K. [Department of Chemistry, Guru Nanak Dev University, Amritsar 143 005 (India)], E-mail: pkbanipal@yahoo.com; Chahal, Amanpreet K. [Department of Chemistry, Guru Nanak Dev University, Amritsar 143 005 (India); Banipal, Tarlok S. [Department of Applied Chemistry, Guru Nanak Dev University, Amritsar 143 005 (India)

    2009-04-15

    The standard partial molar volumes, V{sub 2}{sup {infinity}} at infinite dilution of monosaccharides; D(+)-xylose, D(-)-arabinose, D(-)-ribose, D(+)-mannose, D(+)-galactose, D(-)-fructose and D(+)-glucose, disaccharides; D(+)-melibiose, D(+)-cellobiose, D(+)-maltose monohydrate, D(+)-trehalose dihydrate, D(+)-lactose monohydrate and sucrose, trisaccharide; D(+)-raffinose pentahydrate, methylglycosides; {alpha}-methyl-D(+)-glucoside, methyl-{alpha}-D-xylopyranoside and methyl-{beta}-D-xylopyranoside have been determined in water and in aqueous solutions of potassium chloride (0.5, 1.0, 2.0, and 3.0) mol . kg{sup -1} at T = (288.15, 298.15, 308.15, and 318.15) K from density measurements employing a vibrating-tube densimeter. These results have been utilized to determine the corresponding standard partial molar volumes of transfer, {delta}{sub t}V{sub 2}{sup {infinity}} for the transfer of various saccharides from water to aqueous potassium chloride solutions. The standard transfer volumes have been found to be positive (except for {alpha}- and {beta}-methyl xylopyranosides in 0.5 mol . kg{sup -1} solutions of potassium chloride) whose magnitude increase with the concentration of potassium chloride as well as temperature for all the saccharides. Partial molar expansion coefficients, ({partial_derivative}V{sub 2}{sup {infinity}}/{partial_derivative}T){sub p} and the second derivative ({partial_derivative}{sup 2}V{sub 2}{sup {infinity}}/{partial_derivative}T{sup 2}){sub p} values have been estimated. Pair and higher order volumetric interaction coefficients have also been calculated from {delta}{sub t}V{sub 2}{sup {infinity}} by using the McMillan-Mayer theory. These parameters have been discussed in terms of the solute-cosolute interactions and are used to understand various mixing effects due to these interactions. The effect of substitution of -OH by glycosidic group, -OCH{sub 3} is also discussed. Attempt has also been made to discuss the stereochemical effects

  11. Digestion of Bangka monazite with sulfuric acid

    International Nuclear Information System (INIS)

    Riesna Prassanti

    2012-01-01

    Technology of Bangka monazite processing with alkaline method has been mastered by PPGN BATAN with the product in the form of RE (Rare Earth) which is contain U < 2 ppm and Th 12 - 16 ppm. Hence, as comparator, the research of Bangka monazite processing with acid method using sulfuric acid has been done. The aim of this research is to obtain the optimal condition of Bangka monazite's digestion using sulfuric acid so that all elements contained in the monazite that are U, Th, RE, PO 4 dissolved as much as possible. The research parameter's arc monazite particle's size, sulfuric acid consumption (weight ratio of monazite ore : sulfuric acid), digestion temperature, digestion time and consumption of wash water. The results showed that the optimal conditions of digestion are 250+ 325 mesh of monazite particle's size, 1 : 2.5 of weight ratio of monazite ore: sulfuric acid, 190°C of digestion temperature, 3 hours of digestion time and 8 times of weight monazite's feed of wash water with the recovery of digested U = 99.90 %, Th = 99.44 %, RE = 98.64 % and PO 4 = 99.88 %. (author)

  12. Simultaneous alloy-silicate fractionation of carbon, nitrogen, and sulfur at high pressures and temperatures: Implications for establishing the volatile budget of the Earth

    Science.gov (United States)

    Grewal, D. S.; Dasgupta, R.; Sun, C.; Tsuno, K.

    2017-12-01

    Constraining the origin, distribution and evolution of volatiles such as carbon (C), nitrogen (N) and sulfur (S) in terrestrial planets is essential to understand planetary differentiation, habitability and comparative planetology [1]. C/N ratio of Bulk Silicate Earth (BSE) is superchondritic (40 ± 8), while C/S ratio is nearly chondritic (0.49 ± 0.14) [2]. Accretion, core formation, and magma ocean (MO) crystallization are the key processes that could have set the relative budgets of C, N and S in different planetary reservoirs [3]. However, experiments using either C-N or C-S-bearing systems have shown that C is more siderophile than N and S, consequently core formation would have left behind subchondritic C/N and C/S ratios in BSE [4-6]. Accretion of extremely C-rich bodies during core formation or/and as a late veneer along with an early atmospheric blow-off are amongst the scenarios that have been suggested to explain C/N ratio while the addition of a differentiated body with a C-rich mantle has been suggested to explain C/S ratio in BSE [4-6]. However, no internally consistent explanations exist on the origin of all the volatile elements. We performed piston cylinder and multi-anvil experiments, using Fe-Ni-N-C±S alloy with variable amounts of S and mafic-ultramafic silicate mixtures in graphite saturated conditions at 1-7 GPa, 1600-1800 °C, and fO2 ranging from ΔIW of -1.1 to -0.3. EPMA and SIMS were used to determine major elements and volatile abundances in the coexisting alloy and silicate melt phases, while the speciation of the volatiles was determined using Raman spectroscopy. Our experimental data reveals that C becomes less siderophile in the presence of N and S during core-mantle differentiation involving an S-rich alloy. Using a set of inverse Monte-Carlo simulations, we propose that a disequilibrium merger of a Mars-sized planetary embryo with a C-saturated, S-rich core to a volatile-depleted proto-Earth during the main stage of accretion

  13. Removal and recovery of nitrogen and sulfur oxides from gaseous mixtures containing them

    International Nuclear Information System (INIS)

    Cooper, H.B.H.

    1984-01-01

    A cyclic process for removing lower valence nitrogen oxides from gaseous mixtures includes treating the mixtures with an aqueous media including alkali metal carbonate and alkali metal bicarbonate and a preoxygen oxidant to form higher valence nitrogen oxides and to capture these oxides as alkali metal salts, expecially nitrites and nitrates, in a carbonate/bicarbonate-containing product aqueous media. Highly selective recovery of nitrates in high purity and yield may then follow, as by crystallization, with the carbonate and bicarbonate alkali metal salts strongly increasing the selectivity and yield of nitrates. The product nitrites are converted to nitrates by oxidation after lowering the product aqueous media pH to below about 9. A cyclic process for removing sulfur oxides from gas mixtures includes treating these mixtures includes treating these mixtures with aqueous media including alkali metal carbonate and alkali metal bicarbonate where the ratio of alkali metal to sulfur dioxide is not less than 2. The sulfur values may be recovered from the resulting carbonate/bicarbonate/-sulfite containing product aqueous media as alkali metal sulfate or sulfite salts which are removed by crystallization from the carbonate-containing product aqueous media. As with the nitrates, the carbonate/bicarbonate system strongly increases yield of sulfate or sulfite during crystallization. Where the gas mixtures include both sulfur dioxide and lower valence nitrogen oxides, the processes for removing lower valence nitrogen oxides and sulfur dioxide may be combined into a single removal/recovery system, or may be effected in sequence

  14. Study by neutron diffusion of local order liquid sulfur around the polymerization transition

    International Nuclear Information System (INIS)

    Descotes, L.

    1994-05-01

    We studied the liquid sulfur according to the temperature. The sulfur is one of the most complicated elementary liquid. We experimented the neutron diffusion by the powder orthorhombic sulfur. The complexity at the polymerization transition are only accompanied by weak local structural transfer. 231 refs., 48 figs., 8 tabs., 3 annexes

  15. D{sub 2}O−H{sub 2}O solvent isotope effects on the enthalpies of bicaret hydration and dilution of its aqueous solutions at different temperatures

    Energy Technology Data Exchange (ETDEWEB)

    Ivanov, Evgeniy V., E-mail: evi@isc-ras.ru [Laboratory of Thermodynamics of Solutions of Non-electrolytes and Biologically Active Substances, G.A. Krestov Institute of Solution Chemistry, Russian Academy of Sciences, 1 Akademicheskaya Str., 153045 Ivanovo (Russian Federation); Batov, Dmitriy V. [Incorporated Physicochemical Center of Solution Researches, G.A. Krestov Institute of Solution Chemistry, Russian Academy of Sciences, 1 Akademicheskaya Str., 153045, Ivanovo (Russian Federation); Ivanovo' s State University of Chemistry and Technology, 7 Sheremetevsky Ave, 153000 Ivanovo (Russian Federation); Gazieva, Galina A.; Kravchenko, Angelina N. [Laboratory of Nitrogen-containing Compounds, N.D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 47 Leninsky Ave., 199119 Moscow (Russian Federation); Abrosimov, Vladimir K. [Laboratory of Thermodynamics of Solutions of Non-electrolytes and Biologically Active Substances, G.A. Krestov Institute of Solution Chemistry, Russian Academy of Sciences, 1 Akademicheskaya Str., 153045 Ivanovo (Russian Federation)

    2014-08-20

    Graphical abstract: - Highlights: • Enthalpies of solution of bicaret (tetraethylglycoluril) in H{sub 2}O and D{sub 2}O were measured. • D{sub 2}O–H{sub 2}O enthalpy-isotopic effect is negative and decreasing with temperature. • Enthalpic coefficients h{sub 22} for pairwise solute–solute interactions were derived. • Quantity of h{sub 22} is negative and becoming the more negative in heavy water. • Prevailingly hydrophobic hydration of bicaret is weakened with rising temperature. - Abstract: The molar enthalpies of solution of bicaret or 2,4,6,8-tetraethyl-2,4,6,8-tatraazabicyclo[3.3.0]octane-3,7-dione in ordinary (H{sub 2}O) and heavy (D{sub 2}O) water at (278.15, 288.15, 298.15, 308.15, and 318.15) K as well as the enthalpies for dilution of its H/D isotopically distinguishable aqueous solutions at 298.15 K were measured calorimetrically. The standard (at infinite dilution) molar enthalpies and heat capacities of solution, and the enthalpic coefficients for pair (h{sub 22}) and triplet (h{sub 222}) interactions between hydrated solute molecules, along with D{sub 2}O–H{sub 2}O solvent isotope effects (IEs) on the studied quantities were computed. The enthalpic effects of bicaret dissolution and corresponding IEs were found to be negative and decreasing in magnitude with increasing temperature. On the contrary, the h{sub 22} and h{sub 222} values as well as IEs on them were found to be positive. These facts indicate that the bicaret hydration being predominantly hydrophobic is enhanced in the D{sub 2}O medium. The hydration behavior of the solute considered was discussed in comparison with that for mebicar or 2,4,6,8-tetramethyl-2,4,6,8-tatraazabicyclo[3.3.0]octane-3,7-dione using the previously obtained data.

  16. Sm doped mesoporous CeO2 nanocrystals: aqueous solution-based surfactant assisted low temperature synthesis, characterization and their improved autocatalytic activity.

    Science.gov (United States)

    Mandal, Bappaditya; Mondal, Aparna; Ray, Sirsendu Sekhar; Kundu, Amar

    2016-01-28

    Mesoporous Sm(3+) doped CeO2 (Ce-Sm) with a nanocrystalline framework, a high content of Ce(3+) and surface area (184 m(2) g(-1)), have been synthesized through a facile aqueous solution-based surfactant assisted route by using inorganic precursors and sodium dodecyl sulphate as a template. The XRD results indicate that the calcined Ce-Sm and even the as-prepared material have a cubic fluorite structure of CeO2 with no crystalline impurity phase. XRD studies along with HRTEM results confirmed the formation of mesoporous nanocrystalline CeO2 at a lower temperature as low as 100 °C. A detailed analysis revealed that Sm(3+) doping in CeO2 has increased the lattice volume, surface area, mesopore volume and engineered the surface defects. Higher concentrations of Ce(3+) and oxygen vacancies of Ce-Sm resulted in lowering of the band gap. It is evident from the H2-TPR results that Sm(3+) doping in CeO2 strongly modified the reduction behavior of CeO2 by shifting the bulk reduction at a much lower temperature, indicating increased oxygen mobility in the sample which enables enhanced oxygen diffusion at lower temperatures, thus promoting reducibility, i.e., the process of Ce(4+)→ Ce(3+). UV-visible transmission studies revealed improved autocatalytic performance due to easier Ce(4+)/Ce(3+) recycling in the Sm(3+) doped CeO2 nanoparticles. From the in vitro cytotoxicity of both pure CeO2 and Sm(3+) doped CeO2 calcined at 500 °C in a concentration as high as 100 μg mL(-1) (even after 120 h) on MG-63 cells, no obvious decrease in cell viability is observed, confirming their excellent biocompatibility. The presence of an increased amount of surface hydroxyl groups, mesoporosity, and surface defects have contributed towards an improved autocatalytic activity of mesoporous Ce-Sm, which appear to be a potential candidate for biomedical (antioxidant) applications.

  17. Effect of pyrolysis temperature and sulfuric acid during the fast pyrolysis of cellulose and douglas fir in an atmospheric pressure wire mesh reactor

    NARCIS (Netherlands)

    Wang, Zhouhong; Zhou, Shuai; Pecha, Brennan; Westerhof, Roel J M; Garcia-Perez, Manuel

    2014-01-01

    The goal of this study is to better understand important reactions responsible for the suppression of anhydrosugars during the pyrolysis of microcrystalline Avicel, ball-milled Avicel, levoglucosan, cellobiosan, and Douglas fir at varied pyrolysis conditions (heating rate 100°C/s, temperature

  18. Biodesulfurization of refractory organic sulfur compounds in fossil fuels.

    Science.gov (United States)

    Soleimani, Mehran; Bassi, Amarjeet; Margaritis, Argyrios

    2007-01-01

    The stringent new regulations to lower sulfur content in fossil fuels require new economic and efficient methods for desulfurization of recalcitrant organic sulfur. Hydrodesulfurization of such compounds is very costly and requires high operating temperature and pressure. Biodesulfurization is a non-invasive approach that can specifically remove sulfur from refractory hydrocarbons under mild conditions and it can be potentially used in industrial desulfurization. Intensive research has been conducted in microbiology and molecular biology of the competent strains to increase their desulfurization activity; however, even the highest activity obtained is still insufficient to fulfill the industrial requirements. To improve the biodesulfurization efficiency, more work is needed in areas such as increasing specific desulfurization activity, hydrocarbon phase tolerance, sulfur removal at higher temperature, and isolating new strains for desulfurizing a broader range of sulfur compounds. This article comprehensively reviews and discusses key issues, advances and challenges for a competitive biodesulfurization process.

  19. Method of making a sodium sulfur battery

    Science.gov (United States)

    Elkins, Perry E.

    1981-01-01

    A method of making a portion of a sodium sulfur battery is disclosed. The battery portion made is a portion of the container which defines the volume for the cathodic reactant materials which are sulfur and sodium polysulfide materials. The container portion is defined by an outer metal casing with a graphite liner contained therein, the graphite liner having a coating on its internal diameter for sealing off the porosity thereof. The steel outer container and graphite pipe are united by a method which insures that at the operating temperature of the battery, relatively low electrical resistance exists between the two materials because they are in intimate contact with one another.

  20. Determination of Three-Dimensional Morphology and Inner Structure of Second-Phase Inclusions in Metals by Non-Aqueous Solution Electrolytic and Room Temperature Organic Methods

    Directory of Open Access Journals (Sweden)

    Jing Guo

    2018-01-01

    Full Text Available The secondary-phase particles in metals, particularly those composed of non-metallic materials, are often detrimental to the mechanical properties of metals; thus, it is crucial to control inclusion formation and growth. One of the challenges is determining the three-dimensional morphology and inner structures of such inclusions. In this study, a non-aqueous solution electrolytic method and a room-temperature organic technique were developed based on the principle of electrochemistry to determine the three-dimensional morphologies and inner structures of non-metallic inclusions in Al-killed steel, Si-killed steel, and ductile cast iron. The inclusions were first extracted without any damage to the inclusions, and then the collected inclusions were wrapped and cut through Cu ion deposition. The results revealed that the inclusions in Al-killed steel had an irregular morphology, that those in the Si-killed steel were mainly spherical, and that almost all the spheroidal graphite in the ductile cast iron featured a uniform globular morphology. In addition, nucleation was not observed in the inner structures of the inclusions in the Al-killed steel, while some dendritic or rod-like MnS phase precipitates appeared on the silicate inclusion surfaces, and some silicate-rich phases were detected in their inner matrix. For spheroidal graphite, rare-earth oxides (one particle or more were observed as nuclei in the center of almost every graphite particle. The formation and evolution of inclusions in these types of metals can be better understood by means of the two developed methods.

  1. 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.

  2. Effect of concentration, exposure time, temperature, and relative humidity on the toxicity of sulfur dioxide to the spores of Botrytis cinerea

    Energy Technology Data Exchange (ETDEWEB)

    Couey, H.M.; Uota, M.

    1961-12-01

    When spores of Botrytis cinerea are exposed to SO/sub 2/ gas, the subsequent reduction in spore germination is quantitatively proportional to the SO/sub 2/ concentration and the exposure time. The toxicity of SO/sub 2/ increases with increasing relative humidity. In an atmosphere of 96% RH, SO/sub 2/ is more than 20 times as effective as at 75% RH. The toxicity also increases about 1.5 times for each 10/sup 0/C rise in temperature between 0/sup 0/ and 30/sup 0/C. 8 references, 4 figures, 1 table.

  3. 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.

  4. 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.

  5. AQUEOUS BIPHASE EXTRACTION FOR PROCESSING OF FINE COAL

    Energy Technology Data Exchange (ETDEWEB)

    K. Osseo-Asare; X. Zeng

    2002-01-01

    The objective of this research project is to develop an aqueous biphase extraction process for the treatment of fine coals. Aqueous biphase extraction is an advanced separation technology that relies on the ability of an aqueous system consisting of a water-soluble polymer and another component, e.g., another polymer, an inorganic salt, or a nonionic surfactant, to separate into two immiscible aqueous phases. The principle behind the partition of solid particles in aqueous biphase systems is the physicochemical interaction between the solid surface and the surrounding liquid solution. In order to remove sulfur and mineral matter from fine coal with aqueous biphasic extraction, it is necessary to know the partitioning behavior of coal, as well as the inorganic mineral components. Therefore, in this research emphasis was placed on the partitioning behavior of fine coal particles as well as model fine inorganic particles in aqueous biphase systems.

  6. AQUEOUS BIPHASE EXTRACTION FOR PROCESSING OF FINE COAL; FINAL

    International Nuclear Information System (INIS)

    K. Osseo-Asare; X. Zeng

    2002-01-01

    The objective of this research project is to develop an aqueous biphase extraction process for the treatment of fine coals. Aqueous biphase extraction is an advanced separation technology that relies on the ability of an aqueous system consisting of a water-soluble polymer and another component, e.g., another polymer, an inorganic salt, or a nonionic surfactant, to separate into two immiscible aqueous phases. The principle behind the partition of solid particles in aqueous biphase systems is the physicochemical interaction between the solid surface and the surrounding liquid solution. In order to remove sulfur and mineral matter from fine coal with aqueous biphasic extraction, it is necessary to know the partitioning behavior of coal, as well as the inorganic mineral components. Therefore, in this research emphasis was placed on the partitioning behavior of fine coal particles as well as model fine inorganic particles in aqueous biphase systems

  7. 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

  8. Sulfur doping of M/In2O3 (M=Al,W) nanowires with room temperature near infra red emission

    Science.gov (United States)

    Zervos, M.; Mihailescu, C.; Giapintzakis, J.; Othonos, A.; Travlos, A.

    2015-09-01

    We have investigated the growth of Al doped In2O3 nanowires via the vapor-liquid-solid mechanism at 800°C using Au as a catalyst. We find that the Al is not incorporated into the cubic bixbyite crystal structure of In2O3 but nevertheless was detected in the form of Al2O3. The nanowires had metallic like conductivities and exhibited photoluminescence at 2.3 eV which shifted to 1.5 eV after exposure to H2S above 500°C due to the formation of β-In2S3 and deep donor to acceptor transitions with a lifetime of ≈1 μs. The near infra red emission was also observed in W/In2O3 but not in W/SnO2 core-shell nanowires after processing under H2S at 600°C, confirming it is related to β-In2S3. The nanowires remain one dimensional up to 900°C due to the shell which is interesting for the fabrication of high temperature nanowire sensors.

  9. Sulfur doping of M/In2O3 (M=Al,W nanowires with room temperature near infra red emission

    Directory of Open Access Journals (Sweden)

    M. Zervos

    2015-09-01

    Full Text Available We have investigated the growth of Al doped In2O3 nanowires via the vapor-liquid-solid mechanism at 800°C using Au as a catalyst. We find that the Al is not incorporated into the cubic bixbyite crystal structure of In2O3 but nevertheless was detected in the form of Al2O3. The nanowires had metallic like conductivities and exhibited photoluminescence at 2.3 eV which shifted to 1.5 eV after exposure to H2S above 500°C due to the formation of β-In2S3 and deep donor to acceptor transitions with a lifetime of ≈1 μs. The near infra red emission was also observed in W/In2O3 but not in W/SnO2 core-shell nanowires after processing under H2S at 600°C, confirming it is related to β-In2S3. The nanowires remain one dimensional up to 900°C due to the shell which is interesting for the fabrication of high temperature nanowire sensors.

  10. Observations of industrial sulfur flows - Implications for Io

    International Nuclear Information System (INIS)

    Greeley, R.; Lee, S.W.; Crown, D.A.; Lancaster, N.

    1990-01-01

    A study of industrial liquid sulfur flows at about 130 C yields information on the thermal and rheological characteristics of the sulfur encountered in Io's volcanic activity. As the local sulfur flow cools and/or the local flow rate decreases, the formation of a crust over much of the surface does not prevent a continuation of flow underneath. Subsequent rapid development of a durable crust implies the formation of extensive crusts on Ionian sulfur flows, significantly reducing heat loss and extending flow length. It is suggested on the basis of the present laboratory results that the colors of proposed sulfur flows on Io may correlate with neither the temperature nor the inferred rheological properties attributed to the colors. 52 refs

  11. Sulfur self-retention in ash a grain model approach

    Directory of Open Access Journals (Sweden)

    Manović Vasilije

    2002-01-01

    Full Text Available A developed overall model for sulfur self-retention in ash during coal particle combustion is presented in the paper. The total sulfur content in char, after devolatilization, is evaluated using a derived correlation. It is assumed that sulfur retention during char combustion occurs due to the reaction between SO2 and the active part of the Ca in the form of uniformly distributed CaO grains. Parametric analysis shows that the process is limited by solid diffusion through the product layer formed on the CaO grains and that the most important coal characteristics which influence sulfur self-retention are coal rank, content of sulfur forms, molar Ca/S ratio and particle radius. The model predicts relatively well the levels of the experimentally obtained values of SSR efficiencies, as well as the influence of temperature, particle size and the surrounding conditions.

  12. Effects of Temperature, Oxygen Level, Ionic Strength, and pH on the Reaction of Benzene with Hydroxyl Radicals at the Air-Water Interface in Comparison to the Bulk Aqueous Phase.

    Science.gov (United States)

    Heath, Aubrey A; Valsaraj, Kalliat T

    2015-08-06

    Atmospheric aerosols (e.g., fog droplets) are complex, multiphase mediums. Depending on location, time of day, and/or air mass source, there can be considerable variability within these droplets, relating to temperature, pH, and ionic strength. Due to the droplets' inherently small size, the reactions that occur within these droplets are determined by bulk aqueous phase and air-water interfacial conditions. In this study, the reaction of benzene and hydroxyl radicals is examined kinetically in a thin-film flow-tube reactor. By varying the aqueous volume (e.g., film thickness) along the length of the reactor, both bulk and interfacial reaction rates are measured from a single system. Temperature, pH, and ionic strength are varied to model conditions typical of fog events. Oxygen-poor conditions are measured to study oxygen's overall effect on the reaction pathway. Initial rate activation energies and the bulk aqueous phase and interfacial contributions to the overall rate constant are also obtained.

  13. Sulfur isotopic constraints from a single enzyme on the cellular to global sulfur cycles

    Science.gov (United States)

    Sim, M. S.; Adkins, J. F.; Sessions, A. L.; Orphan, V. J.; McGlynn, S.

    2017-12-01

    Since first reported more than a half century ago, sulfur isotope fractionation between sulfate and sulfide has been used as a diagnostic indicator of microbial sulfate reduction, giving added dimensions to the microbial ecological and geochemical studies of the sulfur cycle. A wide range of fractionation has attracted particular attention because it may serve as a potential indicator of environmental or physiological variables such as substrate concentrations or specific respiration rates. In theory, the magnitude of isotope fractionation depends upon the sulfur isotope effect imparted by the involved enzymes and the relative rate of each enzymatic reaction. The former defines the possible range of fractionation quantitatively, while the latter responds to environmental stimuli, providing an underlying rationale for the varying fractionations. The experimental efforts so far have concentrated largely on the latter, the factors affecting the size of fractionation. Recently, however, the direct assessment of intracellular processes emerges as a promising means for the quantitative analysis of microbial sulfur isotope fractionation as a function of environmental or physiological variables. Here, we experimentally determined for the first time the sulfur isotope fractionation during APS reduction, the first reductive step in the dissimilatory sulfate reduction pathway, using the enzyme purified from Desulfovibrio vulgaris Miyazaki. APS reductase carried out the one-step, two-electron reduction of APS to sulfite, without the production of other metabolic intermediates. Nearly identical isotope effects were obtained at two different temperatures, while the rate of APS reduction more than quadrupled with a temperature increase from 20 to 32°C. When placed in context of the linear network model for microbial sulfur isotope fractionation, our finding could provide a new, semi-quantitative constraint on the sulfur cycle at levels from cellular to global.

  14. Determination of sulfur in coal and ash slurry by high-resolution continuum source electrothermal molecular absorption spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Nakadi, Flávio V.; Rosa, Lilian R.; Veiga, Márcia A.M.S. da, E-mail: mamsveiga@ffclrp.usp.br

    2013-10-01

    We propose a procedure for the determination of sulfur in coal slurries by high resolution continuum source electrothermal molecular absorption spectrometry. The slurry, whose concentration is 1 mg mL{sup −1}, was prepared by mixing 50 mg of the sample with 5% v/v nitric acid and 0.04% m/v Triton X-100 and was homogenized manually. It sustained good stability. The determination was performed via CS molecular absorption at 257.592 nm, and the optimized vaporization temperature was 2500 °C. The accuracy of the method was ensured by analysis of certified reference materials SRM 1632b (trace elements in coal) and SRM 1633b (coal fly ash) from the National Institute of Standards and Technology, using external calibration with aqueous standards prepared in the same medium and used as slurry. We achieved good agreement with the certified reference materials within 95% confidence interval, LOD of 0.01% w/w, and RSD of 6%, which confirms the potential of the proposed method. - Highlights: • HR-CS ET MAS as a technique to determine sulfur in coal and ash • Utilization of (coal and coal fly ash) slurry as a sample preparation • Simple and fast method, which uses external calibration with aqueous standards without chemical modifier.

  15. Combination of best promoter and micellar catalyst for chromic acid oxidation of 1-butanol to 1-butanal in aqueous media at room temperature.

    Science.gov (United States)

    Saha, Rumpa; Ghosh, Aniruddha; Saha, Bidyut

    2014-04-24

    In aqueous acidic media, picolinic acid, 2,2'-bipyridine and 1,10-phenanthroline promoted Cr(VI) oxidation of 1-butanol produces 1-butanal. 1-butanal is separated from mixture by fractional distillation. The anionic surfactant (SDS) and neutral surfactant (TX-100) accelerate the process while the cationic surfactant (CPC) retards the reaction. Combination of bipy and SDS is the best choice for chromic acid oxidation of 1-butanol to 1-butanal in aqueous media. Copyright © 2014 Elsevier B.V. All rights reserved.

  16. Process for forming sulfuric acid

    Science.gov (United States)

    Lu, Wen-Tong P.

    1981-01-01

    An improved electrode is disclosed for the anode in a sulfur cycle hydrogen generation process where sulfur dioxie is oxidized to form sulfuric acid at the anode. The active compound in the electrode is palladium, palladium oxide, an alloy of palladium, or a mixture thereof. The active compound may be deposited on a porous, stable, conductive substrate.

  17. Accidents with sulfuric acid

    Directory of Open Access Journals (Sweden)

    Rajković Miloš B.

    2006-01-01

    Full Text Available Sulfuric acid is an important industrial and strategic raw material, the production of which is developing on all continents, in many factories in the world and with an annual production of over 160 million tons. On the other hand, the production, transport and usage are very dangerous and demand measures of precaution because the consequences could be catastrophic, and not only at the local level where the accident would happen. Accidents that have been publicly recorded during the last eighteen years (from 1988 till the beginning of 2006 are analyzed in this paper. It is very alarming data that, according to all the recorded accidents, over 1.6 million tons of sulfuric acid were exuded. Although water transport is the safest (only 16.38% of the total amount of accidents in that way 98.88% of the total amount of sulfuric acid was exuded into the environment. Human factor was the common factor in all the accidents, whether there was enough control of the production process, of reservoirs or transportation tanks or the transport was done by inadequate (old tanks, or the accidents arose from human factor (inadequate speed, lock of caution etc. The fact is that huge energy, sacrifice and courage were involved in the recovery from accidents where rescue teams and fire brigades showed great courage to prevent real environmental catastrophes and very often they lost their lives during the events. So, the phrase that sulfuric acid is a real "environmental bomb" has become clearer.

  18. Mass-dependent sulfur isotope fractionation during reoxidative sulfur cycling

    DEFF Research Database (Denmark)

    Pellerin, André; Bui, Thi Hao; Rough, Mikaella

    2015-01-01

    The multiple sulfur isotope composition of porewater sulfate from the anoxic marine sapropel of Mangrove Lake, Bermuda was measured in order to establish how multiple sulfur isotopes are fractionated during reoxidative sulfur cycling. The porewater-sulfate d34S and D33S dataset exhibits the disti......The multiple sulfur isotope composition of porewater sulfate from the anoxic marine sapropel of Mangrove Lake, Bermuda was measured in order to establish how multiple sulfur isotopes are fractionated during reoxidative sulfur cycling. The porewater-sulfate d34S and D33S dataset exhibits......, informed by the chemistry of sulfur intermediate compounds in Mangrove Lake, reveals that sulfate reduction produces a relatively small intrinsic fractionation and that an active reoxidative sulfur cycle increases the fractionation of the measured values. Based on the model results, the reoxidative cycle...... of Mangrove Lake appears to include sulfide oxidation to elemental sulfur followed by the disproportionation of the elemental sulfur to sulfate and sulfide. This model also indicates that the reoxidative sulfur cycle of Mangrove Lake turns over from 50 to 80% of the sulfide produced by microbial sulfate...

  19. Temperature-induced phase separation and hydration in poly(N-vinylcaprolactam) aqueous solutions: a study by NMR and IR spectroscopy, SAXS, and quantum-chemical calculations

    Czech Academy of Sciences Publication Activity Database

    Spěváček, Jiří; Dybal, Jiří; Starovoytova, Larisa; Zhigunov, Alexander; Sedláková, Zdeňka

    2012-01-01

    Roč. 8, č. 22 (2012), s. 6110-6119 ISSN 1744-683X R&D Projects: GA ČR GA202/09/1281 Institutional research plan: CEZ:AV0Z40500505 Institutional support: RVO:61389013 Keywords : phase separation * coil-globule phase transition * aqueous solution Subject RIV: CD - Macromolecular Chemistry Impact factor: 3.909, year: 2012

  20. Sulfur recirculation for increased electricity production in Waste-to-Energy plants.

    Science.gov (United States)

    Andersson, Sven; Blomqvist, Evalena W; Bäfver, Linda; Jones, Frida; Davidsson, Kent; Froitzheim, Jan; Karlsson, Martin; Larsson, Erik; Liske, Jesper

    2014-01-01

    Sulfur recirculation is a new technology for reducing boiler corrosion and dioxin formation. It was demonstrated in full-scale tests at a Waste to Energy plant in Göteborg (Sweden) during nearly two months of operation. Sulfur was recirculated as sulfuric acid from the flue gas cleaning back to the boiler, thus creating a sulfur loop. The new technology was evaluated by extensive measurement campaigns during operation under normal conditions (reference case) and operation with sulfur recirculation. The chlorine content of both fly ash and boiler ash decreased and the sulfur content increased during the sulfur recirculation tests. The deposit growth and the particle concentration decreased with sulfur recirculation and the dioxin concentration (I-TEQ) of the flue gas was reduced by approximately 25%. Sulfuric acid dew point measurements showed that the sulfuric acid dosage did not lead to elevated SO3 concentrations, which may otherwise induce low temperature corrosion. In the sulfur recirculation corrosion probe exposures, the corrosion rate decreased for all tested materials (16Mo3, Sanicro 28 and Inconel 625) and material temperatures (450 °C and 525 °C) compared to the reference exposure. The corrosion rates were reduced by 60-90%. Sulfur recirculation prevented the formation of transition metal chlorides at the metal/oxide interface, formation of chromate and reduced the presence of zinc in the corrosion products. Furthermore, measured corrosion rates at 525 °C with sulfur recirculation in operation were similar or lower compared to those measured at 450 °C material temperature in reference conditions, which corresponds to normal operation at normal steam temperatures. This implies that sulfur recirculation allows for higher steam data and electricity production without increasing corrosion. Copyright © 2013 The Authors. Published by Elsevier Ltd.. All rights reserved.

  1. Rapid Mercury(II Removal by Electrospun Sulfur Copolymers

    Directory of Open Access Journals (Sweden)

    Michael W. Thielke

    2016-07-01

    Full Text Available Electrospinning was performed with a blend of commercially available poly(methyl methacrylate (PMMA and a sulfur-rich copolymer based on poly(sulfur-statistical-diisopropenylbenzene, which was synthesized via inverse vulcanization. The polysulfide backbone of sulfur-containing polymers is known to bind mercury from aqueous solutions and can be utilized for recycling water. Increasing the surface area by electrospinning can maximize the effect of binding mercury regarding the rate and maximum uptake. These fibers showed a mercury decrease of more than 98% after a few seconds and a maximum uptake of 440 mg of mercury per gram of electrospun fibers. These polymeric fibers represent a new class of efficient water filtering systems that show one of the highest and fastest mercury uptakes for electrospun fibers reported.

  2. Reduced sulfur in euxinic sediments of the Cariaco Basin : Sulfur isotope contraints on organic sulfur formation

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Werne, J.; Lyons, T.W.; Hollander, D.J.; Formolo, M.

    2003-01-01

    Reduced sulfur accumulation in Holocene and latest Pleistocene euxinic marine sediments from the Cariaco Basin, Venezuela, was investigated to constrain the timing and possible pathways of organic matter (OM) sulfurization. Data were collected for a diverse suite of sulfur species, including

  3. Caustic Hydrolysis of Sulfur Mustard

    National Research Council Canada - National Science Library

    Harvey, Steven

    1997-01-01

    The reactions of HD with aqueous calcium hydroxide and aqueous sodium hydroxide were investigated with respect to their potential applicability to a neutralization-based chemical demilitarization process...

  4. Terpolymerization of ethylene, sulfur dioxide and carbon monoxide

    Science.gov (United States)

    Johnson, R.; Steinberg, M.

    This invention relates to high molecular weight terpolymer of ethylene, sulfur dioxide and carbon monoxide stable to 280/sup 0/C and containing as little as 36 mo1% ethylene and about 41 to 51 mo1% sulfur dioxide, and to the method of producing said terpolymer by irradiation of a liquid and gaseous mixture of ethylene, sulfur dioxide and carbon monoxide by means of Co-60 gamma rays or an electron beam, at a temperature of about 10 to 50/sup 0/C, and at a pressure of about 140 to 680 atmospheres, to initiate polymerization.

  5. Calculation of the thermodynamic and transport properties of aqueous species at high pressures and temperatures: Correlation algorithms for ionic species and equation of state predictions to 5 kb and 1000°C

    Science.gov (United States)

    Shock, Everett L.; Helgeson, Harold C.

    1988-08-01

    Correlation algorithms permit prediction of species-dependent parameters in revised equations of state ( TANGER and HELGESON, 1988) for aqueous ions and electrolytes which can be used together with values at 25°C and 1 bar of the standard partial molal entropies ( S0), volumes ( V0), and heat capacities ( C0p) of the ions to calculate their standard partial molal thermodynamic properties at pressures and temperatures to 5 kb and 1000°C. Values of V0 and C0p at 25°C and 1 bar have been calculated for 128 aqueous ions from analysis of published experimental data or from correlations of these properties with S0. Equation of state parameters have also been generated for these ions and examples are given of predicted standard partial molal thermodynamic properties of representative cations and anions at high pressures and temperatures. Close agreement between independently predicted and experimentally determined equilibrium constants for acid anion dissociation reactions at high temperatures supports the validity and generality of the predictive algorithms.

  6. Ultrasound assisted regioselective sulfonation of aromatic compounds with sulfuric acid.

    Science.gov (United States)

    Qureshi, Ziyauddin S; Deshmukh, Krishna M; Jagtap, Sachin R; Nandurkar, Nitin S; Bhanage, Bhalchandra M

    2009-03-01

    A simple and convenient methodology for selective sulfonation of aromatic compounds using sulfuric acid under sonication is described. The present methodology shows a considerable enhancement in the reaction rate along with improved selectivity compared with the reactions performed under silent conditions. The effect of various parameters such as agitation speed, sulfuric acid concentration, and temperature on reaction system have been investigated and are explained on the basis of ultrasonically generated cavitational effects.

  7. [Transformation of sulfur forms during coal pyrolysis and partial gasification in a fixed bed reactor].

    Science.gov (United States)

    Li, Bin; Cao, Yan; Zhang, Jianmin; Huang, Jiejie; Wang, Yang; Chen, Fuyan

    2003-03-01

    The development of various process to the pre-desulfurization of coal was drawn more attention. In present study, the transformation of sulfur forms of three different ranks high sulfur coals during coal pyrolysis and partial gasification were investigated in a fixed bed reactor. The sulfur and carbon content analysis of original coal and coal char produced were determined by LECO SC-444 and wet chemical analysis according to Sugawara's method. The results showed that half of inorganic sulfur and partial of organic sulfur were removed during coal pyrolysis. And the sulfur removal was much more than carbon during pyrolysis process; and the sulfur in the coal char, especially the sulfide sulfur was removed completely during partial gasification process for both Datong coal and Xishan coal, the degree of sulfide sulfur removal could be increased with increasing temperature. At the same time, the results of Yima coal showed that the effect of fixed-sulfur by alkaline metals increased when the temperature was higher than 700 degrees C, which attribute to the increase of the fixed sulfur reaction rate and the decrease of mass-transfer limitation.

  8. The Influence of pH and Temperature on the Stability of N-[(Piperidinemethylene]daunorubicin Hydrochloride and a Comparison of the Stability of Daunorubicin and Its Four New Amidine Derivatives in Aqueous Solutions

    Directory of Open Access Journals (Sweden)

    Mikołaj Piekarski

    2014-01-01

    Full Text Available The influence of pH and temperature on the stability of N-[(piperidinemethylene]daunorubicin hydrochloride (PPD was investigated. Degradation was studied using an HPLC method. Specific acid-base catalysis of PPD involves hydrolysis of protonated molecules of PPD catalyzed by hydrogen ions and spontaneous hydrolysis under the influence of water zwitterions, unprotonated molecules, and monoanions of PPD. The thermodynamic parameters of these reactions, energy, enthalpy, and entropy, were calculated. Also, the stability of daunorubicin and its new amidine derivatives (piperidine, morpholine, pyrrolidine, and hexahydroazepin-1-yl in aqueous solutions was compared and discussed.

  9. Stable isotope compositions of serpentinite seamounts in the Mariana forearc: Serpentinization processes, fluid sources and sulfur metasomatism

    Science.gov (United States)

    Alt, J.C.; Shanks, Wayne C.

    2006-01-01

    The Mariana and Izu-Bonin arcs in the western Pacific are characterized by serpentinite seamounts in the forearc that provide unique windows into the mantle wedge. We present stable isotope (O, H, S, and C) data for serpentinites from Conical seamount in the Mariana forearc and S isotope data for Torishima seamount in the Izu-Bonin forearc in order to understand the compositions of fluids and temperatures of serpentinization in the mantle wedge, and to investigate the transport of sulfur from the slab to the mantle wedge. Six serpentine mineral separates have a restricted range of ??18O (6.5-8.5???). Antigorite separates have ??D values of -29.5??? to -45.5??? that reflect serpentinization within the mantle wedge whereas chrysotile has low ??D values (-51.8??? to -84.0???) as the result of re-equilibration with fluids at low temperatures. Fractionation of oxygen isotopes between serpentine and magnetite indicate serpentinization temperatures of 300-375 ??C. Two late cross-fiber chrysotile veins have higher ??18O values of 8.9??? to 10.8??? and formed at lower temperatures (as low as ???100 ??C). Aqueous fluids in equilibrium with serpentine at 300-375 ??C had ??18O = 6.5-9??? and ??D = -4??? to -26???, consistent with sediment dehydration reactions at temperatures aragonite veins in metabasalt and siltstone clasts within the serpentinite flows have ??18O = 16.7-24.5???, consistent with the serpentinizing fluids at temperatures <250 ??C. ??13C values of 0.1-2.5??? suggest a source in subducting carbonate sediments. The ??34S values of sulfide in serpentinites on Conical Seamount (-6.7??? to 9.8???) result from metasomatism through variable reduction of aqueous sulfate (??34S = 14???) derived from slab sediments. Despite sulfur metasomatism, serpentinites have low sulfur contents (generally < 164 ppm) that reflect the highly depleted nature of the mantle wedge. The serpentinites are mostly enriched in 34S (median ??34Ssulfide = 4.5???), consistent with a 34S

  10. Sulfur in zircons: A new window into melt chemistry

    Science.gov (United States)

    Tang, H.; Bell, E. A.; Boehnke, P.; Barboni, M.; Harrison, T. M.

    2017-12-01

    The abundance and isotopic composition of sulfur are important tools for exploring the photochemistry of the atmosphere, the thermal history of mantle and igneous rocks, and ancient metabolic processes on the early Earth. Because the oldest terrestrial samples are zircons, we developed a new in-situ procedure to analyze the sulfur content of zircons using the CAMECA ims 1290 at UCLA. We analyzed zircons from three metaluminous/I-type granites (reduced and oxidized Peninsular range and Elba), which exhibit low sulfur abundance with the average of 0.5ppm, and one peraluminous/S-type zircon (Strathbogie Range), which shows an elevated sulfur level with the average of 1.5ppm. Additionally, we found that sulfur content ranges between 0.4 and 2.3 ppm in young volcanic zircons (St. Lucia). Our analyses of zircons from the Jack Hills, Western Australia, whose ages range between 3.4 and 4.1 Ga, show a variety of sulfur contents. Three out of the ten zircons are consistent with the sulfur contents of S-type zircons; the rest have low sulfur contents, which are similar to those of I-type zircons. The high sulfur content in some of these Jack Hills zircons can be interpreted as indicating their origin in either a S-type granite or a volcanic reservoir. We favor the former interpretation since the Ti-in-zircon temperatures of our Jack Hills zircons is lower than those of volcanic zircons. Future work will be undertaken to develop a systematic understanding of the relationship between melt volatile content, melt chemistry, and zircon sulfur content.

  11. 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.

  12. Temperature-induced phase separation and hydration in aqueous polymer solutions studied by NMR and IR spectroscopy: comparison of poly(N-vinylcaprolactam) and acrylamide-based polymers

    Czech Academy of Sciences Publication Activity Database

    Spěváček, Jiří; Dybal, Jiří

    2014-01-01

    Roč. 336, č. 1 (2014), s. 39-46 ISSN 1022-1360. [International IUPAC Conference on Polymer-Solvent Complexes and Intercalates /9./ - POLYSOLVAT-9. Kiev, 11.09.2012-14.09.2012] R&D Projects: GA ČR GA202/09/1281 Institutional support: RVO:61389013 Keywords : aqueous polymer solutions * FT-IR * NMR Subject RIV: CD - Macromolecular Chemistry

  13. Bulk Fluidity and Apparent Wall Slip of Aqueous Kaolin Suspensions Studied Using the Cone-cone (KK) Sensor: The Effect of Concentration and Temperature.

    Czech Academy of Sciences Publication Activity Database

    Pěnkavová, Věra; Tihon, Jaroslav; Wein, Ondřej

    2016-01-01

    Roč. 511, DEC 20 (2016), s. 272-284 ISSN 0927-7757 R&D Projects: GA MŠk(CZ) LD13018 Grant - others:COST- European Coperation in Science and Technology (XE) MP1305; COST- European Coperation in Science and Technology (XE) MP1106 Program:LD COST Institutional support: RVO:67985858 Keywords : aqueous kaolin suspensions * apparent wall slip * cone-cone (KK) sensor Subject RIV: CI - Industrial Chemistry, Chemical Engineering Impact factor: 2.714, year: 2016

  14. Dynamics of a Novel Class of Polymers: Polymerized Sulfur

    Science.gov (United States)

    Masser, Kevin; Kim, Jenny; Oleshko, Vladimir; Griebel, Jared; Chung, Woo; Simmons, Adam; Pyun, Jeff; Soles, Christopher

    2013-03-01

    In this study we investigate the dynamics of a new type of polymer, consisting mainly of sulfur. Room-temperature stable polymerized sulfur samples were prepared by crosslinking the well-known living sulfur polymers formed at elevated temperatures by the addition of a crosslinking agent. This reverse vulcanization process was used to create a series of samples with different amounts of crosslinking agent. These polymers show great promise for use in advanced batteries as cathode materials. Each system exhibits a glassy-state beta relaxation, with the intensity of this relaxation proportional to the crosslinking content. A dynamic glass transition is also observed for each system, and the glass transition temperature/segmental relaxation moves to higher temperatures with increased crosslink content as is typically observed in crosslinked systems. As is typical of polymers, ion motion in these systems is closely coupled to the backbone motion of the host polymer. National Research Council Postdoctoral Fellowship

  15. Aqueous Corrosion Characteristics of Nickel Aluminides

    International Nuclear Information System (INIS)

    Kim, Jung Gu

    1996-01-01

    The aqueous corrosion characteristics of three nickel aluminides were studied by using (a) immersion corrosion test and (b) cyclic anodic polarization measurements. The immersion tests were conducted in 15 different solutions at 25 .deg. C and 95 .deg. C. The nickel aluminides were found to have good corrosion resistance in inorganic acids, organic acids and basic solutions 25 .deg. C except at a higher concentration of hydrochloric acid in ferric chloride solution at the temperature. All three nickel aluminides were suitably resistant to corrosion in the organic acids (oxalic acid, acetic acid), sodium chloride solution, and bases (sodium hydoxide, ammonium hydroxide) at 95 .deg. C. The cyclic anodic polarization curves were developed in N 2 -deaerated solution at 25 .deg. C and 95 .deg. C. In addition, open-circuit corrosion potentials were determined for the solutions in the aerated condition at 25 .deg. C to compare with the anodic curves. At 25 .deg. C, although all materials exhibited active-passive behavior in all solutions except the hydrofluoric acid, at E corr (aerated), passive corrosion was only indicated for the acetic acid, sodium hydroxide, and sodium chloride solutions. Nevertheless, in all cases, the predicted dissolution rates were consistent with immersion test results. Hysteresis loops indicating susceptibility to localized corrosion were observed in 0.6M sodium chloride(pH=7) solution. At 95 .deg. C, active-passive behavior was demonstrated in the acetic acid, sodium chloride, and to a limited extent in the nitric acid: but only active behavior was shown in the sulfuric and hydrofluoric acids. From the above results, it was noted that anodic dissolution of nickel aluminides significantly increased with increasing temperature and that the Cr-containing compositions had better corrosion resistance in several solutions than the Cr-free composition. Prior manufacturing procedures, i.e., casting and powder metallurgy processes did not appear to

  16. Determination of the sulfur mustard hydrolysis product thiodiglycol by microcolumn liquid chromatography coupled on-line with sulfur flame photometric detection using large-volume injections and peak

    NARCIS (Netherlands)

    Hooijschuur, E.W.J.; Kientz, C.E.; Brinkman, U.A.T.

    1999-01-01

    A selective, direct and relatively rapid method has been developed for the determination of thiodiglycol (TDG) in aqueous samples. TDG is the main hydrolysis product of the chemical warfare agent sulfur mustard. The method of analysis is based on the on-line coupling of reversed-phase microcolumn

  17. 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.

  18. temperature

    Directory of Open Access Journals (Sweden)

    G. Polt

    2015-10-01

    Full Text Available In-situ X-ray diffraction was applied to isotactic polypropylene with a high volume fraction of α-phase (α-iPP while it has been compressed at temperatures below and above its glass transition temperature Tg. The diffraction patterns were evaluated by the Multi-reflection X-ray Profile Analysis (MXPA method, revealing microstructural parameters such as the density of dislocations and the size of coherently scattering domains (CSD-size. A significant difference in the development of the dislocation density was found compared to compression at temperatures above Tg, pointing at a different plastic deformation mechanism at these temperatures. Based on the individual evolutions of the dislocation density and CSD-size observed as a function of compressive strain, suggestions for the deformation mechanisms occurring below and above Tg are made.

  19. Flow of Aqueous Humor

    Science.gov (United States)

    ... Home Flow of Aqueous Humor Flow of Aqueous Humor Most, but not all, forms of glaucoma are ... remains normal when some of the fluid (aqueous humor) produced by the eye's ciliary body flows out ...

  20. Calculation of the standard partial molal thermodynamic properties and dissociation constants of aqueous HCl 0 and HBr 0 at temperatures to 1000°C and pressures to 5 kbar

    Science.gov (United States)

    Pokrovskii, Vitalii A.

    1999-04-01

    Dissociation constants of aqueous ion pairs HCl 0 and HBr 0 derived in the literature from vapor pressure and supercritical conductance measurements (Quist and Marshall, 1968b; Frantz and Marshall, 1984) were used to calculate the standard partial molal thermodynamic properties of the species at 25°C and 1 bar. Regression of the data with the aid of revised Helgeson-Kirkham-Flowers equations of state (Helgeson et al., 1981; Tanger and Helgeson, 1988; Shock et al., 1989) resulted in a set of equations-of-state parameters that permits accurate calculation of the thermodynamic properties of the species at high temperatures and pressures. These properties and parameters reproduce generally within 0.1 log unit (with observed maximum deviation of 0.23 log unit) the log K values for HBr 0 and HCl 0 given by Quist and Marshall (1968b) and Frantz and Marshall (1984), respectively, at temperatures to 800°C and pressures to 5 kbar.

  1. Thermodynamic properties of Sodium Dodecyl Sulfate aqueous solutions with Methanol, Ethanol, n-Propanol and iso-Propanol at different temperatures

    Directory of Open Access Journals (Sweden)

    Md. Abdul Motin

    2015-03-01

    The ΔH# values that are positive for all the studied systems indicate that positive work has to be done to overcome the energy barrier for the flow process. The variation of ΔS# is reversing the variation of the ΔH#. The excess parameters (ΔG#E, ΔH#E data have been fitted by the least square method to the four parameter Redlich–Kister equation and the values of the parameter aj have been reported. The observed increase of thermodynamic values in the aqueous SDS region are thought to be mainly due to the combined effect of hydrophobic hydration and hydrophilic effect.

  2. Some thoughts on GAIA and the sulfur cycle

    Science.gov (United States)

    Lovelock, J. E.

    1985-01-01

    The data hypothesis states that the composition, oxidation reduction state, and temperature of the troposphere are actively regulated by the biota for the biota. One of the early predictions of the Gaia hypothesis was that there should be a sulfur compound made by the biota in the oceans. It would need to be stable enough against oxidation in water to allow its transfer to the air. Either the sulfur compound itself or its atmospheric oxidation product would have to return sulfur from the sea to the land surfaces. The most likely candidate for this role was dimethyl sulfide. Another sulfur compound of interest from a Gaian viewpoint CS2 (carbon disulfide) is discussed. Theories on the production of dimethyl sulfide and carbon disulfide related to the Gaian hypothesis are examined.

  3. Geometrical isomerization of fatty acids with sulfur as a catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Grompone, M.A.; Tancredi, N.A. (Catedra de Fisicoquimica, Facultad de Quimica, General Flores 2124, Montevideo, 00598 (UY))

    1991-08-01

    This paper reports on the kinetics of the geometrical isomerization of oleic and palmitoleic acids, both contained in U.S.P. oleic acid that were studied. Sulfur powder was used as a catalyst. The methyl esters of fatty acids were analyzed by GLC with 15% OV-275 columns. The sulfur-catalyzed isomerization at 180 and 225{degrees} C proceeds via two consecutive mechanisms. The position of equilibrium is reached by the second mechanism. For this, at any particular initial concentration of sulfur, the pseudo- first-order rate dependence on substrate for a reversible reaction holds. The full rate has been shown to be proportional to the initial sulfur concentration taken to the 1.2 power. The rate constants at both temperatures and the activation energies were calculated.

  4. Microbiological disproportionation of inorganic sulfur compounds

    DEFF Research Database (Denmark)

    Finster, Kai

    2008-01-01

    The disproportionation of inorganic sulfur intermediates at moderate temperatures (0-80 °C) is a microbiologically catalyzed chemolithotrophic process in which compounds like elemental sulfur, thiosulfate, and sulfite serve as both electron donor and acceptor, and generate hydrogen sulfide...... and sulfate. Thus the overall process is comparable to the fermentation of organic compounds such as glucose and is consequently often described as 'inorganic fermentation'. The process is primarily carried out by microorganisms with phylogenetic affiliation to the so called sulfate-reducing bacteria within...... the delta subclass of Proteobacteria. The organisms grow with sulfate as their external electron acceptor and low-molecular weight organic compounds or hydrogen as energy sources. Studies of the biochemistry of a few isolates indicate that the disproportionating microbes reverse the sulfate reduction...

  5. Potentially hazardous sulfur conditions on beef cattle ranches in the United States.

    Science.gov (United States)

    Gould, Daniel H; Dargatz, David A; Garry, Franklyn B; Hamar, Dwayne W; Ross, Paul F

    2002-09-01

    To analyze the sulfur content of water and forage samples from a geographically diverse sample of beef cow-calf operations in the United States and to estimate frequency and distribution of premises where forage and water resources could result in consumption of hazardous amounts of sulfur by cattle. Cross-sectional study. 709 forage samples from 678 beef cow-calf operations and individual water samples from 498 operations in 23 states. Sulfur content of forage samples and sulfate concentration of water samples were measured. Total sulfur intake was estimated for pairs of forage and water samples. Total sulfur intake was estimated for 454 pairs of forage and water samples. In general, highest forage sulfur contents did not coincide with highest water sulfate concentrations. Overall, 52 of the 454 (11.5%) sample pairs were estimated to yield total sulfur intake (as a percentage of dry matter) > or = 0.4%, assuming water intake during conditions of high ambient temperature. Most of these premises were in north-central (n = 19) or western (19) states. Results suggest that on numerous beef cow-calf operations throughout the United States, consumption of forage and water could result in excessively high sulfur intake. All water sources and dietary components should be evaluated when assessing total sulfur intake. Knowledge of total sulfur intake may be useful in reducing the risk of sulfur-associated health and performance problems in beef cattle.

  6. Isotope evidence for the microbially mediated formation of elemental sulfur: A case study from Lake Peten Itza, Guatemala

    Science.gov (United States)

    Turchyn, A. V.; Bennett, V. A.; Hodell, D. A.

    2013-12-01

    Elemental, or native, sulfur nodules or veins can be formed during aqueous diagenesis and have been found in a range of natural environments, including lake sediments. What governs the formation of elemental sulfur remains enigmatic, although it is widely thought to be microbially-mediated. While most of the literature suggests elemental sulfur is formed by partial re-oxidation of hydrogen sulphide, elemental sulfur can also form during incomplete bacterial sulfate reduction or during aborted sulfur disproportionation. Lake Peten Itza, in Northern Guatemala, which was cored during the International Continental Drilling program in 2006, is one of the few places where elemental sulfur nodules are forming during microbial diagenesis today. Sulfur isotopes are strongly partitioned during bacterial sulfate reduction and the magnitude of the partitioning yields insight into the microbial reactions and environmental conditions. For example, sulfate reduction that terminates at elemental sulfur likely requires the use of the intracellular trithonite pathway, which may drive larger overall sulfur isotope fractionation between the precursor sulfate and the elemental sulfur product. Sulfur isotopes combined with oxygen isotopes in the precursor sulfate may provide even more information about microbial mechanisms. We present coupled pore fluid sulfate concentrations and sulfur and oxygen isotope measurements, as well as co-existing nodule sulfur isotopes from the Lake Peten Itza sediments. The δ34S of the nodules in the lake sediments ranges from +12 to -13‰, often within a single nodule. This suggests formation from an open system where sulfate is replenished by diffusion, as might be expected during pore fluid diagenesis. The δ34S of the pore fluid sulfate at the depth of nodule formation is between 50 and 60‰ (versus the precursor gypsum which is 17 to 18‰) suggesting a large sulfur isotope fractionation between sulfate and elemental sulfur (38 to 73‰). Pyrite was

  7. Transient Studies of a Sodium Sulfur Cell

    Science.gov (United States)

    Caprio, Sarah

    entropy change. Species conservation equations are written in the sulfur electrode by considering the phase transition and change in the composition depending on the SOD. The electrochemical reactions are modeled by using Arrhenius-type rate equations with temperature-dependent terms and varying species concentration depending on the SOD. Species conservation equations are written in the beta"-alumina electrolyte for the ionic species by considering the change in composition due to diffusion and migration. In addition, the potential distribution, and the cell resistance for this spatially distributed system has been modeled. The physicochemical properties are considered to be temperature-dependent. The model is used to study both charging and discharging characteristics of the cell at varying current densities. The PDE-based model is solved in Aspen Custom Modeler by using method of lines. Our work shows that an appropriate thermal management strategy is necessary for high current-density operation, especially in the case of high penetration of the renewable energy into the grid.

  8. Study on the utilization of a sodium-sulfuric acid solution for the uranium minerals' leaching

    International Nuclear Information System (INIS)

    Echenique, Patricia; Fruchtenicht, Fernando; Gil, Daniel; Vigo, Daniel; Bouza, Angel; Vert, Gabriela; Becquart, Elena

    1988-01-01

    Argentine uranium minerals have been leached at bench scale with a different agent trying to reduce sulfuric acid consumption. The leaching agent was a sodium sulfate-sulfuric acid solution and the ore was from Sierra Pintada (San Rafael - Mendoza). The work was performed in stirred vessel at atmospheric pressure. The influence of different variables, pH, temperature, oxidant agent, sodium sulfate concentration and time, in the sulfuric acid consumption and the uranium yield was studied. (Author) [es

  9. Lithium-Sulfur Capacitors.

    Science.gov (United States)

    Kim, Mok-Hwa; Kim, Hyun-Kyung; Xi, Kai; Kumar, R Vasant; Jung, Dae Soo; Kim, Kwang-Bum; Roh, Kwang Chul

    2018-02-21

    Although many existing hybrid energy storage systems demonstrate promising electrochemical performances, imbalances between the energies and kinetics of the two electrodes must be resolved to allow their widespread commercialization. As such, the development of a new class of energy storage systems is a particular challenge, since future systems will require a single device to provide both a high gravimetric energy and a high power density. In this context, we herein report the design of novel lithium-sulfur capacitors. The resulting asymmetric systems exhibited energy densities of 23.9-236.4 Wh kg -1 and power densities of 72.2-4097.3 W kg -1 , which are the highest reported values for an asymmetric system to date. This approach involved the use of a prelithiated anode and a hybrid cathode material exhibiting anion adsorption-desorption in addition to the electrochemical reduction and oxidation of sulfur at almost identical rates. This novel strategy yielded both high energy and power densities, and therefore establishes a new benchmark for hybrid systems.

  10. EFFECT OF DIATOMEAOUS EARTH TREATMENT USING HYDROGEN CHLORIDE AND SULFURIC ACID ON KINETICS OF CADMIUM(II ADSORPTION

    Directory of Open Access Journals (Sweden)

    Nuryono Nuryono

    2010-06-01

    Full Text Available In this research, treatment of diatomaceous earth, Sangiran, Central Java using hydrogen chloride (HCl and sulfuric acid (H2SO4 on kinetics of Cd(II adsorption in aqueous solution has been carried out. The work was conducted by mixing an amount of grounded diatomaceous earth (200 mesh in size with HCl or H2SO4 solution in various concentrations for two hours at temperature range of 100 - 150oC. The mixture was then filtered and washed with water until the filtrate pH is approximately 7 and then the residue was dried for four hours at a temperature of 70oC. The product was used as an adsorbent to adsorb Cd(II in aqueous solution with various concentrations. The Cd(II adsorbed was determined by analyzing the rest of Cd(II in the solution using atomic absorption spectrophotometry. The effect of treatment was evaluated from kinetic parameter of adsorption rate constant calculated based on the simple kinetic model. Results showed  that before equilibrium condition reached, adsorpstion of Cd(II occurred through two steps, i.e. a step tends to follow a reaction of irreversible first order  (step I followed by reaction of reversible first order (step II. Treatment with acids, either hydrogen chloride or sulfuric acid, decreased adsorption rate constant for the step I from 15.2/min to a range of 6.4 - 9.4/min.  However, increasing concentration of acid (in a range of concentration investigated did not give significant and constant change of adsorption rate constant. For step II process,  adsorption involved physical interaction with the sufficient low adsorption energy (in a range of 311.3 - 1001 J/mol.     Keywords: adsorption, cdmium, diatomaceous earth, kinetics.

  11. Sol-gel transition behavior of aqueous peptide-amphiphile (C16-W3K) solutions: effects of alkyl-tail length, mechanical shear, temperature, and salt

    Science.gov (United States)

    Yamamoto, Masashi; Otsuka, Takahiro; Orimo, Yoshinori; Maeda, Tomoki; Hotta, Atsushi

    Peptide amphiphiles (PA) possess nanoscale micelle structures and excellent biocompatibility. In aqueous PA solution, PA molecules can self-assemble through various configurations into spherical and wormlike micelles, which can occasionally form hydrogels. C16-W3K is one of the unique PA, whose micelle configurations can transfer from spherical to wormlike structures in its aqueous solution over time, while the wormlike micelles could also lead to gelation. In our recent research, the effects of the length of the hydrophobic alkyl tail and other external factors of C16-W3K on the gelation behavior of the C16-W3K solution have been discussed. It has been revealed that longer alkyl-tails could facilitate the gelation of the C16-W3K solution, and that the external stimuli, such as mechanical shear and heat, could promote faster gelation of the C16-W3K solution. It was also found that salt could adjust the pH of the C16-W3K solution, having profound influence on the gelation behavior of the C16-W3K solution. In fact, the gelation of the C16-W3K with a higher storage modulus could be obtained from relatively acidic solutions, while the gelation of the C16-W3K solution was firmly suppressed in highly basic solutions. This work was supported by a Grant-in-Aid for Scientific Research (A) (No. 15H02298 to A.H.) and a Grant-in-Aid for Research Activity Start-up (No.15H06586 to T.M.) from JSPS: KAKENHI.

  12. THERMODYNAMICS OF ETHANOLAMMONIUM CATIONES DISSOCIATION IN AQUEOUS SOLUTIONS

    Directory of Open Access Journals (Sweden)

    R. E. Khoma

    2017-03-01

    Full Text Available The literature data on the thermodynamics of ethanolamines onium cations dissociation have been systematized and generalized. The correlation between these cations dissociation thermodynamic functions (DH and DS and physicochemical properties (Tmp., Tbp, Pp, lgPow et al. has been revealed. There was a correlation between lipophilicity determined experimentally and calculated by QSAR. For monoethanolammonium, diethanolammonium, and their N-methyl and N-ethyl derivatives it was found dissociation thermodynamic functions to depend on bases lgPow. Acid-base dissociation of TRIS and triethanolamine onium cations does not correspond to said relationship because TRIS (primary amine, TEA (tertiary amine act differently on aqueous solutions of SO2. TEA, unlike MEA, DEA and MMEA, has a salting out effect towards sulfur dioxide because of competing hydration that promotes sulfite «onium» salts hydrolysis. TRIS promotes S(IV → S(VI sulphooxidation, in contrast to another ethanolamines. Enthalpy–enthropy compensation with isothermodynamic temperature 303 K has been recorded. The revealed correlations may be useful in developing of procedures for air sanitary cleaning from acidic gases; chemisorbents immobilized for gas and ion exchange chromatography; potentiometric methods for fluorocomplex acids determinations. The use of monoethanolamine is most promising to obtain chemisorbents because the thermodynamic functions of its onium cation acid-base dissociation are least dependent on temperature compared to other etanolammonium cations.

  13. Effect of sodium acetate on the volumetric behaviour of some mono-, di-, and tri-saccharides in aqueous solutions over temperature range (288.15 to 318.15) K

    Energy Technology Data Exchange (ETDEWEB)

    Banipal, Parampaul K., E-mail: pkbanipal@yahoo.co [Department of Chemistry, Guru Nanak Dev University, Amritsar 143 005 (India); Singh, Vickramjeet [Department of Chemistry, Guru Nanak Dev University, Amritsar 143 005 (India); Banipal, Tarlok S. [Department of Applied Chemistry, Guru Nanak Dev University, Amritsar 143 005 (India)

    2010-01-15

    The standard partial molar volumes, V{sub 2}{sup 0} at infinite dilution of eight monosaccharides [D(+)-xylose, D(-)-arabinose, D(-)-ribose, L(-)-sorbose, D(-)-fructose, D(+)-galactose, D(+)-glucose, and D(+)-mannose], six disaccharides [D(+)-cellobiose, sucrose, D(+)-melibiose, D(+)-lactose monohydrate, D(+)-trehalose dihydrate, and D(+)-maltose monohydrate] and two trisaccharides [D(+)-melizitose and D(+)-raffinose pentahydrate] (molalities of saccharides range from (0.03 to 0.12) mol . kg{sup -1}) have been determined in water and in (0.5, 1.0, 2.0, and 3.0) mol . kg{sup -1} aqueous sodium acetate solutions at temperatures, T = (288.15, 298.15, 308.15, and 318.15) K from density measurements using a vibrating-tube digital densimeter. From these results, corresponding standard partial molar volumes of transfer, DELTA{sub t}V{sub 2}{sup 0} have been determined for the transfer of various saccharides from water to aqueous solutions of sodium acetate. Positive values of DELTA{sub t}V{sub 2}{sup 0} were obtained for most of the saccharides, whose magnitude increase with the concentration of sodium acetate as well as temperature. However, negative DELTA{sub t}V{sub 2}{sup 0} values were observed for L(-)-sorbose, D(-)-fructose and D(+)-xylose at lower concentrations of co-solute. The negative magnitude of DELTA{sub t}V{sub 2}{sup 0} values decrease with rise of temperature from (288.15 to 318.15) K. Pair and higher order volumetric interaction coefficients have been determined by using McMillan-Mayer theory. Partial molar expansion coefficients, (partial derivV{sub 2}{sup 0}/partial derivT){sub p} and the second derivatives (partial deriv{sup 2}V{sub 2}{sup 0}/partial derivT{sup 2}){sub p} have also been estimated. These parameters have been utilized to understand various mixing effects in aqueous solutions due to the interactions between solute (saccharide) and co-solute (sodium acetate).

  14. Ab initio molecular dynamics study of the reaction of water with formaldehyde in sulfuric acid solution.

    NARCIS (Netherlands)

    Sprik, M.; Meijer, E.M.

    1998-01-01

    Ab initio molecular dynamics methods have been used to study the reaction mechanism of acidcatalyzed addition of water to formaldehyde in a model system of an aqueous solution of sulfuric acid. Using the method of constraints we find that an H

  15. High pressure sulfuric acid decomposition experiments for the sulfur-iodine thermochemical cycle.

    Energy Technology Data Exchange (ETDEWEB)

    Velasquez, Carlos E; Reay, Andrew R.; Andazola, James C.; Naranjo, Gerald E.; Gelbard, Fred

    2005-09-01

    A series of three pressurized sulfuric acid decomposition tests were performed to (1) obtain data on the fraction of sulfuric acid catalytically converted to sulfur dioxide, oxygen, and water as a function of temperature and pressure, (2) demonstrate real-time measurements of acid conversion for use as process control, (3) obtain multiple measurements of conversion as a function of temperature within a single experiment, and (4) assess rapid quenching to minimize corrosion of metallic components by undecomposed acid. All four of these objectives were successfully accomplished. This report documents the completion of the NHI milestone on high pressure H{sub 2}SO{sub 4} decomposition tests for the Sulfur-Iodine (SI) thermochemical cycle project. All heated sections of the apparatus, (i.e. the boiler, decomposer, and condenser) were fabricated from Hastelloy C276. A ceramic acid injection tube and a ceramic-sheathed thermocouple were used to minimize corrosion of hot liquid acid on the boiler surfaces. Negligible fracturing of the platinum on zirconia catalyst was observed in the high temperature decomposer. Temperature measurements at the exit of the decomposer and at the entry of the condenser indicated that the hot acid vapors were rapidly quenched from about 400 C to less than 20 C within a 14 cm length of the flow path. Real-time gas flow rate measurements of the decomposition products provided a direct measurement of acid conversion. Pressure in the apparatus was preset by a pressure-relief valve that worked well at controlling the system pressure. However, these valves sometimes underwent abrupt transitions that resulted in rapidly varying gas flow rates with concomitant variations in the acid conversion fraction.

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

    Energy Technology Data Exchange (ETDEWEB)

    Robert C. Brown; Maohong Fan

    2001-12-01

    We propose a process that uses sulfur dioxide from coal combustion as a raw material to synthesize polymeric ferric sulfate (PFS), a water treatment agent. The process uses sodium chlorate as an oxidant and ferrous sulfate as an absorbent. The major chemical mechanisms in this reaction system include oxidation, hydrolysis, and polymerization. Oxidation determines sulfur conversion efficiency while hydrolysis and polymerization control the quality of product. Many factors, including SO{sub 2} inlet concentration, flow rate of simulated flue gas, reaction temperature, addition rate of oxidant and stirring rate, may affect the efficiencies of SO{sub 2} removal. Currently, the effects of SO{sub 2} inlet concentration, the flow rate of simulated flue gas and addition rate of flue gas on removal efficiencies of SO{sub 2}, are being investigated. Experiments shown in this report have demonstrated that the conversion efficiencies of sulfur dioxide with ferrous sulfate as an absorbent are in the range of 60-80% under the adopted process conditions. However, the conversion efficiency of sulfur dioxide may be improved by optimizing reaction conditions to be investigated. Partial quality indices of the synthesized products, including Fe{sup 2+} concentration and total iron concentration, have been evaluated.

  17. The importance of temperature in the effective sanitization of aqueous effluents: A review of the case for a thermal treatment that is environmentally and economically credible

    International Nuclear Information System (INIS)

    Burtun, C.

    2009-01-01

    The survival time of pathogens in the environment is normally longest in cold conditions. A large number of published studies have demonstrated a fall in this period from months or years down to a matter of weeks as the ambient temperature rises into the twenties. The effect of temperature is thus not surprisingly a key actor in the sanitizing efficiency of any biological treatment process as conditions move through the mesophilic range (30 to 45 degree centigrade) towards thermophilic conditions (over 50 degree centigrade) again, many publications report a substantial positive impact of such elevated temperatures on many harmful organisms. (Author)

  18. Preservation of organic matter on Mars by sulfur

    Science.gov (United States)

    Eigenbrode, J. L.; Steele, A.; Summons, R. E.; McAdam, A.; Sutter, B.; Franz, H. B.; Freissinet, C.; Millan, M.; Glavin, D. P.; Szopa, C.; Conrad, P. G.; Mahaffy, P. R.

    2016-12-01

    Deltaic-lacustrine mudstones at Pahrump Hills, Gale Crater, Mars yielded a variety of sulfur-containing volatiles upon heating to 500-860°C, as detected by the Sample Analysis at Mars (SAM) instrument onboard the Curiosity rover. The detection of organosulfur compounds comprising thiophenes, dimethylsulfide and thiols by gas chromatography-mass spectrometry and evolved gas analyses, together with aromatic and other hydrocarbon molecules with distributions specific to the sample (i.e., not from the SAM background) indicate that some or all of these organic fragments released at high temperatures are indigenous to the mudstones. The organosulfur compounds are most likely derived from sulfur organics in the sediments. However, there is a possibility that sulfurization of some organic fragments occurred in the oven. On Earth, sulfurization of organic matter is a key process that aids preservation over geological time-scales. This is because it reduces reactive functional groups and adds cross links between small unstable molecules thereby converting them into recalcitrant macromolecules. Sulfurization of organic materials prior to deposition and during early diagenesis may have been a key mechanism responsible for organic matter preservation in the Murray formation mudstones. Sulfur-bearing organics have also been observed in carbonaceous meteorites and there is indication of their presence in the Tissint martian meteorite. A quantitative assessment of organosulfur compounds relative to their non-organic counterparts will be presented for the Murray formation mudstones analyzed by SAM and meteorites analyzed in the laboratory under similar analytical conditions.

  19. Fossilization of melanosomes via sulfurization.

    Science.gov (United States)

    McNamara, Maria E; van Dongen, Bart E; Lockyer, Nick P; Bull, Ian D; Orr, Patrick J

    2016-05-01

    Fossil melanin granules (melanosomes) are an important resource for inferring the evolutionary history of colour and its functions in animals. The taphonomy of melanin and melanosomes, however, is incompletely understood. In particular, the chemical processes responsible for melanosome preservation have not been investigated. As a result, the origins of sulfur-bearing compounds in fossil melanosomes are difficult to resolve. This has implications for interpretations of original colour in fossils based on potential sulfur-rich phaeomelanosomes. Here we use pyrolysis gas chromatography mass spectrometry (Py-GCMS), fourier transform infrared spectroscopy (FTIR) and time of flight secondary ion mass spectrometry (ToF-SIMS) to assess the mode of preservation of fossil microstructures, confirmed as melanosomes based on the presence of melanin, preserved in frogs from the Late Miocene Libros biota (NE Spain). Our results reveal a high abundance of organosulfur compounds and non-sulfurized fatty acid methyl esters in both the fossil tissues and host sediment; chemical signatures in the fossil tissues are inconsistent with preservation of phaeomelanin. Our results reflect preservation via the diagenetic incorporation of sulfur, i.e. sulfurization (natural vulcanization), and other polymerization processes. Organosulfur compounds and/or elevated concentrations of sulfur have been reported from melanosomes preserved in various invertebrate and vertebrate fossils and depositional settings, suggesting that preservation through sulfurization is likely to be widespread. Future studies of sulfur-rich fossil melanosomes require that the geochemistry of the host sediment is tested for evidence of sulfurization in order to constrain interpretations of potential phaeomelanosomes and thus of original integumentary colour in fossils.

  20. Evaluation of Sulfur 'Concrete' for Use as a Construction Material on the Lunar Surface

    Science.gov (United States)

    Grugel, R. N.

    2008-01-01

    Combining molten sulfur with any number of aggregate materials forms, when solid, a mixture having attributes similar, if not better, to conventional water-based concrete. As a result the use of sulfur "concrete" on Earth is well established, particularly in corrosive environments. Consequently, discovery of troilite (FeS) on the lunar surface prompted numerous scenarios about its reduction to elemental sulfur for use, in combination with lunar regolith, as a potential construction material; not requiring water, a precious resource, for its manufacture is an obvious advantage. However, little is known about the viability of sulfur concrete in an environment typified by extreme temperatures and essentially no atmosphere. The experimental work presented here evaluates the response of pure sulfur and sulfur concrete subjected to laboratory conditions that approach those expected on the lunar surface, the results suggesting a narrow window of application.

  1. Volumetric and ultrasonic studies of an antidepressant drug in aqueous and alcoholic medium over temperature range 298.15-313.15 k

    International Nuclear Information System (INIS)

    Jamal, M.A.; Khosa, M.K.; Muneer, M.; Shahzad, K.

    2013-01-01

    Escitalopram oxalate is an amphiphilic serotonin specific reuptake inhibitor-antidepressant drug. Ultrasonic velocity (u) and density (d) measurements were carried out for Escitalopram oxalate in aqueous and alcoholic systems as a function of concentration in a range of molality, m (0.0075-0.04) mol Kg-1 at 298.15-313.15 K using an Anton Paar density sound analyzer (DSA 5000M). Using these experimental values, the acoustical parameters such as apparent molar adiabatic compressibility and partial molar volume (V phi) was apparent molar volume (V phi (K computed for all the systems. The Partial molar expansivity (E/sup 0/) and second derivative values, (partial drive V/sup 0/partial drive T/sup 2/), have also been estimated. The critical micelle concentrations of this drug were obtained from ultrasound velocity measurement by using recently developed least square fitting algorithm. The results are interpreted in the light of structure-making or structure-breaking effects of escitalopram oxalate in the mixtures. (author)

  2. Changes in Nafion® 117 internal structure and related properties during exposure to elevated temperature and pressure in an aqueous environment

    Czech Academy of Sciences Publication Activity Database

    Mališ, J.; Paidar, M.; Bystroň, T.; Brožová, Libuše; Zhigunov, Alexander; Bouzek, K.

    2018-01-01

    Roč. 262, 1 February (2018), s. 264-275 ISSN 0013-4686 Institutional support: RVO:61389013 Keywords : Nafion * elevated temperature * excessive swelling Subject RIV: CG - Electrochemistry OBOR OECD: Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis) Impact factor: 4.798, year: 2016

  3. 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..

  4. 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

  5. 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.

  6. Solubility of sulfur in Fe-Cr-Ni alloys

    International Nuclear Information System (INIS)

    Bogolyubskij, S.D.; Petrova, E.F.; Rogov, A.I.; Shvartsman, L.A.

    1979-01-01

    The solubility of 35 S was determined in Fe-Cr-Ni alloys in the range of temperatures between 910 and 1050 deg C by the method of radiometric analysis. It was found that the solubility of sulfur increases with the concentration of chromium in alloys with 20% Ni

  7. ascorbic acid retention in canned lime juice preserved with sulfur ...

    African Journals Online (AJOL)

    ASCORBIC ACID RETENTION IN CANNED LIME JUICE. PRESERVED WITH SULFUR DIOXIDE AND BENZOIC ACID. Francis M Malhooko“ and Elizabeth N Kiniiya'. ABSTRACT. The effects of two levels each of sodium metabisulfite and sodium benzoate on the shelf-life of canned lime juice stored at ambient temperature ...

  8. Silica sulfuric acid: a versatile and reusable heterogeneous catalyst ...

    African Journals Online (AJOL)

    All the reactions were done at room temperature and the N-acyl carbamates and oxazolidinones were obtained with high yields and purity via an easy work-up procedure. This method is attractive and is in a close agreement with green chemistry. KEY WORDS: N-Acyl carbamates, N-Acyl oxazolidinones, Silica sulfuric acid, ...

  9. For sale: Sulfur emissions

    International Nuclear Information System (INIS)

    Heiderscheit, J.

    1992-01-01

    The allowance trading market has started a slow march to maturity. Competitive developers should understand the risks and opportunities now presented. The marketplace for sulfur dioxide (SO 2 ) emissions allowances - the centerpiece of Title 4's acid rain reduction program - remains enigmatic 19 months after the Clean Air Act amendments of 1990 were passed. Yet it is increasingly clear that the emission allowance market will likely confound the gloom and doom of its doubters. The recently-announced $10 million dollar Wisconsin Power and Light allowance sales to Duquesne Light and the Tennessee Valley Authority are among the latest indications of momentum toward a stabilizing market. This trend puts additional pressure on independent developers to finalize their allowance strategies. Developers who understand what the allowance trading program is and what it is not, know the key players, and grasp the unresolved regulatory issues will have a new competitive advantage. The topics addressed in this article include the allowance marketplace, marketplace characteristics, the regulatory front, forward-looking strategies, and increasing marketplace activity

  10. Diffusion of sulfuric acid in protective organic coatings

    DEFF Research Database (Denmark)

    Wang, Ting; Møller, Victor Buhl; Dam-Johansen, Kim

    Organic protective coatings and linings are widely used to prevent corrosion in industrial processes. However, the permeation of aggressive chemicals through coatings can induce failures. These are described in the literature, but rarely quantified. To measure the diffusion rates of aggressive...... chemicals through organic coatings, a diffusion cell was designed. The diffusion cell designed is simple, small and suitable for scaling up to a battery of cells. A concentration profile of H3O+ through epoxy coatings was achieved for sulfuric acid aqueous solutions, which can be used to estimate diffusion...

  11. The effect of temperature and flow rate on the clarification of the aqueous stevia-extract in a fixed-bed column with zeolites

    Directory of Open Access Journals (Sweden)

    Mantovaneli I. C. C.

    2004-01-01

    Full Text Available Stevia is being used as a sweetener due to its low calorific value and its taste, which is very similar to that of sucrose. After extraction from dried leaves, stevia extract is dark in colour so needs to be clarified for better acceptance by consumers. Adsorption is one of the most important processes in this clarification. In this work the clarification of extract stevia extract in fixed-bed columns with calcium zeolites was studied. Two temperatures (10ºC and 30ºC and six different flow rates (2, 5, 9, 12, 16 and 19 mL/min were studied. The results showed that the mass-transfer coeffcient increases with an increase in flow rate and the length of unused bed reaches a maximum at 9 mL/min for both temperatures. The fit of the Thomas model with the breakthrough data was not very good.

  12. NMR and DSC study of temperature-induced phase transition in aqueous solutions of poly(N-isopropylmethacrylamide-co-acrylamide) copolymers

    Czech Academy of Sciences Publication Activity Database

    Šťastná, J.; Hanyková, L.; Spěváček, Jiří

    2012-01-01

    Roč. 290, č. 17 (2012), s. 1811-1817 ISSN 0303-402X R&D Projects: GA ČR GA202/09/1281 Institutional research plan: CEZ:AV0Z40500505 Institutional support: RVO:61389013 Keywords : temperature induced phase transition * thermosensitive copolymer * poly(N-isopropylmethacrylamide-co- acrylamide ) Subject RIV: CD - Macromolecular Chemistry Impact factor: 2.161, year: 2012

  13. Selective Oxidation of Glycerol to Glyceric Acid in Base-Free Aqueous Solution at Room Temperature Catalyzed by Platinum Supported on Carbon Activated with Potassium Hydroxide

    KAUST Repository

    Tan, Hua

    2016-04-18

    Pt supported on KOH-activated mesoporous carbon (K-AMC) was used to catalyze glycerol oxidation under base-free conditions at room temperature. To study the relationship between the carbon surface chemistry and the catalytic performance of the K-AMC-based Pt catalysts, different levels of surface oxygen functional groups (SOFGs) on the AMC supports were induced by thermal treatment at different temperatures under inert or H2 gas. A strong effect of the surface chemistry was observed on AMC-supported Pt catalysts for glycerol oxidation. The presence of carboxylic acid groups impedes the adsorption of glycerol, which leads to the reduction of catalytic activity, whereas the presence of high-desorption-temperature SOFGs, such as phenol, ether, and carbonyl/quinone groups, provide hydrophilicity to the carbon surface that improves the adsorption of glycerol molecules on Pt metal surface, which is beneficial for the catalytic activity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Flash pyrolysis of coal, coal maceral, and coal-derived pyrite with on-line characterization of volatile sulfur compounds

    Science.gov (United States)

    Chou, I.-Ming; Lake, M.A.; Griffin, R.A.

    1988-01-01

    A Pyroprobe flash pyrolysis-gas chromatograph equipped with a flame photometric detector was used to study volatile sulfur compounds produced during the thermal decomposition of Illinois coal, coal macerals and coal-derived pyrite. Maximum evolution of volatile organic sulfur compounds from all coal samples occurred at a temperature of approximately 700??C. At this temperature, the evolution of thiophene, its alkyl isomers, and short-chain dialkyl sulfide compounds relative to the evolution of benzothiophene and dibenzothiophene compounds was greater from coal high in organic sulfur than from coal low in organic sulfur. The variation in the evolution of sulfur compounds observed for three separate coal macerals (exinite, vitrinite, and inertinite) was similar to that observed for whole coal samples. However, the variation trend for the macerals was much more pronounced. Decomposition of coal-derived pyrite with the evolution of elemental sulfur was detected at a temperature greater than 700??C. The results of this study indicated that the gas chromotographic profile of the volatile sulfur compounds produced during flash pyrolysis of coals and coal macerals varied as a function of the amount of organic sulfur that occurred in the samples. Characterization of these volatile sulfur compounds provides a better understanding of the behavior of sulfur in coal during the thermolysis process, which could be incorporated in the design for coal cleaning using flash pyrolysis techniques. ?? 1988.

  15. Continuous-flow ultrasound assisted oxidative desulfurization (UAOD) process: An efficient diesel treatment by injection of the aqueous phase.

    Science.gov (United States)

    Rahimi, Masoud; Shahhosseini, Shahrokh; Movahedirad, Salman

    2017-11-01

    A new continuous-flow ultrasound assisted oxidative desulfurization (UAOD) process was developed in order to decrease energy and aqueous phase consumption. In this process the aqueous phase is injected below the horn tip leading to enhanced mixing of the phases. Diesel fuel as the oil phase with sulfur content of 1550ppmw and an appropriate mixture of hydrogen peroxide and formic acid as the aqueous phase were used. At the first step, the optimized condition for the sulfur removal has been obtained in the batch mode operation. Hence, the effect of more important oxidation parameters; oxidant-to-sulfur molar ratio, acid-to-sulfur molar ratio and sonication time were investigated. Then the optimized conditions were obtained using Response Surface Methodology (RSM) technique. Afterwards, some experiments corresponding to the best batch condition and also with objective of minimizing the residence time and aqueous phase to fuel volume ratio have been conducted in a newly designed double-compartment reactor with injection of the aqueous phase to evaluate the process in a continuous flow operation. In addition, the effect of nozzle diameter has been examined. Significant improvement on the sulfur removal was observed specially in lower sonication time in the case of dispersion method in comparison with the conventional contact between two phases. Ultimately, the flow pattern induced by ultrasonic device, and also injection of the aqueous phase were analyzed quantitatively and qualitatively by capturing the sequential images. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. The enhanced anisotropic properties of the Fe sub 3 sub - sub x M sub x O sub 4 (M = Fe, Co, Mn) films deposited on glass surface from aqueous solutions at low temperature

    CERN Document Server

    Kim, T Y; Kim, Y I; Lee, C S; Park, J C; Kim, D

    2003-01-01

    The enhancement of structural anisotropy and magnetic anisotropy in ferrite films, Fe sub 3 sub - sub x M sub x O sub 4 (M = Fe, Co, Mn), which were deposited on glass substrates from aqueous solutions by thin liquid film (TLF) method at a low temperature (358 K), was compared in x-ray diffraction, conversion electron Moessbauer spectroscopy, and vibrating sample magnetometer measurements. The experimental results showed that the highly coercive Fe sub 3 sub - sub x Co sub x O sub 4 films, maximum coercivity of 0.21 T at room temperature, have a preferential growing direction along the magnetic easy axis of the magnetite, (111). While anisotropy was enhanced by the addition of Co sup 2 sup + ions in the reaction solution, no enhancement was observed in the TLF-films of Fe sub 3 O sub 4 and Fe sub 3 sub - sub x Mn sub x O sub 4. The enhanced anisotropy is probably caused by the extra stabilization energy of the Co sup 2 sup + ions in the octahedral sites of the spinel and the interactions between the Co sup 2 ...

  17. Calculation of the standard partial molal thermodynamic properties and dissociation constants of aqueous HCl{sup 0} and HBr{sup 0} at temperatures to 1000 C and pressures to 5 kbar

    Energy Technology Data Exchange (ETDEWEB)

    Pokrovskii, V.A. [ETH Zentrum, Zuerich (Switzerland). Dept. Erdwissenschaften NO

    1999-04-01

    Dissociation constants of aqueous ion pairs HCl{sup 0} and HBr{sup 0} derived in the literature from vapor pressure and supercritical conductance measurements (Quist and Marshall, 1968b; Frantz and Marshall, 1984) were used to calculate the standard partial molal thermodynamic properties of the species at 25 C and 1 bar. Regression of the data with the aid of revised Helgeson-Kirkham-Flowers equations of state (Helgeson et al., 1981; Tanger and Helgeson, 1988; Shock et al., 1989) resulted in a set of equations-of-state parameters that permits accurate calculation of the thermodynamic properties of the species at high temperatures and pressures. These properties and parameters reproduce generally within 0.1 log unit (with observed maximum deviation of 0.23 log unit) the log K values for HBr{sup 0} and HCl{sup 0} given by Quist and Marshall (1968b) and Frantz and Marshall (1984), respectively, at temperatures to 800 C and pressures to 5 kbar.

  18. Efficient indium-tin-oxide free inverted organic solar cells based on aluminum-doped zinc oxide cathode and low-temperature aqueous solution processed zinc oxide electron extraction layer

    International Nuclear Information System (INIS)

    Chen, Dazheng; Zhang, Chunfu; Wang, Zhizhe; Zhang, Jincheng; Tang, Shi; Wei, Wei; Sun, Li; Hao, Yue

    2014-01-01

    Indium-tin-oxide (ITO) free inverted organic solar cells (IOSCs) based on aluminum-doped zinc oxide (AZO) cathode, low-temperature aqueous solution processed zinc oxide (ZnO) electron extraction layer, and poly(3-hexylthiophene-2, 5-diyl):[6, 6]-phenyl C 61 butyric acid methyl ester blend were realized in this work. The resulted IOSC with ZnO annealed at 150 °C shows the superior power conversion efficiency (PCE) of 3.01%, if decreasing the ZnO annealing temperature to 100 °C, the obtained IOSC also shows a PCE of 2.76%, and no light soaking issue is observed. It is found that this ZnO film not only acts as an effective buffer layer but also slightly improves the optical transmittance of AZO substrates. Further, despite the relatively inferior air-stability, these un-encapsulated AZO/ZnO IOSCs show comparable PCEs to the referenced ITO/ZnO IOSCs, which demonstrates that the AZO cathode is a potential alternative to ITO in IOSCs. Meanwhile, this simple ZnO process is compatible with large area deposition and plastic substrates, and is promising to be widely used in IOSCs and other relative fields.

  19. Growth kinetics of step edges on celestite (0 0 1) surfaces as a function of temperature, saturation state, ionic strength, and aqueous strontium:sulfate ratio: An in-situ atomic force microscopy study

    Science.gov (United States)

    Bracco, Jacquelyn N.; Gooijer, Yiscka; Higgins, Steven R.

    2016-02-01

    Step velocities on the celestite (0 0 1) surface have been measured as a function of temperature (23-45 °C), saturation state (S = 1.1-2.2), ionic strength (I = 0.01, 0.06, and 0.1 M), and aqueous strontium:sulfate ratio (r = 0.01-100) using atomic force microscopy (AFM). Celestite growth hillocks were flanked by [0 1 0]-aligned step edges, which are polar, and step edges vicinal to , which are non-polar. [0 1 0] step velocities increased with temperature and saturation state, however step velocities did not vary significantly with ionic strength. Step velocities were non-linear with saturation state, suggesting a change in mechanism at high S as compared with low S. At constant S, the step velocities were maximized at r = 1 and decreased significantly at extreme r, demonstrating the governing role of solute stoichiometry. We successfully fit the step velocity data as a function of r using the Stack and Grantham (2010) nucleation and propagation model. Based on the results as a function of ionic strength and r, the mechanism at low S is likely ion-by-ion attachment to the step with an activation energy of 75 (±10) kJ mol-1. At high S the mechanism is a combination of the one at low S and possibly attachment of a neutral species such as an ion pair with an activation energy of 43 (±9) kJ mol-1.

  20. The effect of potential upon the high-temperature fatigue crack growth response of low-alloy steels. Part 1: Crack growth results

    International Nuclear Information System (INIS)

    James, L.A.; Moshier, W.C.

    1997-01-01

    Corrosion-fatigue crack propagation experiments were conducted on several low-alloy steels in elevated temperature aqueous environments, and experimental parameters included temperature, sulfur content of the steel, applied potential level, and dissolved hydrogen (and in one case, dissolved oxygen) concentration in the water. Specimen potentials were controlled potentiostatically, and the observation (or non-observation) of accelerated fatigue crack growth rates was a complex function of the above parameters. Electrochemical results and the postulated explanation for the complex behavior are given in Part II

  1. Numerical Simulation of Condensation of Sulfuric Acid and Water in a Large Two-stroke Marine Diesel Engine

    DEFF Research Database (Denmark)

    Walther, Jens Honore; Karvounis, Nikolas; Pang, Kar Mun

    2016-01-01

    on the sulfuric acid gas phase. A linear correlation is found between the fuel sulfur content and the sulfuric acid condensation rate. The initial in-cylinder water content is found not to affect the sulfuric acid condensation but it has a high impact on water condensation. The scavenging pressure level shows...... an inverse correlation between pressure and condensation rate due to change in the flame propagation speed. Finally, increasing the cylinder liner temperature significantly decreases water condensation but has a negligible influence on the condensation of sulfuric acid.......We present results from computational fluid dynamics simulations of the condensation of sulfuric acid (H2SO4) and water (H2O) in a large two-stroke marine diesel engine. The model uses a reduced n-heptane skeletal chemical mechanism coupled with a sulfur subsetto simulate the combustion process...

  2. Photocatalytic transformations of organic sulfur compounds and H2S

    Science.gov (United States)

    Vorontsov, A. V.

    2008-10-01

    Modern views on the products, pathways and kinetic features of liquid- and gas-phase photocatalytic reactions of sulfur compounds in the presence of heterogeneous and homogeneous photocatalysts are generalised. Attention is focussed on the aliphatic and aromatic reduced sulfur compounds and pesticides. The reaction rate in the liquid and gas phases are analysed as function of solution pH, temperature, catalyst content, substrate concentration, solvent type, air moisture and added oxidants. Photocatalyst deactivation and the ways for recovery of its activity are considered.

  3. Volcanogenic Sulfur on Earth and Io: Composition and Spectroscopy

    Science.gov (United States)

    Kargel, J.S.; Delmelle, P.; Nash, D.B.

    1999-01-01

    The causes of Io's variegated surface, especially the roles of sulfur, and the geochemical history of sulfur compounds on Io are not well understood. Suspecting that minor impurities in sulfur might be important, we have investigated the major and trace element chemistry and spectroscopic reflectance of natural sulfur from a variety of terrestrial volcanic-hydrothermal environments. Evidence suggests that Io may be substantially coated with impure sulfur. On Earth, a few tenths of a percent to a few percent of chalcophile trace elements (e.g., As and Se) comonly occur in sulfur and appear to stabilize material of yellow, brown, orange, and red hues, which may persist even at low temperatures. Percentage levels of chalcophile impurities are reasonably expected to occur on Io in vapor sublimate deposits and flows derived from such deposits. Such impurities join a host of other mechanisms that might explain Io's reds and yellows. Two-tenths to two percent opaque crystalline impurities, particularly pyrite (FeS2), commonly produces green, gray, and black volcanic sulfur on Earth and might explain areas of Io having deposits of these colors. Pyrite produces a broad absorption near 1 ??m that gradually diminishes out to 1.6 ??m - similar but not identical to the spectrum of Io seen in Galileo NIMS data. Percentage amounts of carbonaceous impurities and tens of percent SiO2 (as silicates) also strongly affect the spectral properties of Earth's sulfur. Io's broad absorption between 0.52 and 0.64 ??m remains unexplained by these data but could be due to sodium sulfides, as suggested previously by others, or to As, Se, or other impurities. These impurities and others, such as P and Cl (which could exist on Io's surface in amounts over 1% that of sulfur), greatly alter the molecular structure of molten and solid sulfur. Minor impurities could impact Io's geology, such as the morphology of sulfur lava flows and the ability of sulfur to sustain high relief. We have not found

  4. 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.

  5. Calculation of the Aqueous Thermodynamic Properties of Citric Acid Cycle Intermediates and Precursors and the Estimation of High Temperature and Pressure Equation of State Parameters

    Directory of Open Access Journals (Sweden)

    Mitchell Schulte

    2009-06-01

    Full Text Available The citric acid cycle (CAC is the central pathway of energy transfer for many organisms, and understanding the origin of this pathway may provide insight into the origins of metabolism. In order to assess the thermodynamics of this key pathway for microorganisms that inhabit a wide variety of environments, especially those found in high temperature environments, we have calculated the properties and parameters for the revised Helgeson-Kirkham-Flowers equation of state for the major components of the CAC. While a significant amount of data is not available for many of the constituents of this fundamental pathway, methods exist that allow estimation of these missing data.

  6. Assessment of environmental control technology for coal conversion aqueous wastes

    Energy Technology Data Exchange (ETDEWEB)

    Klein, J.A.; Barker, R.E.

    1978-07-01

    A hydrocarbonization process has been studied to assess environmental control technology for coal conversion wastewaters. Fifteen major wastewater streams were identified; 2 present serious environmental problems not routinely encountered in industry. These are the hydrocarbonization condensate and the ash sluicing waste from the gasifier. The hydrocarbonization product water is high in phenolics, ammonia, cyanide, thiocyanate, and other sulfur compounds. This stream will present a significant wastewater treatment problem unless the stream can be recycled internally. The gasifier-ash sluicing water will probably be similar to ash sluicing water from coal-fired power generating plants. However, the large quantity of toxic trace elements may be more easily dissolved from ash produced at the lower-temperature and reducing conditions encountered in gasification. A number of cleanup technologies relevant to the cleanup of coal conversion aqueous effluents have ben assessed for their adaptability to the specific pollutants found in coal hydrocarbonization wastewater. A summary of these processes lists the potential applicability, economics, raw material requirements, process compatibility, operating conditions, state of development, environmental problems, energy requirements, and availability of each. Indications are that almost any level of removal can be achieved if one is willing to pay the cost. The optimum amount of cleanup will require much future interaction between industry, environmental control technology developers, human and environmental effects assessors, and federal effluent regulations administrators.

  7. Aqueous Hybrids of Silica Nanoparticles and Hydrophobically Associating Hydrolyzed Polyacrylamide Used for EOR in High-Temperature and High-Salinity Reservoirs

    Directory of Open Access Journals (Sweden)

    Dingwei Zhu

    2014-06-01

    Full Text Available Water-soluble polymers are known to be used in chemically enhanced oil recovery (EOR processes, but their applications are limited in high-temperature and high-salinity oil reservoirs because of their inherent poor salt tolerance and weak thermal stability. Hydrophobic association of partially hydrolyzed polyacryamide (HAHPAM complexed with silica nanoparticles to prepare nano-hybrids is reported in this work. The rheological and enhanced oil recovery (EOR properties of such hybrids were studied in comparison with HAHPAM under simulated high-temperature and high-salinity oil reservoir conditions (T: 85 °C; total dissolved solids: 32,868 mg∙L−1; [Ca2+] + [Mg2+]: 873 mg∙L−1. It was found that the apparent viscosity and elastic modulus of HAHPAM solutions increased with addition of silica nanoparticles, and HAHPAM/silica hybrids exhibit better shear resistance and long-term thermal stability than HAHPAM in synthetic brine. Moreover, core flooding tests show that HAHPAM/silica hybrid has a higher oil recovery factor than HAHPAM solution.

  8. The removal of reactive dyes from aqueous solutions using chemically modified mesoporous silica in the presence of anionic surfactant-The temperature dependence and a thermodynamic multivariate analysis

    International Nuclear Information System (INIS)

    Cestari, Antonio R.; Vieira, Eunice F.S.; Vieira, Glaucia S.; Costa, Luiz P. da; Tavares, Andrea M.G.; Loh, Watson; Airoldi, Claudio

    2009-01-01

    The three-parameter Sips adsorption model was successfully employed to modeled equilibrium adsorption data of a yellow and a red dye onto a mesoporous aminopropyl-silica, in the presence of the surfactant sodium dodecylbenzenesulfonate (DBS) from 25 to 55 deg. C. The results were evaluated in relation to the previously reported surface tension measurements. The presence of curvatures of the vant Hoff plots suggested the presence of non-zero heat capacities terms (Δ ads C p ). For the yellow dye, it is observed that the values of Δ ads H are almost all positive and they decrease in endothermicity, in the absence and in the presence of DBS, from 25 to 55 deg. C. For the red dye, there is an increase in endothermicity in relation to the temperature increase. The negative Δ ads G values indicate spontaneous adsorption processes. Almost all adsorption entropy values (Δ ads S) were positive. This suggests that entropy is a driving force of adsorption. The adsorption thermodynamic parameters were also evaluated using a new 2 3 full factorial design analysis. The multivariate polynomial modelings indicated that the thermodynamic parameters are also affected by important interactive effects of the experimental factors and not by the temperature changes alone

  9. Reactions of SIV species with organic compounds: formation mechanisms of organo-sulfur derivatives in atmospheric aerosols

    Science.gov (United States)

    Passananti, Monica; Shang, Jing; Dupart, Yoan; Perrier, Sébastien; George, Christian

    2015-04-01

    Secondary organic aerosol (SOA) have an important impact on climate, air quality and human health. However the chemical reactions involved in their formation and growth are not fully understood or well-constrained in climate models. It is well known that inorganic sulfur (mainly in oxidation states (+IV) and (+VI)) plays a key role in aerosol formation, for instance sulfuric acid is known to be a good nucleating gas. In addition, acid-catalyzed heterogeneous reactions of organic compounds has shown to produce new particles, with a clear enhancement in the presence of ozone (Iinuma 2013). Organosulfates have been detected in tropospheric particles and aqueous phases, which suggests they are products of secondary organic aerosol formation process (Tolocka 2012). Originally, the production of organosulfates was explained by the esterification reaction of alcohols, but this reaction in atmosphere is kinetically negligible. Other formation pathways have been suggested such as hydrolysis of peroxides and reaction of organic matter with sulfite and sulfate radical anions (SO3-, SO4-) (Nozière 2010), but it remains unclear if these can completely explain atmospheric organo-sulfur aerosol loading. To better understand the formation of organo-sulfur compounds, we started to investigate the reactivity of SIV species (SO2 and SO32-) with respect to specific functional groups (organic acids and double bonds) on atmospherically relevant carboxylic acids and alkenes. The experiments were carried out in the homogeneous aqueous phase and at the solid-gas interface. A custom built coated-wall flow tube reactor was developed to control relativity humidity, SO2 concentration, temperature and gas flow rate. Homogeneous and heterogeneous reaction kinetics were measured and resulting products were identified using liquid chromatography coupled with an orbitrap mass spectrometer (LC-HR-MS). The experiments were performed with and without the presence of ozone in order to evaluate any

  10. 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

  11. Production of petroleum bitumen by oxidation of heavy oil residue with sulfur

    Science.gov (United States)

    Tileuberdi, Ye.; Akkazyn, Ye. A.; Ongarbayev, Ye. K.; Imanbayev, Ye. I.; Mansurov, Z. A.

    2018-03-01

    In this paper production of bitumen adding elemental sulfur at oxidation of oil residue are investigated. The objects of research were distilled residue of Karazhanbas crude oil and elemental sulfur. These oil residue characterized by a low output of easy fractions and the high content of tar-asphaltene substances, therefore is the most comprehensible feedstock for producing bitumen. The sulfur is one of the oil product collected in oil extraction regions. Oxidation process of hydrocarbons carried out at temperatures from 180 up to 210 °С without addition of sulfur and with the addition of sulfur (5-10 wt. %) for 4 hours. At 200 °С oxidation of hydrocarbons with 5, 7 and 10 wt.% sulfur within 3-4 h allows receiving paving bitumen on the mark BND 200/300, BND 130/200, BN 90/130 and BN 70/30. Physical and mechanical characteristics of oxidation products with the addition of 5-7 wt. % sulfur corresponds to grade of paving bitumen BND 40/60. At the given temperature oxidized for 2.5-3 h, addition of 10 wt. % sulfur gave the products of oxidation describing on parameters of construction grades of bitumen (BN 90/10).

  12. ADDITIVE TESTING FOR IMPROVED SULFUR RETENTION: PRELIMINARY REPORT

    Energy Technology Data Exchange (ETDEWEB)

    Amoroso, J.; Fox, K.

    2011-09-07

    The Savannah River National Laboratory is collaborating with Alfred University to evaluate the potential for additives in borosilicate glass to improve sulfur retention. This preliminary report provides further background on the incorporation of sulfur in glass and outlines the experiments that are being performed by the collaborators. A simulated waste glass composition has been selected for the experimental studies. The first phase of experimental work will evaluate the impacts of BaO, PbO, and V{sub 2}O{sub 5} at concentrations of 1.0, 2.0, and 5.0 wt % on sulfate retention in simulated high level waste borosilicate glass. The second phase of experimental work will evaluate the effects of time at the melt temperature on sulfur retention. The resulting samples will be characterized to determine the amount of sulfur remaining as well as to identify the formation of any crystalline phases. The results will be used to guide the future selection of frits and glass forming chemicals in vitrifying Department of Energy wastes containing high sulfur concentrations.

  13. ENERGY EFFICIENCY LIMITS FOR A RECUPERATIVE BAYONET SULFURIC ACID DECOMPOSITION REACTOR FOR SULFUR CYCLE THERMOCHEMICAL HYDROGEN PRODUCTION

    Energy Technology Data Exchange (ETDEWEB)

    Gorensek, M.; Edwards, T.

    2009-06-11

    A recuperative bayonet reactor design for the high-temperature sulfuric acid decomposition step in sulfur-based thermochemical hydrogen cycles was evaluated using pinch analysis in conjunction with statistical methods. The objective was to establish the minimum energy requirement. Taking hydrogen production via alkaline electrolysis with nuclear power as the benchmark, the acid decomposition step can consume no more than 450 kJ/mol SO{sub 2} for sulfur cycles to be competitive. The lowest value of the minimum heating target, 320.9 kJ/mol SO{sub 2}, was found at the highest pressure (90 bar) and peak process temperature (900 C) considered, and at a feed concentration of 42.5 mol% H{sub 2}SO{sub 4}. This should be low enough for a practical water-splitting process, even including the additional energy required to concentrate the acid feed. Lower temperatures consistently gave higher minimum heating targets. The lowest peak process temperature that could meet the 450-kJ/mol SO{sub 2} benchmark was 750 C. If the decomposition reactor were to be heated indirectly by an advanced gas-cooled reactor heat source (50 C temperature difference between primary and secondary coolants, 25 C minimum temperature difference between the secondary coolant and the process), then sulfur cycles using this concept could be competitive with alkaline electrolysis provided the primary heat source temperature is at least 825 C. The bayonet design will not be practical if the (primary heat source) reactor outlet temperature is below 825 C.

  14. Magmatic (silicates/saline/sulfur-rich/CO2) immiscibility and zirconium and rare-earth element enrichment from alkaline magma chamber margins : Evidence from Ponza Island, Pontine Archipelago, Italy

    Science.gov (United States)

    Belkin, H.E.; de Vivo, B.; Lima, A.; Torok, K.

    1996-01-01

    Fluid inclusions were measured from a feldspathoid-bearing syenite xenolith entrained in trachyte from Ponza, one of the islands of the Pontine Archipelago, located in the Gulf of Gaeta, Italy. The feldspathoid-bearing syenite consists mainly of potassium feldspar, clinopyroxene, amphibole, biotite, titanite, manganoan magnetite, apatite with minor nosean, Na-rich feldspar, pyrrhotite, and rare cheralite. Baddeleyite and zirkelite occur associated with manganoan magnetite. Detailed electron-microprobe analysis reveals enrichments in REE, Y, Nb, U, Th as well as Cl and F in appropriate phases. Fluid inclusions observed in potassium feldspar are either silicate-melt or aqueous inclusions. The aqueous inclusions can be further classified as. (1) one-phase vapor, (2) two-phase (V + L) inclusions, vapor-rich inclusions with a small amount of CO2 in most cases; homogenization of the inclusions always occurred in the vapor phase between 359 and 424??C, salinities vary from 2.9 to 8.5 wt. % NaCl equivalent; and. (3) three-phase and multiphase inclusions (hypersaline/sulfur-rich aqueous inclusions sometimes with up to 8 or more solid phases). Daughter minerals dissolve on heating before vapor/liquid homogenization. Standardless quantitative scanning electron microscope X-ray fluorescence analysis has tentatively identified the following chloride and sulfate daughter crystals; halite, sylvite, glauberite. arcanite, anhydrite, and thenardite. Melting of the daughter crystals occurs between 459 and 536??C (54 to 65 wt. % NaCI equivalent) whereas total homogenization is between 640 and 755??C. The occurrence of silicate-melt inclusions and high-temperature, solute-rich aqueous inclusions suggests that the druse or miarolitic texture of the xenolith is late-stage magmatic. The xenolith from Ponza represents a portion of the peripheral magma chamber wall that has recorded the magmatic/hydrothermal transition and the passage of high solute fluids enriched in chlorides, sulfur, and

  15. Sulfur loaded in micropore-rich carbon aerogel as cathode of lithium-sulfur battery with improved cyclic stability

    Science.gov (United States)

    Li, Zihao; Li, Xiaogang; Liao, Youhao; Li, Xiaoping; Li, Weishan

    2016-12-01

    We report a novel composite of sulfur loaded in micropore-rich carbon aerogel (CA-S), as cathode of lithium-sulfur battery. Carbon aerogel (CA) is synthesized through phenol-formaldehyde reaction with a low catalyst concentration and carbonization under high temperature, and loaded with sulfur via chemical deposition and heat treatment. The physical properties of the resulting CA and the electrochemical performances of the resulting CA-S are investigated by scanning electron microscopy, thermal gravimetric analysis, Brunauer-Emmett-Teller characterization, electrochemical impedance spectroscopy, and galvanostatic discharge/charge test, with a comparison of a common carbon material, acetylene black (AB), and sulfur loaded in AB (AB-S). It is found that the CA is micropore-rich with micropore volume over 66% of total pore volume, and the CA-S exhibits significantly improved cyclic stability compared with AB-S. The improved performance of CA-S is attributed to the confinement of the micropores in CA to small sulfur allotropes and corresponding lithium sulfides.

  16. Catalysis and stability of an alkaline protease from a haloalkaliphilic bacterium under non-aqueous conditions as a function of pH, salt and temperature.

    Science.gov (United States)

    Pandey, Sandeep; Rakholiya, Kalpna D; Raval, Vikram H; Singh, Satya P

    2012-09-01

    A haloalkaliphilic bacterium, isolated from Coastal Gujarat (India) was identified as Oceanobacillus sp. (GQ162111) based on 16S rRNA gene sequence. The organism grew and secreted extra cellular protease in presence of various organic solvents. At 30% (v/v) concentration of hexane, heptane, isooctane, dodecane and decane, significant growth and protease production was evident. The alkaline protease was purified in a single step on phenyl sepharose 6 FF with 28% yield. The molecular mass as judged by SDS-PAGE was 30 kDa. The temperature optimum of protease was 50°C and the enzyme retained 70% activity in 10% (v/v) isooctane. Effect of salt and pH was investigated in combination to assess the effect of isooctane. In organic solvents, the enzyme was considerably active at pH 8-11, with optimum activity at pH 10. Salt at 2 M was optimum for activity and enzyme maintained significant stability up to 18 h even at 3 M salt concentration. Patters of growth, protease production, catalysis and stability of the enzyme are presented. The study resumes significance as limited information is available on the interaction of haloalkaliphilic bacteria and their enzymes with organic solvents. Copyright © 2012 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

  17. Piezoelectric and opto-electrical properties of silver-doped ZnO nanorods synthesized by low temperature aqueous chemical method

    Directory of Open Access Journals (Sweden)

    E. S. Nour

    2015-07-01

    Full Text Available In this paper, we have synthesized Zn1−xAgxO (x = 0, 0.03, 0.06, and 0.09 nanorods (NRs via the hydrothermal method at low temperature on silicon substrate. The characterization and comparison between the different Zn1−xAgxO samples, indicated that an increasing Ag concentration from x = 0 to a maximum of x = 0.09; All samples show a preferred orientation of (002 direction with no observable change of morphology. As the quantity of the Ag dopant was changed, the transmittances, as well as the optical band gap were decreased. X-ray photoelectron spectroscopy data clearly indicate the presence of Ag in ZnO crystal lattice. A nanoindentation-based technique was used to measure the effective piezo-response of different concentrations of Ag for both direct and converse effects. The value of the piezoelectric coefficient (d33 as well as the piezo potential generated from the ZnO NRs and Zn1−xAgxO NRs was found to decrease with the increase of Ag fraction. The finding in this investigation reveals that Ag doped ZnO is not suitable for piezoelectric energy harvesting devices.

  18. Investigation of a fusion technique for the determination of total sulfur in geological samples by ion chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Stallings, E.A.; Candelaria, L.M.; Gladney, E.S.

    1988-06-01

    The authors have encountered the need for a rapid, accurate, precise, and sensitive method for measuring total sulfur in large numbers of geological samples. Numerous environmental studies of sulfur deposition due to sulfur dioxide emission from combustion and industry are currently under way. Several techniques for measuring total sulfur in soils and other silicate materials have been published including neutron activation analysis, thermal neutron capture prompt ..gamma..-ray spectrometry, inductively coupled plasma atomic emission spectrometry, isotope dilution mass spectrometry, X-ray fluorescence, turbidimetry, ion chromatography (IC), iodimetric titration, and fluorometry. However, none of these methods is completely satisfactory for routine analysis of large numbers of samples. Many have levels of detection that are inadequate for measuring low levels of total sulfur (<100 ..mu..g/g) often encountered in soils. Several utilize only aqueous extracts of the soils and do not provide a total sulfur determination. Others require extensive sample preparation, are susceptible to loss of sulfur during oxidation, or produce incomplete conversion of sulfur species to sulfate. The objective of this work was to evaluate the accuracy of IC determination of sulfate for Na/sub 2/O/sub 2/ soil fusions by comparing the results obtained for reference materials with literature values reported for other techniques. They were also interested in determining if this fusion method would be rapid enough to handle large numbers of samples.

  19. Synchrotron x-ray spectroscopy of EuHN O3 aqueous solutions at high temperatures and pressures and Nb-bearing silicate melt phases coexisting with hydrothermal fluids using a modified hydrothermal diamond anvil cell and rail assembly

    Science.gov (United States)

    Mayanovic, Robert A.; Anderson, Alan J.; Bassett, William A.; Chou, I.-Ming

    2007-01-01

    A modified hydrothermal diamond anvil cell (HDAC) rail assembly has been constructed for making synchrotron x-ray absorption spectroscopy, x-ray fluorescence, and x-ray mapping measurements on fluids or solid phases in contact with hydrothermal fluids up to ???900??C and 700 MPa. The diamond anvils of the HDAC are modified by laser milling grooves or holes, for the reduction of attenuation of incident and fluorescent x rays and sample cavities. The modified HDAC rail assembly has flexibility in design for measurement of light elements at low concentrations or heavy elements at trace levels in the sample and the capability to probe minute individual phases of a multiphase fluid-based system using focused x-ray microbeam. The supporting rail allows for uniform translation of the HDAC, rotation and tilt stages, and a focusing mirror, which is used to illuminate the sample for visual observation using a microscope, relative to the direction of the incident x-ray beam. A structure study of Eu(III) aqua ion behavior in high-temperature aqueous solutions and a study of Nb partitioning and coordination in a silicate melt in contact with a hydrothermal fluid are described as applications utilizing the modified HDAC rail assembly. ?? 2007 American Institute of Physics.

  20. Determination of the sulfur mustard hydrolysis product thiodiglycol by microcolumn liquid chromatography coupled on-line with sulfur flame photometric detection using large-volumn injections and peak compression.

    NARCIS (Netherlands)

    Hooijschuur, E.W.J.; Kientz, C.E.; Brinkman, U.A.T.

    1999-01-01

    A selective, direct and relatively rapid method has been developed for the determination of thiodiglycol (TDG) in aqueous samples. TDG is the main hydrolysis product of the chemical warfare agent sulfur mustard. The method of analysis is based on the on-line coupling of reversed-phase microcolumn

  1. Growth of the acidophilic iron-sulfur bacterium Acidithiobacillus ferrooxidans under Mars-like geochemical conditions

    Science.gov (United States)

    Bauermeister, Anja; Rettberg, Petra; Flemming, Hans-Curt

    2014-08-01

    The question of life on Mars has been in focus of astrobiological research for several decades, and recent missions in orbit or on the surface of the planet are constantly expanding our knowledge on Martian geochemistry. For example, massive stratified deposits have been identified on Mars containing sulfate minerals and iron oxides, which suggest the existence of acidic aqueous conditions in the past, similar to acidic iron- and sulfur-rich environments on Earth. Acidophilic organisms thriving in such habitats could have been an integral part of a possibly widely extinct Martian ecosystem, but remains might possibly even exist today in protected subsurface niches. The chemolithoautotrophic strain Acidithiobacillus ferrooxidans was selected as a model organism to study the metabolic capacities of acidophilic iron-sulfur bacteria, especially regarding their ability to grow with in situ resources that could be expected on Mars. The experiments were not designed to accurately simulate Martian physical conditions (except when certain single parameters such as oxygen partial pressure were considered), but rather the geochemical environment that can be found on Mars. A. ferrooxidans could grow solely on the minerals contained in synthetic Mars regolith mixtures with no added nutrients, using either O2 as an external electron acceptor for iron oxidation, or H2 as an external electron donor for iron reduction, and thus might play important roles in the redox cycling of iron on Mars. Though the oxygen partial pressure of the Martian atmosphere at the surface was not sufficient for detectable iron oxidation and growth of A. ferrooxidans during short-term incubation (7 days), alternative chemical O2-generating processes in the subsurface might yield microhabitats enriched in oxygen, which principally are possible under such conditions. The bacteria might also contribute to the reductive dissolution of Fe3+-containing minerals like goethite and hematite, which are

  2. Lunar Sulfur Capture System, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — The Lunar Sulfur Capture System (LSCS) is an innovative method to recover sulfur compounds from lunar soil using sorbents derived primarily from in-situ resources....

  3. Advanced Lithium Sulfur Battery, Phase II

    Data.gov (United States)

    National Aeronautics and Space Administration — CRG proposes to develop an Advanced Lithium Sulfur Battery (LSB) based on combining a novel super ion conducting ceramic electrolyte, entrapped sulfur cathode, and a...

  4. Advanced Lithium Sulfur Battery, Phase I

    Data.gov (United States)

    National Aeronautics and Space Administration — CRG proposes to develop an Advanced Lithium Sulfur Battery (LSB) based on combining a novel super ion conducting ceramic electrolyte, entrapped sulfur cathode, and a...

  5. Lunar Sulfur Capture System, Phase II

    Data.gov (United States)

    National Aeronautics and Space Administration — The Lunar Sulfur Capture System (LSCS) is an innovative method to capture greater than 90 percent of sulfur gases evolved during thermal treatment of lunar soils....

  6. Electrochemical processing of WC-Ni pseudo alloys in sulfuric acid solutions to ammonium paratungstate and nickel(II) sulfate

    International Nuclear Information System (INIS)

    Kuntyj, O.I.; Ivashkiv, V.R.; Yavorskij, V.T.; Zozulya, G.I.

    2007-01-01

    Electrolysis of a WC-Ni pseudo alloy in aqueous sulfuric acid solutions was studied to develop a method for secondary tungsten waste utilization. A flowsheet for production of ammonium paratungstate and nickel(II) sulfate is suggested, in which the process solutions are recycled. The major electrolysis parameters are presented [ru

  7. 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

  8. 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

  9. Genetic engineering of sulfur-degrading Sulfolobus

    Energy Technology Data Exchange (ETDEWEB)

    Ho, N.W.Y.

    1991-01-01

    The objectives of the proposed research is to first establish a plasmid-mediated genetic transformation system for the sulfur degrading Sulfolobus, and then to clone and overexpress the genes encoding the organic-sulfur-degrading enzymes from Sulfolobus- as well as from other microorganisms, to develop a Sulfolobus-based microbial process for the removal of both organic and inorganic sulfur from coal.

  10. 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...

  11. 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...

  12. 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;…

  13. Eagle-Picher Industries Sodium Sulfur Program

    Science.gov (United States)

    Silvey, Ronald L.

    1993-02-01

    Viewgraphs of the sodium sulfur program are presented. Sodium sulfur low earth orbit (LEO) cells are described. Topics covered include cell sizes, areas of improvement, and NaS cell testing. Sodium sulfur cell and battery designs continue to evolve with significant improvement demonstrated in resistance, rechargeability, cycle life, energy density, and electrolyte characterization.

  14. Design and cost of the sulfuric acid decomposition reactor for the sulfur based hydrogen processes - HTR2008-58009

    International Nuclear Information System (INIS)

    Hu, T. Y.; Connolly, S. M.; Lahoda, E. J.; Kriel, W.

    2008-01-01

    The key interface component between the reactor and chemical systems for the sulfuric acid based processes to make hydrogen is the sulfuric acid decomposition reactor. The materials issues for the decomposition reactor are severe since sulfuric acid must be heated, vaporized and decomposed. SiC has been identified and proven by others to be an acceptable material. However, SiC has a significant design issue when it must be interfaced with metals for connection to the remainder of the process. Westinghouse has developed a design utilizing SiC for the high temperature portions of the reactor that are in contact with the sulfuric acid and polymeric coated steel for low temperature portions. This design is expected to have a reasonable cost for an operating lifetime of 20 years. It can be readily maintained in the field, and is transportable by truck (maximum OD is 4.5 meters). This paper summarizes the detailed engineering design of the Westinghouse Decomposition Reactor and the decomposition reactor's capital cost. (authors)

  15. Thermodynamic equilibrium calculations of sulfur poisoning in Ce-O-S and La-O-S systems

    Energy Technology Data Exchange (ETDEWEB)

    Karjalainen, Heidi; Lassi, Ulla; Rahkamaa-Tolonen, Katariina; Kroeger, Virpi; Keiski, Riitta L. [University of Oulu, Department of Process and Environmental Engineering, P.O. Box 4300, FIN-90014 Oulu (Finland)

    2005-02-28

    Sulfur poisoning is still a problem in many application areas of exhaust gas catalysts despite the fact that the sulfur levels, e.g. in gasoline are being continuously reduced. The aim of this study was to calculate thermodynamic equilibrium compositions of sulfur in Ce-O-S and La-O-S systems in the presence of precious metals (Pt, Pd, and Rh), which all were considered as bulk materials, in order to understand the experimentally observed sulfur poisoning under the real applications of exhaust gas catalysts. Depending on temperature and oxygen partial pressure, sulfur can be present in the form of sulfates, sulfides and oxysulfides. It is thermodynamically favorable that cerium oxide reacts with SO{sub 2} to form cerium sulfate at low temperatures and cerium oxysulfides at high temperatures. Lanthanum oxide reacts with SO{sub 2} to form sulfate under oxidizing conditions and sulfides under reducing conditions.

  16. 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.

  17. Aqueous Peroxyoxalate Chemiluminescence.

    Science.gov (United States)

    1982-01-01

    Mannich reaction of the appropriate chlorophenols with morpholine and formaldehyde as outlined in Scheme 31. T "i Page 95 Scheme 3]1 H + + CH 2 0 f-NCR 2 -V...solution has been obtained from the reaction of hydrogen peroxide with bis-[N-2-(N’-methyl-2’-pyridinium)ethyl-N-trifluoro- methylsulfonyljjoxamide in the...SYSTEMS 4 A. RESULTS 4 I. AQUEOUS REACTIONS 4 2. NON-AQUEOUS REACTIONS 38 B. DISCUSSION 52 1. AQUEOUS REACTIONS 52 2. NON-AQUEOUS REACTIONS 56 IV. SYNTHESES

  18. Fixation à haute et moyenne température de l'hydrogène sulfuré par des masses de captation régénérables Hydrogen-Sulfide Fixation At High and Medium Temperature by Regenerable Capture Masses

    Directory of Open Access Journals (Sweden)

    Hotier G.

    2006-11-01

    Full Text Available L'intérêt de la désulfuration haute température comparée à la même opération conduite à basse température est renforcé quand la désulfuration a lieu entre deux opérations de niveau thermique élevé comme la gazéification du charbon et la production d'électricité par cycles combinés turbine à gaz-turbine à vapeur. Les masses absorbantes à base d'oxyde de fer peuvent réaliser une bonne désulfuration mais résistent mal aux chocs thermiques. Un agent de régénération particulièrement efficace est le dioxyde de soufre qui peut réoxyder le sulfure de fer par une réaction légèrement endothermique. Un des principaux avantages de cette réaction est la production directe de soufre élémentaire. Ses désavantages sont une faible conversion par passe et la sulfatation de l'oxyde de calcium (une des nombreuses impuretés des boues rouges qui composent la masse. Lorsque l'on emploie de la vapeur pour diluer le SO2 deux autres réactions ont lieu. La production de soufre est augmentée et la sulfatation disparaît. Les productions principales du procédé sont du soufre élémentaire et de la vapeur haute pression. On rencontre deux zones de réactions (l'une de captation, l'autre de régénération séparées par un tampon de gaz inerte et une circulation de la masse. Aucune autre unité de traitement de soufre n'est requise sur le site. Une évaluation économique préliminaire montre que ce procédé est compétitif lorsqu'on le compare à un lavage des gaz par solvant, à froid. The interest of a high temperature unit compared to a low temperature one is enhanced when desulphurization takes place between two hotoperations like coal gasification and power generation by combined cycles. Iron oxide based sorbents such as redmuds can achieve good desulphurization but cannot withstand high temperature gradients. An efficient regenerating agent is sulphur dioxide. SO2 can regenerate iron sulphide with a slightly endothermic

  19. Thermal transformations of organic and inorganic sulfur in Type II kerogen quantified by S-XANES

    Science.gov (United States)

    Kelemen, Simon R.; Sansone, Michael; Walters, Clifford C.; Kwiatek, Peter J.; Bolin, Trudy

    2012-04-01

    Sulfur X-ray Absorption Near Edge Structure Spectroscopy (S-XANES) was used to quantify the thermal transformations of organic and inorganic sulfur forms in pyrite-containing Type II kerogens and kerogen chars after open system pyrolysis for a series of well-defined times and temperatures. These results are compared to identical experiments conducted on the same kerogens treated to be pyrite-free. No significant differences were found in the thermal transformations of organic sulfur between the pyrite-containing and pyrite-free kerogen. The loss of aliphatic sulfur forms occurs early (equivalent Ro 1.5%). In pyrite-containing kerogens, the complete conversion of pyrite (FeS2) into pyrrhotite (Fe1-xS) occurs by a laboratory equivalent Ro = 1.5%, followed by the conversion of pyrrhotite into troilite (FeS) at higher maturity. The availability of hydrogen from hydrocarbons generated from kerogen accelerates the initial decomposition of pyrite resulting in pyrrhotite and H2S evolution. H2S evolution up to Ro = 2.4% corresponds to the sulfur loss associated with pyrrhotite and troilite formation and aliphatic sulfur loss, indicating that sulfur from pyrite results almost exclusively in H2S evolution with no significant incorporation and retention of sulfur into the organic matter of the kerogen chars under the current set of open system pyrolysis conditions.

  20. Determination of total sulfur content via sulfur-specific chemiluminescence detection

    Energy Technology Data Exchange (ETDEWEB)

    Kubala, S.W.; Campbell, D.N. [Fluid Data, Inc., Angleton, TX (United States); DiSanzo, F.P. [Paulsboro Research Lab., NJ (United States)

    1995-12-31

    A specially designed system, based upon sulfur-specific chemiluminescence detection (SSCD), was developed to permit the determination of total sulfur content in a variety of samples. This type of detection system possesses several advantages such as excellent linearity and selectivity, low minimum detectable levels, and an equimolar response to various sulfur compounds. This paper will focus on the design and application of a sulfur-specific chemiluminescence detection system for use in determining total sulfur content in gasoline.

  1. Rhodanese functions as sulfur supplier for key enzymes in sulfur energy metabolism.

    Science.gov (United States)

    Aussignargues, Clément; Giuliani, Marie-Cécile; Infossi, Pascale; Lojou, Elisabeth; Guiral, Marianne; Giudici-Orticoni, Marie-Thérèse; Ilbert, Marianne

    2012-06-08

    How microorganisms obtain energy is a challenging topic, and there have been numerous studies on the mechanisms involved. Here, we focus on the energy substrate traffic in the hyperthermophilic bacterium Aquifex aeolicus. This bacterium can use insoluble sulfur as an energy substrate and has an intricate sulfur energy metabolism involving several sulfur-reducing and -oxidizing supercomplexes and enzymes. We demonstrate that the cytoplasmic rhodanese SbdP participates in this sulfur energy metabolism. Rhodaneses are a widespread family of proteins known to transfer sulfur atoms. We show that SbdP has also some unusual characteristics compared with other rhodaneses; it can load a long sulfur chain, and it can interact with more than one partner. Its partners (sulfur reductase and sulfur oxygenase reductase) are key enzymes of the sulfur energy metabolism of A. aeolicus and share the capacity to use long sulfur chains as substrate. We demonstrate a positive effect of SbdP, once loaded with sulfur chains, on sulfur reductase activity, most likely by optimizing substrate uptake. Taken together, these results lead us to propose a physiological role for SbdP as a carrier and sulfur chain donor to these key enzymes, therefore enabling channeling of sulfur substrate in the cell as well as greater efficiency of the sulfur energy metabolism of A. aeolicus.

  2. Aqueous Wetting Films on Fused Quartz.

    Science.gov (United States)

    Mazzoco; Wayner

    1999-06-15

    Using an image analyzing interferometer, IAI, the interfacial characteristics of an isothermal constrained vapor bubble, CVB, in a quartz cuvette were studied as a precursor to heat transfer research. The effects of pH and electrolyte concentration on the meniscus properties (curvature and adsorbed film thickness) and the stability of the aqueous wetting films were evaluated. The surface potential in the electric double layer was a function of the cleaning and hydroxylation of the quartz surface. The disjoining pressure isotherm for pure water was very close to that predicted by the Langmuir equation. For aqueous solutions of moderate electrolyte concentration, the Gouy-Chapman theory provided a good representation of the electrostatic effects in the film. The effect of temperature on the film properties of aqueous solutions and pure water was also evaluated: The meniscus curvature decreased with increasing temperature, while Marangoni effects, intermolecular forces, and local evaporation and condensation enhanced waves on the adsorbed film layer. Pure water wetting films were mechanically metastable, breaking into droplets and very thin films (less than 10 nm) after a few hours. Aqueous wetting films with pH 12.4 proved to be stable during a test of several months, even when subjected to temperature and mechanical perturbations. The mechanical stability of wetting films can explain the reported differences between the critical heat fluxes of pure water and aqueous solutions. The IAI-CVB technique is a simple and versatile experimental technique for studying the characteristics of interfacial systems. Copyright 1999 Academic Press.

  3. Bacterial sulfur cycle shapes microbial communities in surface sediments of an ultramafic hydrothermal vent field

    DEFF Research Database (Denmark)

    Schauer, Regina; Røy, Hans; Augustin, Nico

    2011-01-01

    RNA sequence analysis, was characterized by the capability to metabolize sulfur components. High sulfate reduction rates as well as sulfide depleted in (34)S further confirmed the importance of the biogeochemical sulfur cycle. In contrast, methane was found to be of minor relevance for microbial life in mat......, these sediments were investigated in order to determine biogeochemical processes and key organisms relevant for primary production. Temperature profiling at two mat-covered sites showed a conductive heating of the sediments. Elemental sulfur was detected in the overlying mat and metal-sulfides in the upper...

  4. Thermal Regeneration of Sulfuric Acid Hydrates after Irradiation

    Science.gov (United States)

    Loeffler, Mark J.; Hudson, Reggie L.

    2012-01-01

    In an attempt to more completely understand the surface chemistry of the jovian icy satellites, we have investigated the effect of heating on two irradiated crystalline sulfuric acid hydrates, H2SO4 4H2O and H2SO4 H2O. At temperatures relevant to Europa and the warmer jovian satellites, post-irradiation heating recrystallized the amorphized samples and increased the intensities of the remaining hydrate's infrared absorptions. This thermal regeneration of the original hydrates was nearly 100% efficient, indicating that over geological times, thermally-induced phase transitions enhanced by temperature fluctuations will reform a large fraction of crystalline hydrated sulfuric acid that is destroyed by radiation processing. The work described is the first demonstration of the competition between radiation-induced amorphization and thermally-induced recrystallization in icy ionic solids relevant to the outer Solar System.

  5. Removal of patulin from aqueous solutions by propylthiol functionalized SBA-15.

    Science.gov (United States)

    Appell, Michael; Jackson, Michael A; Dombrink-Kurtzman, Mary Ann

    2011-03-15

    Propylthiol functionalized SBA-15 silica was investigated to detoxify aqueous solutions contaminated with the regulated mycotoxin patulin. Micelle templated silicas with a specific pore size were synthetically modified to possess propylthiol groups, a functional group known to form Michael reaction products with the conjugated double bond system of patulin. BET surface area analysis indicated the propylthiol functionalized SBA-15 possesses channels with the pore size of 5.4 nm and a surface area of 345 m(2)g(-1). Elemental analysis indicates the silicon/sulfur ratio to be 10:1, inferring one propylthiol substituent for every ten silica residues. The propylthiol modified SBA-15 was effective at significantly reducing high levels of patulin from aqueous solutions (pH 7.0) in batch sorption assays at room temperature. The material was less effective at lower pH; however heating low pH solutions and apple juice to 60 °C in the presence of propylthiol functionalized SBA-15 significantly reduced the levels of patulin in contaminated samples. Composite molecular models developed by semi-empirical PM3 and empirical force field methods support patulin permeation through the mesoporous channels of propylthiol functionalized SBA-15. Density functional study at the B3LYP/6-31G(d,p) level predicts the proposed patulin adducts formed by reaction with the thiol residues exhibit less electrophilic properties than patulin. It is demonstrated the use of propylthiol functionalized SBA-15 is a viable approach to reduce patulin levels in aqueous solutions, including contaminated apple juice. Published by Elsevier B.V.

  6. Removal of patulin from aqueous solutions by propylthiol functionalized SBA-15

    Energy Technology Data Exchange (ETDEWEB)

    Appell, Michael, E-mail: michael.appell@ars.usda.gov [Bacterial Foodborne Pathogens and Mycology Research Unit, United States Department of Agriculture, Agricultural Research Service, National Center for Agricultural Utilization Research, 1815 N. University St., Peoria, IL 61604 (United States); Jackson, Michael A.; Dombrink-Kurtzman, Mary Ann [Renewable Product Technology Research Unit, United States Department of Agriculture, Agricultural Research Service, National Center for Agricultural Utilization Research, 1815 N. University St., Peoria, IL 61604 (United States)

    2011-03-15

    Propylthiol functionalized SBA-15 silica was investigated to detoxify aqueous solutions contaminated with the regulated mycotoxin patulin. Micelle templated silicas with a specific pore size were synthetically modified to possess propylthiol groups, a functional group known to form Michael reaction products with the conjugated double bond system of patulin. BET surface area analysis indicated the propylthiol functionalized SBA-15 possesses channels with the pore size of 5.4 nm and a surface area of 345 m{sup 2} g{sup -1}. Elemental analysis indicates the silicon/sulfur ratio to be 10:1, inferring one propylthiol substituent for every ten silica residues. The propylthiol modified SBA-15 was effective at significantly reducing high levels of patulin from aqueous solutions (pH 7.0) in batch sorption assays at room temperature. The material was less effective at lower pH; however heating low pH solutions and apple juice to 60 deg, C in the presence of propylthiol functionalized SBA-15 significantly reduced the levels of patulin in contaminated samples. Composite molecular models developed by semi-empirical PM3 and empirical force field methods support patulin permeation through the mesoporous channels of propylthiol functionalized SBA-15. Density functional study at the B3LYP/6-31G(d,p) level predicts the proposed patulin adducts formed by reaction with the thiol residues exhibit less electrophilic properties than patulin. It is demonstrated the use of propylthiol functionalized SBA-15 is a viable approach to reduce patulin levels in aqueous solutions, including contaminated apple juice.

  7. Removal of patulin from aqueous solutions by propylthiol functionalized SBA-15

    International Nuclear Information System (INIS)

    Appell, Michael; Jackson, Michael A.; Dombrink-Kurtzman, Mary Ann

    2011-01-01

    Propylthiol functionalized SBA-15 silica was investigated to detoxify aqueous solutions contaminated with the regulated mycotoxin patulin. Micelle templated silicas with a specific pore size were synthetically modified to possess propylthiol groups, a functional group known to form Michael reaction products with the conjugated double bond system of patulin. BET surface area analysis indicated the propylthiol functionalized SBA-15 possesses channels with the pore size of 5.4 nm and a surface area of 345 m 2 g -1 . Elemental analysis indicates the silicon/sulfur ratio to be 10:1, inferring one propylthiol substituent for every ten silica residues. The propylthiol modified SBA-15 was effective at significantly reducing high levels of patulin from aqueous solutions (pH 7.0) in batch sorption assays at room temperature. The material was less effective at lower pH; however heating low pH solutions and apple juice to 60 deg, C in the presence of propylthiol functionalized SBA-15 significantly reduced the levels of patulin in contaminated samples. Composite molecular models developed by semi-empirical PM3 and empirical force field methods support patulin permeation through the mesoporous channels of propylthiol functionalized SBA-15. Density functional study at the B3LYP/6-31G(d,p) level predicts the proposed patulin adducts formed by reaction with the thiol residues exhibit less electrophilic properties than patulin. It is demonstrated the use of propylthiol functionalized SBA-15 is a viable approach to reduce patulin levels in aqueous solutions, including contaminated apple juice.

  8. Mars Aqueous Processing System

    Science.gov (United States)

    Berggren, Mark; Wilson, Cherie; Carrera, Stacy; Rose, Heather; Muscatello, Anthony; Kilgore, James; Zubrin, Robert

    2012-01-01

    The goal of the Mars Aqueous Processing System (MAPS) is to establish a flexible process that generates multiple products that are useful for human habitation. Selectively extracting useful components into an aqueous solution, and then sequentially recovering individual constituents, can obtain a suite of refined or semi-refined products. Similarities in the bulk composition (although not necessarily of the mineralogy) of Martian and Lunar soils potentially make MAPS widely applicable. Similar process steps can be conducted on both Mars and Lunar soils while tailoring the reaction extents and recoveries to the specifics of each location. The MAPS closed-loop process selectively extracts, and then recovers, constituents from soils using acids and bases. The emphasis on Mars involves the production of useful materials such as iron, silica, alumina, magnesia, and concrete with recovery of oxygen as a byproduct. On the Moon, similar chemistry is applied with emphasis on oxygen production. This innovation has been demonstrated to produce high-grade materials, such as metallic iron, aluminum oxide, magnesium oxide, and calcium oxide, from lunar and Martian soil simulants. Most of the target products exhibited purities of 80 to 90 percent or more, allowing direct use for many potential applications. Up to one-fourth of the feed soil mass was converted to metal, metal oxide, and oxygen products. The soil residue contained elevated silica content, allowing for potential additional refining and extraction for recovery of materials needed for photovoltaic, semiconductor, and glass applications. A high-grade iron oxide concentrate derived from lunar soil simulant was used to produce a metallic iron component using a novel, combined hydrogen reduction/metal sintering technique. The part was subsequently machined and found to be structurally sound. The behavior of the lunar-simulant-derived iron product was very similar to that produced using the same methods on a Michigan iron

  9. New ZnO-Based Regenerable Sulfur Sorbents for Fluid-Bed/Transport Reactor Applications

    Energy Technology Data Exchange (ETDEWEB)

    Slimane, R.B.; Lau, F.S.; Abbasian, J.; Ho, K.H.

    2002-09-19

    The overall objective of the ongoing sorbent development work at GTI is the advancement to the demonstration stage of a promising ZnO-TiO2 sulfur sorbent that has been developed under DCCA/ICCI and DOE/NETL sponsorship. This regenerable sorbent has been shown to possess an exceptional combination of excellent chemical reactivity, high effective capacity for sulfur absorption, high resistance to attrition, and regenerability at temperatures lower than required by typical zinc titanates.

  10. 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.

  11. Exposure experiments of trees to sulfur dioxide gas. Part I

    Energy Technology Data Exchange (ETDEWEB)

    Otani, A.

    1974-12-01

    The effects of gaseous sulfur dioxide on trees were studied. Twenty species of plant seedlings (70 cm in height) including Cedrus deodara, Metasequoia glyptostroboides, Ginkgo biloba, Celmus parvifolia var. albo-marginata, Pinus thumbergii, P. densiflora, Cryptomeria japonica, and Quercus myrsinaefolia, were exposed in a room to gaseous sulfur dioxide at 0.8 ppm for 7.5 hr/day (from 9 am to 4:30 pm) for 24 days at a temperature of 20-35 deg C and RH of 55-75%. Visible damage to plants was lighter in C.j. and Chamae cyparis obtusa, more severe in P.t., G.b., and C.d. The damage appeared earlier in G.b., Cinnamomum camphona, and Ilex rotunda, and the change of early symptoms was smaller in P.t., C.j., and C.o. The leaves of the 4-5th positions from the sprout were apt to be damaged. Although the sulfur content of exposed leaves increased markedly, that in other parts did not increase. Because of the high concentration of the gas and the short period of exposure, the absorption of sulfur into leaves should have differed from the situation in fields where longer exposure to lower concentrations of the gas would be expected. 6 references.

  12. Volatile earliest Triassic sulfur cycle

    DEFF Research Database (Denmark)

    Schobben, Martin; Stebbins, Alan; Algeo, Thomas J.

    2017-01-01

    Marine biodiversity decreases and ecosystem destruction during the end-Permian mass extinction (EPME) have been linked to widespread marine euxinic conditions. Changes in the biogeochemical sulfur cycle, microbial sulfate reduction (MSR), and marine dissolved sulfate concentrations during...... is based on the S isotope fractionation between sulfate and sulfide associated with MSR in natural aquatic environments. This fractionation is proxied by the difference in S isotope compositions between chromium-reducible sulfur (CRS) and carbonate-associated sulfate (CAS), i.e., δ34SCAS-CRS. We show that......, despite region-specific redox conditions, δ34SCAS-CRS exhibits a nearly invariant value of 15-16‰ in both study sections. By comparing our record with a δ34Ssulfate-sulfide density distribution for modern marine sediments, we deduce that porewater Rayleigh distillation, carbonate diagenesis, and other...

  13. Infrared optical constants of aqueous sulfate-nitrate-ammonium multi-component tropospheric aerosols from attenuated total reflectance measurements-Part I: Results and analysis of spectral absorbing features

    International Nuclear Information System (INIS)

    Boer, Gregory J.; Sokolik, Irina N.; Martin, Scot T.

    2007-01-01

    In this paper, the first part of two, we present new high-spectral-resolution infrared (IR) optical constants for multi-component aqueous solutions composed of ammonium sulfate, ammonium nitrate, sulfuric acid and nitric acid over a range of compositions and temperatures representative of tropospheric conditions and atmospheric aerosols. The optical constants were determined from ATR measurements via a Kramers-Kronig transformation. To accomplish this, we adapted an existing technique for estimating the real index of refraction of aqueous sulfate and nitrate solutions at multiple visible frequencies as a function of concentration and temperature. An approximation of the low-frequency behavior of the ATR spectrum was also used to reduce the error associated with using ATR data of finite frequency range. This paper also provides a brief examination of absorption spectra for analyzed mixtures in relation to their composition and temperature and discusses possible implications. The new optical constants will be of great utility to high-spectral-resolution IR remote sensing as well as radiative balance analysis in climate studies because they will enable researchers for the first time to model the impacts of tropospheric aqueous sulfate-nitrate-ammonium multi-component aerosols, including their mixtures with other important species such as dust or soot

  14. Study by neutron diffusion of local order liquid sulfur around the polymerization transition; Etude par diffusion de neutrons de l`ordre local du soufre liquide autour de la transition de polymerisation

    Energy Technology Data Exchange (ETDEWEB)

    Descotes, L.

    1994-05-01

    We studied the liquid sulfur according to the temperature. The sulfur is one of the most complicated elementary liquid. We experimented the neutron diffusion by the powder orthorhombic sulfur. The complexity at the polymerization transition are only accompanied by weak local structural transfer. 231 refs., 48 figs., 8 tabs., 3 annexes.

  15. Viscosity of plasticized sulfur-extended asphalt: two-factor sequential optimization

    Directory of Open Access Journals (Sweden)

    Gladkikh Vitaliy

    2017-01-01

    Full Text Available The compounding properties of construction materials for pavements strongly depend on dynamic viscosity of the binder. The favorable class of binder is plasticized sulfur-extended asphalt. Unfortunately, the viscosity of such a binder has not been studied in detail. In the present work we have performed experimental two-factor sequential constrained optimization of the viscosity. The binders under examination were made of asphalt, sulfur and paraffin. It was revealed that the addition of sulfur and paraffin leads to a significant decrease of the dynamic viscosity. The obtained results allowed us to estimate mixture and temperature that correspond to optimal compounding properties of the sulfur-extended asphalt concrete. In particular, for plasticized asphalt concrete with 30% of sulfur and 5% of paraffin, the optimal processing temperature is 25 °C lower than for ordinary asphalt. Since low preparation temperatures correspond to low emission of toxic gases and low processing costs, we can consider the concretes that will be based on plasticized sulfur-extended asphalt as green paving materials.

  16. Reaction kinetics of waste sulfuric acid using H2O2catalytic oxidation.

    Science.gov (United States)

    Wang, Jiade; Hong, Binxun; Tong, Xinyang; Qiu, Shufeng

    2016-12-01

    The process of recovering waste sulfuric acids using H 2 O 2 catalytic oxidation is studied in this paper. Activated carbon was used as catalyst. Main operating parameters, such as temperature, feed rate of H 2 O 2 , and catalyst dosage, have effects on the removal of impurities from waste sulfuric acids. The reaction kinetics of H 2 O 2 catalytic oxidation on impurities are discussed. At a temperature of 90°C, H 2 O 2 feeding rate of 50 g (kg waste acid) -1 per hour, and catalyst dosage of 0.2 wt% (waste acid weight), the removal efficiencies of COD and chrominance were both more than 99%, the recovery ratio of sulfuric acid was more than 95%, and the utilization ratio of H 2 O 2 was 88.57%. Waste sulfuric acid is a big environmental problem in China. The amount of waste sulfuric acid is huge every year. Many small and medium-sized businesses produced lots of waste acids, but they don't have an appropriate method to treat and recover them. H 2 O 2 catalytic oxidation has been used to treat and recover waste sulfuric acid and activated carbon is the catalyst here. Main parameters, such as temperature, feed rate of H 2 O 2 , and catalyst dosage, have been investigated. The reaction kinetics are discussed. This method can be economical and feasible for most small and medium-sized businesses.

  17. Sulfur globule oxidation in green sulfur bacteria is dependent on the dissimilatory sulfite reductase system

    DEFF Research Database (Denmark)

    Holkenbrink, Carina; Ocón Barbas, Santiago; Mellerup, Anders

    2011-01-01

    Green sulfur bacteria oxidize sulfide and thiosulfate to sulfate with extracellular globules of elemental sulfur as intermediate. Here we investigated which genes are involved in the formation and consumption of these sulfur globules in the green sulfur bacterium Chlorobaculum tepidum. We show...... that sulfur globule oxidation is strictly dependent on the dissimilatory sulfite reductase (DSR) system. Deletion of dsrM/CT2244 or dsrT/CT2245 or the two dsrCABL clusters (CT0851-CT0854, CT2247-2250) abolished sulfur globule oxidation and prevented formation of sulfate from sulfide, whereas deletion of dsr...

  18. Iron-niobium-aluminum alloy having high-temperature corrosion resistance

    Science.gov (United States)

    Hsu, Huey S.

    1988-04-14

    An alloy for use in high temperature sulfur and oxygen containing environments, having aluminum for oxygen resistance, niobium for sulfur resistance and the balance iron, is discussed. 4 figs., 2 tabs.

  19. Electrochemical improvement of low-temperature petroleum cokes by chemical oxidation with H2O2 for their use as anodes in lithium ion batteries

    International Nuclear Information System (INIS)

    Concheso, A.; Santamaria, R.; Menendez, R.; Jimenez-Mateos, J.M.; Alcantara, R.; Lavela, P.; Tirado, J.L.

    2006-01-01

    The electrochemical performance of non-graphitized petroleum cokes has been improved by mild oxidation using hydrogen peroxide, a procedure used for the first time in these materials. For this purpose, various carbonisation temperatures and H 2 O 2 treatments were tested. For low sulfur content cokes, the aqueous oxidative treatment significantly increases the capacity values above 372 mAh/g during the first cycles. In contrast, cokes with a sulfur content of ca. 5%, did not shown a real improvement. The former results have been interpreted in terms of an effective oxidation of the particles surface, which removes unorganized carbon, where lithium can be irreversibly trapped. Moreover, a stable and less resistive passivating layer grows during the first discharge of lithium, as revealed by impedance spectroscopy. Therefore, chemical procedures, as mild oxidation, open an interesting field of research for the improvement of disordered carbons as anode materials in lithium ion batteries

  20. Solvation properties of N-substituted cis and trans amides are not identical: significant enthalpy and entropy changes are revealed by the use of variable temperature 1H NMR in aqueous and chloroform solutions and ab initio calculations.

    Science.gov (United States)

    Troganis, Anastassios N; Sicilia, Emilia; Barbarossou, Klimentini; Gerothanassis, Ioannis P; Russo, Nino

    2005-12-29

    The cis/trans conformational equilibrium of N-methyl formamide (NMF) and the sterically hindered tert-butylformamide (TBF) was investigated by the use of variable temperature gradient 1H NMR in aqueous solution and in the low dielectric constant and solvation ability solvent CDCl3 and various levels of first principles calculations. The trans isomer of NMF in aqueous solution is enthalpically favored relative to the cis (deltaH(o) = -5.79 +/- 0.18 kJ mol(-1)) with entropy differences at 298 K (298 x deltaS(o) = -0.23 +/- 0.17 kJ mol(-1)) playing a minor role. The experimental value of the enthalpy difference strongly decreases (deltaH(o) = -1.72 +/- 0.06 kJ mol(-1)), and the contribution of entropy at 298 K (298 x deltaS(o) = -1.87 +/- 0.06 kJ mol(-1)) increases in the case of the sterically hindered tert-butylformamide. The trans isomer of NMF in CDCl3 solution is enthalpically favored relative to the cis (deltaH(o) = -3.71 +/- 0.17 kJ mol(-1)) with entropy differences at 298 K (298 x deltaS(o) = 1.02 +/- 0.19 kJ mol(-1)) playing a minor role. In the sterically hindered tert-butylformamide, the trans isomer is enthalpically disfavored (deltaH(o) = 1.60 +/- 0.09 kJ mol(-1)) but is entropically favored (298 x deltaS(o) = 1.71 +/- 0.10 kJ mol(-1)). The results are compared with literature data of model peptides. It is concluded that, in amide bonds at 298 K and in the absence of strongly stabilizing sequence-specific inter-residue interactions involving side chains, the free energy difference of the cis/trans isomers and both the enthalpy and entropy contributions are strongly dependent on the N-alkyl substitution and the solvent. The significant decreasing enthalpic benefit of the trans isomer in CDCl3 compared to that in H2O, in the case of NMF and TBF, is partially offset by an adverse entropy contribution. This is in agreement with the general phenomenon of enthalpy versus entropy compensation. B3LY/6-311++G** and MP2/6-311++G** quantum chemical calculations

  1. 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)

  2. Development of a CO2 Sequestration Module by Integrating Mineral Activation and Aqueous Carbonation

    Energy Technology Data Exchange (ETDEWEB)

    George Alexander; Parvana Aksoy; John Andresen; Mercedes Maroto-Valer; Harold Schobert

    2006-08-14

    Mineral carbonation is a promising concept for permanent CO{sub 2} sequestration due to the vast natural abundance of the raw materials and the permanent storage of CO{sub 2} in solid form as carbonates. The sequestration of CO{sub 2} through the employment of magnesium silicates--olivine and serpentine--is beyond the proof of concept stage. For the work done in this project, serpentine was chosen as the feedstock mineral due to its abundance and availability. Although the reactivity of olivine is greater than that of serpentine, physical and chemical treatments have been shown to increase greatly the reactivity of serpentine. The primary drawback to mineral carbonation is reaction kinetics. To accelerate the carbonation, aqueous processes are preferred, where the minerals are first dissolved in solution. In aqueous carbonation, the key step is the dissolution rate of the mineral, where the mineral dissolution reaction is likely to be surface-controlled. The relatively low reactivity of serpentine has warranted research into physical and chemical treatments that have been shown to greatly increase its reactivity. The use of sulfuric acid as an accelerating medium for the removal of magnesium from serpentine has been investigated. To accelerate the dissolution process, the mineral can be ground to very fine particle size, <37 {micro}m, but this is a very energy-intensive process. Previous work in our laboratory showed that chemical surface activation helps to dissolve magnesium from the serpentine (of particle size {approx} 100 {micro}m) and that the carbonation reaction can be conducted under mild conditions (20 C and 4.6 MPa) compared to previous studies that required >185 C, >13 MPa, and <37 {micro}m particle size. This work also showed that over 70% of the magnesium can be extracted at ambient temperature, leaving an amorphous silica with surface area of about 330 m{sup 2}/g. The overall objective of this research program is to optimize the active carbonation

  3. Role of Sulfur in the Formation of Magmatic-Hydrothermal Copper-Gold Deposits

    Science.gov (United States)

    Seo, J.; Guillong, M.; Heinrich, C.

    2009-05-01

    Sulfur plays essential roles in hydrothermal ore-forming processes [1], which calls for precise and accurate quantitative sulfur determination in fluid inclusions. Feasibility tests for sulfur quantification by comparing data from both LA-Quadrupole (Q) - ICP-MS and LA-High Resolution (HR) - ICP-MS show that reliable sulfur quantification in fluid inclusions is possible [2], provided that a very careful baseline correction is applied. We investigate the metal transporting capabilities of sulfur by measuring sulfur together with copper and other elements in cogenetic brine and vapor inclusions ('boiling assemblages') in single healed crack hosted by quartz veins. Samples are from high-temperature magmatic-hydrothermal ore deposits and miarolitic cavities of barren granitoid. Clear compositional correlations of sulfur with copper and gold were found. A molar S/Cu ratio commonly close to 2 but never above 2, indicates sulfur-complexed metal transportation in the high-temperature hydrothermal vapor, and probably also in the Na-Fe-K-Cl-enriched brines. Vapor/brine partitioning trends of the S and Cu are shown to be related with the chemistry of the fluids (possibly by various sulfur speciations in varying pH, fO2) and causative magma source. In the boiling hydrothermal environments, higher vapor partitioning of Cu and S is observed at reduced and peraluminous Sn-W granite, whereas oxidized and perakaline porphyry-style deposits have a lower partitioning to the vapor although the total concentration of S, Cu, Au in both fluid phase is higher than in the Sn-W granite [3]. Vapor inclusion in the boiling assemblages from magmatic-hydrothermal ore deposits and granitic intrusions generally contain an excess of sulfur over ore metals such as Cu, Fe, and Mo. This allows efficient sulfide ore precipitation in high-temperature porphyry-type deposits, and complexation of gold by the remaining sulfide down to lower temperatures. The results confirm earlier interpretations [1] and

  4. Precipitation of gold by the reaction of aqueous gold(III)-chloride with cyanobacteria at 25-80 C -- Studied by x-ray absorption spectroscopy

    International Nuclear Information System (INIS)

    Lengke, M. F.; Ravel, B.; Fleet, M. E.; Wanger, G.; Gordon, R. A.; Southam, G.

    2007-01-01

    The mechanisms of gold precipitation by the interaction of cyanobacteria (Plectonema boryanum UTEX 485) and gold(III) chloride aqueous solutions (7.6 mmol/L final gold) have been studied at 25, 60, and 80 C, using both laboratory and real-time synchrotron radiation absorption spectroscopy experiments. Addition of aqueous gold(III) chloride to the cyanobacterial culture initially promoted the precipitation of amorphous gold(I) sulfide at the cell walls and finally caused the formation of octahedral (111) platelets (<1 to 6 (micro)m) of gold metal near cell surfaces and in solutions. X-ray absorption spectroscopy results confirmed that the reduction mechanism of gold(III) chloride to elemental gold by cyanobacteria involves the formation of an intermediate Au(I) species, gold(I) sulfide, with sulfur originating from cyanobacterial proteins, presumably cysteine or methionine. Although the bioreduction of gold(III) chloride to gold(I) sulfide was relatively rapid at all temperatures, the reaction rate increased with the increase in temperature. At the completion of the experiments, elemental gold was the major species present at all temperatures

  5. Sulfur and nitrogen compounds in urban aerosols

    Energy Technology Data Exchange (ETDEWEB)

    Tanner, R L

    1979-01-01

    This paper reports results from a detailed chemical and meteorological data base that has been accumulated for the New York City subregion. Aerosol sampling during August 1976 and February 1977 sampling periods was done only in an urban New York site and a background site at High Point, NJ. The sampling program was expanded to Brookhaven (Long Island) and New Haven, Connecticut sites during summer 1977 and winter 1978 sampling. Time resolution for aerosol filter samples was 6 hr, with some 3 hr sampling for the latter three periods. Parameters measured included chemical constituents: strong acid (quartz filters only), ammonium, sulfate and nitrate, sulfuric acid (limited data); physical parameters: aerosol size distributions by cascade impactor, cyclone sampler, EAA, on optical counter and a special diffusion battery-CNC apparatus; light scattering nephelometer and other instrumentation; chemically-speciated size classification by diffusion sampler; trace metals by atomic absorption; halogen compounds by NAA; meteorological measurements of RH, temperature, wind speed and direction; gaseous measurements of SO/sub 2/, ozone, NO/sub x/ and hydrocarbons at some locations for some sampling periods. The existence of aerosol sulfate in the ambient environment predominantly in the chemical form of sulfuric acid mostly neutralized by ammonia is now well documented. The average composition of fine particle (< 3.5 ..mu..m) sulfate in summer 1976 aerosols was approximately that letovicite ((NH/sub 4/)/sub 3/H(SO/sub 4/)/sub 2/). Based on the impactor data, about 85% of the aerosol sulfate mass was in the fine particle fraction. About 50% of this aerosol sulfate was deduced to be in the suboptical size regime (< 0.25 ..mu..m) from diffusion processor data. The H/sup +//SO/sub 4//sup 2 -/ ratio in suboptical aerosols did not significantly differ from that in fine fraction aerosol. The coarse particle sulfate was not associated with H/sup +/ or NH/sub 4//sup +/ and comprised

  6. Computation of Equilibrium Partial Vapor Pressures of Aqueous Ammonia Solutions

    National Research Council Canada - National Science Library

    Field, Paul

    2000-01-01

    This report evaluates all available vapor-liquid equilibria (VLE) data from low-to-moderate pressures over the normal liquid water temperature range for the highly non-ideal aqueous ammonia solutions spanning nearly a century...

  7. A dynamic study on the sulfuric acid distillation column for VHTR-assisted hydrogen production systems

    International Nuclear Information System (INIS)

    Youngjoon, Shin; Heesung, Shin; Jiwoon, Jang; Kiyoung, Lee; Jonghwa, Chang

    2007-01-01

    The sulfur-iodine (SI) cycle and the Westinghouse sulfur hybrid cycle coupled to a very high temperature gas-cooled reactor (VHTR) are well known as a feasible technology to produce hydrogen. The concentration of the sulfuric acid solution and its decomposition are essential parts in both cycles. In this paper, the thermophysical properties which are the boiling point, latent heat, and the partial pressures of water, sulfuric acid, and sulfur trioxide have been correlated as a function of the sulfuric acid concentration for the H 2 SO 4 and H 2 O binary chemical system, based on the data in Perry's chemical engineers' hand-book and other experimental data. By using these thermophysical correlations, a dynamic analysis of a sulfuric acid distillation column has been performed to establish the column design requirements and its optimum operation condition. From the results of the dynamic analysis, an optimized column system is anticipated for a distillation column equipped with 2 ideal plates and a second plate feeding system from the bottom plate. The effects of the hold-up of the re-boiler and the reflux ratio from the top product stream on the elapsing time when the system progresses toward a steady state have been analyzed. (authors)

  8. 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.

  9. 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.

  10. Macroporous Activated Carbon Derived from Rapeseed Shell for Lithium–Sulfur Batteries

    Directory of Open Access Journals (Sweden)

    Mingbo Zheng

    2017-10-01

    Full Text Available Lithium–sulfur batteries have drawn considerable attention because of their extremely high energy density. Activated carbon (AC is an ideal matrix for sulfur because of its high specific surface area, large pore volume, small-size nanopores, and simple preparation. In this work, through KOH activation, AC materials with different porous structure parameters were prepared using waste rapeseed shells as precursors. Effects of KOH amount, activated temperature, and activated time on pore structure parameters of ACs were studied. AC sample with optimal pore structure parameters was investigated as sulfur host materials. Applied in lithium–sulfur batteries, the AC/S composite (60 wt % sulfur exhibited a high specific capacity of 1065 mAh g−1 at 200 mA g−1 and a good capacity retention of 49% after 1000 cycles at 1600 mA g−1. The key factor for good cycling stability involves the restraining effect of small-sized nanopores of the AC framework on the diffusion of polysulfides to bulk electrolyte and the loss of the active material sulfur. Results demonstrated that AC materials derived from rapeseed shells are promising materials for sulfur loading.

  11. Sulfur Partitioning During Vitrification of INEEL Sodium Bearing Waste: Status Report

    Energy Technology Data Exchange (ETDEWEB)

    Darab, John G.; Graham, Dennis D.; Macisaac, Brett D.; Russell, Renee L.; Smith, Harry D.; Vienna, John D.; Peeler, David K.

    2001-07-31

    The sodium bearing tank waste (SBW) at Idaho National Engineering and Environmental Laboratory (INEEL) contains high concentrations of sulfur (roughly 5 mass% of SO3 on a nonvolatile oxide basis). The amount of sulfur that can be feed to the melter will ultimately determine the loading of SBW in glass produced by the baseline (low-temperature, joule-heated, liquid-fed, ceramic-lined) melter. The amount of sulfur which can be fed to the melter is determined by several major factors including: the tolerance of the melter for an immiscible salt layer accumulation, the solubility of sulfur in the glass melt, the fraction of sulfur removed to the off-gas, and the incorporation of sulfur into the glass up to it?s solubility limit. This report summarizes the current status of testing aimed at determining the impacts of key chemical and physical parameters on the partitioning of sulfur between the glass, a molten salt, and the off-gas.

  12. 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

  13. Need total sulfur content? Use chemiluminescence

    Energy Technology Data Exchange (ETDEWEB)

    Kubala, S.W.; Campbell, D.N. [Fluid Data, Inc., Angleton, TX (United States); DiSanzo, F.P. [Mobil Technology Co., Paulsboro, NJ (United States)

    1996-09-01

    Regulations issued by the United States Environmental Protection Agency require petroleum refineries to reduce or control the amount of total sulfur present in their refined products. These legislative requirements have led many refineries to search for online instrumentation that can produce accurate and repeatable total sulfur measurements within allowed levels. Several analytical methods currently exist to measure total sulfur content. They include X-ray fluorescence (XRF), microcoulometry, lead acetate tape, and pyrofluorescence techniques. Sulfur-specific chemiluminescence detection (SSCD) has recently received much attention due to its linearity, selectivity, sensitivity, and equimolar response. However, its use has been largely confined to the area of gas chromatography. This article focuses on the special design considerations and analytical utility of an SSCD system developed to determine total sulfur content in gasoline. The system exhibits excellent linearity and selectivity, the ability to detect low minimum levels, and an equimolar response to various sulfur compounds. 2 figs., 2 tabs.

  14. 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...

  15. 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.

  16. Charles H. Winston and Confederate Sulfuric Acid

    Science.gov (United States)

    Reithmiller, Steven

    1995-07-01

    Sulfuric acid turned out to be one of the critical chemicals made in the South during the Civil War. It was necessary for the manufacture of mercury fulminate which was used in the production of percussion caps and sulfuric acid was used in the Daniells cell to produce electricity. Charles H. Winston, president of the Richmond Female Institute and later professor at the University of Richmond (VA) was instrumental in the establishment of a plant to manufacture sulfuric acid in Charlotte, North Carolina. His patent and method of manufacture plus the uses of sulfuric acid during the Civil War are discussed.

  17. Dilute-sulfuric acid pretreatment of cattails for cellulose conversion.

    Science.gov (United States)

    Zhang, Bo; Wang, Lijun; Shahbazi, Abolghasem; Diallo, Oumou; Whitmore, Allante

    2011-10-01

    The use of aquatic plant cattails to produce biofuel will add value to land and reduce emissions of greenhouse gases by replacing petroleum products. Dilute-sulfuric acid pretreatment of cattails was studied using a Dionex accelerated solvent extractor (ASE) varying acid concentration (0.1-1%), treatment temperature (140-180 °C), and residence time (5-10 min). The highest total glucose yield for both the pretreatment and enzyme hydrolysis stages (97.1% of the cellulose) was reached at a temperature of 180 °C, a sulfuric acid concentration of 0.5%, and a time of 5 min. Cattails pretreated with 0.5% sulfuric acid are digestible with similar results at enzyme loadings above 15 FPU/g glucan. Glucose from cattails cellulose can be efficiently fermented to ethanol with an approximately 90% of the theoretical yield. The results in this study indicate that cattails are a promising source of feedstock for advanced renewable fuel production. Copyright © 2011 Elsevier Ltd. All rights reserved.

  18. Reaction of isoprene on thin sulfuric acid films: kinetics, uptake, and product analysis.

    Science.gov (United States)

    Connelly, Brandon M; Tolbert, Margaret A

    2010-06-15

    A high vacuum Knudsen flow reactor was used to determine the reactive uptake coefficient, gamma, of isoprene on sulfuric acid films as a function of sulfuric acid weight percent, temperature, and relative humidity. No discernible dependence was observed for gamma over the range of temperatures (220 - 265 K) and pressures (10(-7) Torr -10(-4) Torr) studied. However, the uptake coefficient increased with increased sulfuric acid concentration between the range of 78 wt % (gamma(i) approximately 10(-4)) and 93 wt % (gamma(i) approximately 10(-3)). In addition to the Knudsen Cell, a bulk study was conducted between 60 and 85 wt % H(2)SO(4) to quantify uptake at lower acid concentrations and to determine reaction products. After exposing sulfuric acid to gaseous isoprene the condensed phase products were extracted and analyzed using gas chromatography/mass spectrometry (GC/MS). Isoprene was observed to polymerize in the sulfuric acid and form yellow/red colored monoterpenes and cyclic sesquiterpenes. Finally, addition of water to the 85 wt % sulfuric acid/isoprene product mixture released these terpenes from the condensed phase into the gas phase. Together these experiments imply that direct isoprene uptake will not produce significant SOA; however, terpene production from the small uptake may be relevant for ultrafine particles and could affect growth and nucleation.

  19. 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...

  20. X-ray spectral determination of chemical state of phosphorus and sulfur in anodic oxide films on niobium

    International Nuclear Information System (INIS)

    Bokij, L.P.; Kostikov, Yu.P.

    1989-01-01

    Chemical forms of phosphorus and sulfur in niobium oxide anodic film, obtained by electrochemical technique using niobium in H 2 SO 4 and H 3 PO 4 aqueous solutions, are determined using data on chemical shifts of X-ray emission lines. Films represent Nb 2 O 5(1-γ) (SO 4 ) 5γ and Nb 2 O 5(1-γ) (PO 4 ) 10γ/3 (γ -share of oxygen substituted by acid anion) composition oxosalts. Electrolyte role in formation of niobium anodic oxide structure and effect of phosphorus and sulfur compounds on anodic film conductivity are determined

  1. Electrical properties of a new sulfur-containing polymer for optoelectronic application

    Science.gov (United States)

    ElAkemi, ElMehdi; Jaballah, Nejmeddine; Ouada, Hafedh Ben; Majdoub, Mustapha

    2015-06-01

    An original polythiophene derivative was characterized to develop the optoelectronic properties of sulfur-containing π-conjugated polymer. The optical properties of the polymer were investigated by UV-visible absorption spectroscopy and atomic force microscopy. Investigations of the electrical characteristics of polymer diodes are reported. We present current-voltage characteristics and impedance spectroscopy measurements performed on partially sulfur-containing thin films in sandwich structure ITO/sulfur-containing polymer/Al. The conduction mechanisms in these layers are identified to be a space-charge-limited current. The AC electrical transport of the sulfur-containing polymer is studied as a function of frequency (100 Hz-10 MHz) and temperature in impedance spectroscopy analyses. We interpreted Cole-Cole plots in terms of the equivalent circuit model as a single parallel resistance and a capacitance network in series with a relatively small resistance. The evolution of the electrical parameters deduced from fitting of the experimental data is discussed.

  2. A sulfuric-lactic acid process for efficient purification of fungal chitosan with intact molecular weight.

    Science.gov (United States)

    Naghdi, Mitra; Zamani, Akram; Karimi, Keikhosro

    2014-02-01

    The most recent method of fungal chitosan purification, i.e., two steps of dilute sulfuric acid treatment, pretreatment of cell wall at room temperature for phosphate removal and extraction of chitosan from the phosphate free cell wall at high temperature, significantly reduces the chitosan molecular weight. This study was aimed at improvement of this method. In the pretreatment step, to choose the best conditions, cell wall of Rhizopus oryzae, containing 9% phosphate, 10% glucosamine, and 21% N-acetyl glucosamine, was treated with sulfuric, lactic, acetic, nitric, or hydrochloric acid, at room temperature. Sulfuric acid showed the best performance in phosphate removal (90%) and cell wall recovery (89%). To avoid depolymerisation of chitosan, hot sulfuric acid extraction was replaced with lactic acid treatment at room temperature, and a pure fungal chitosan was obtained (0.12 g/g cell wall). Similar pretreatment and extraction processes were conducted on pure shrimp chitosan and resulted in a chitosan recovery of higher than 87% while the reduction of chitosan viscosity was less than 15%. Therefore, the sulfuric-lactic acid method purified the fungal chitosan without significant molecular weight manipulation. Copyright © 2013 Elsevier B.V. All rights reserved.

  3. Method of making sulfur-resistant composite metal membranes

    Science.gov (United States)

    Way, J Douglas [Boulder, CO; Lusk, Mark [Golden, CO; Thoen, Paul [Littleton, CO

    2012-01-24

    The invention provides thin, hydrogen-permeable, sulfur-resistant membranes formed from palladium or palladium-alloy coatings on porous, ceramic or metal supports. Also disclosed are methods of making these membranes via sequential electroless plating techniques, wherein the method of making the membrane includes decomposing any organic ligands present on the substrate, reducing the palladium crystallites on the substrate to reduced palladium crystallites, depositing a film of palladium metal on the substrate and then depositing a second, gold film on the palladium film. These two metal films are then annealed at a temperature between about 200.degree. C. and about 1200.degree. C. to form a sulfur-resistant, composite PdAu alloy membrane.

  4. Transferring the Incremental Capacity Analysis to Lithium-Sulfur Batteries

    DEFF Research Database (Denmark)

    Knap, Vaclav; Kalogiannis, Theodoros; Purkayastha, Rajlakshmi

    2017-01-01

    In order to investigate the battery degradation and to estimate their health, various techniques can be applied. One of them, which is widely used for Lithium-ion batteries, is the incremental capacity analysis (ICA). In this work, we apply the ICA to Lithium-Sulfur batteries, which differ in many...... aspects from Lithium-ion batteries and possess unique behavior. One of the challenges of applying the ICA to Lithium-Sulfur batteries is the representation of the IC curves, as their voltage profiles are often non-monotonic, resulting in more complex IC curves. The ICA is at first applied to charge...... and discharge processes at various temperature levels and afterward the technique is applied to a cell undergoing cycling degradation. It is shown that the ageing processes are trackable from the IC curves and it opens a possibility for their utilization for state-of-health estimation....

  5. Combination of best promoter and micellar catalyst for more than kilo-fold rate acceleration in favor of chromic acid oxidation of D-galactose to D-galactonic acid in aqueous media at room temperature

    Science.gov (United States)

    Saha, Rumpa; Ghosh, Aniruddha; Sar, Pintu; Saha, Indrajit; Ghosh, Sumanta K.; Mukherjee, Kakali; Saha, Bidyut

    2013-12-01

    Picolinic acid, 2,2‧-bipyridine and 1,10-phenanthroline promoted Cr(VI) oxidation of D-galactose to D-galactonic acid in three representative aqueous micellar media has been studied. The anionic surfactant (SDS) accelerated the rate of reaction while the cationic surfactant (CPC) and neutral surfactant (TX-100) retarded the reaction rate. Combination of bipy and SDS is the best choice for chromic acid oxidation of D-galactose to D-galactonic acid in aqueous media although 1,10-phenanthroline is best promoter in absence of micellar catalyst.

  6. New progresses in safe, clean and efficient development technologies for high-sulfur gas reservoirs

    Directory of Open Access Journals (Sweden)

    Liming Huang

    2015-10-01

    Full Text Available In China, there are a lot of high-sulfur gas reservoirs with total proved reserves of over 1 trillion m3, most of which were discovered in the Sichuan Basin. Most high-sulfur gas reservoirs in China, distributed in marine carbonate zones, are characterized by great buried depths, complex geologic conditions, high temperatures, high pressures, high H2S and CO2 content, presenting various challenges in gas field development engineering and production safety. Since the development of Sinian high-sulfur gas reservoirs in the Weiyuan area of the Sichuan Basin started in the 1960s, Wolonghe, Zhongba and other medium to small-scale gas reservoirs with medium to low sulfur content have been developed. Ever since 2009, successful production of Longgang and Puguang in the Sichuan Basin, together with some other high-sulfur gas reservoirs highlighted the breakthroughs in development technologies for high-sulfur gas reservoirs in China. This paper reviews the progress made in gas reservoir engineering, drilling and completion engineering, gas production, pipeline transportation, corrosion control, natural gas purification, HSE and other aspects with consideration of specific requirements related to safe, clean and high-efficient development of high-sulfur gas reservoirs since the “12th Five-Year Plan” period. Finally, considering the challenges in the development of high-sulfur gas reservoirs in China, we summarized the trend in future technological development with the following goals of reducing risks, minimizing environmental damages, and enhancing the efficiency of high-sulfur gas reservoir development.

  7. Chemically modified olive stone: a low-cost sorbent for heavy metals and basic dyes removal from aqueous solutions.

    Science.gov (United States)

    Aziz, Abdellah; Ouali, Mohand Said; Elandaloussi, El Hadj; De Menorval, Louis Charles; Lindheimer, Marc

    2009-04-15

    In the present work, we have investigated the sorption efficiency of treated olive stones (TOS) towards cadmium and safranine removal from their respective aqueous solutions. TOS material was prepared by treatment of olive stones with concentrated sulfuric acid at room temperature followed up by a subsequent neutralization with 0.1 M NaOH aqueous solution. The resulting material has been thoroughly characterized by SEM, energy-dispersive X-ray (EDX), MAS (13)C NMR, FTIR and physicochemical parameters were calculated. The sorption study of TOS at the solid-liquid interface was investigated using kinetics, sorption isotherms, pH effect and thermodynamic parameters. The preliminary results indicate that TOS exhibit a better efficiency in terms of sorption capacities toward the two pollutants (128.2 and 526.3 mg/g for cadmium and safranine, respectively) than those reported so far in the literature. Moreover, the sorption process is ascertained to occur fast enough so that the equilibrium is reached in less than 15 min of contact time. The results found in the course of this study suggest that ion exchange mechanism is the most appropriate mechanism involved in cadmium and safranine removal. Finally, the sorption efficiency of TOS is compared to those of other low-cost sorbents materials yet described in the literature.

  8. Sulfur Dioxide Analyzer Instrument Handbook

    Energy Technology Data Exchange (ETDEWEB)

    Springston, Stephen R. [Brookhaven National Lab. (BNL), Upton, NY (United States)

    2016-05-01

    The Sulfur Dioxide Analyzer measures sulfur dioxide based on absorbance of UV light at one wavelength by SO2 molecules which then decay to a lower energy state by emitting UV light at a longer wavelength. Specifically, SO2 + hυ1 →SO2 *→SO2 + hυ2 The emitted light is proportional to the concentration of SO2 in the optical cell. External communication with the analyzer is available through an Ethernet port configured through the instrument network of the AOS systems. The Model 43i-TLE is part of the i-series of Thermo Scientific instruments. The i-series instruments are designed to interface with external computers through the proprietary Thermo Scientific iPort Software. However, this software is somewhat cumbersome and inflexible. Brookhaven National Laboratory (BNL) has written an interface program in National Instruments LabView that both controls the Model 43i-TLE Analyzer AND queries the unit for all measurement and housekeeping data. The LabView vi (the software program written by BNL) ingests all raw data from the instrument and outputs raw data files in a uniform data format similar to other instruments in the AOS and described more fully in Section 6.0 below.

  9. The Relationship Between Corrosion and the Biological Sulfur Cycle

    National Research Council Canada - National Science Library

    Little, Brenda

    2000-01-01

    .... Sulfur and sulfur compounds, including sulfides, bisulfides, hydrogen sulfide (H2S), thiosulfates, polythionates and sulfuric acid, may be trapped or bound up in biofilms causing direct corrosion of materials...

  10. Multiphysics Modelling of Sodium Sulfur Battery

    Science.gov (United States)

    Mason, Jerry Hunter

    Due to global climate change and the desire to decrease greenhouse gas emissions, large scale energy storage has become a critical issue. Renewable energy sources such as wind and solar will not be a viable energy source unless the storage problem is solved. One of the practical and cost effective solutions for this problem is sodium sulfur batteries. These batteries are comprised of liquid electrode materials suspended in porous media and operate at relatively high temperatures (>300°C). The sodium anode and the sulfur/sodium-polysulfide cathode are separated by a solid electrolyte made of beta-alumina or NASICON material. Due to the use of porous materials in the electrodes, capillary pressure and the combination of capillary action and gravity become important. Capillary pressure has a strong dependence on the wetting phase (liquid electrode material) saturation; therefore sharp concentration gradients can occur between the inert gas and the electrode liquid, especially within the cathode. These concentration gradients can have direct impacts on the electrodynamics of the battery as they may produce areas of high electrical potential variation, which can decrease efficiency and even cause failures. Then, thermal management also becomes vital since the electrochemistry and material properties are sensitive to temperature gradients. To investigate these phenomena in detail and to attempt to improve upon battery design a multi-dimensional, multi-phase code has been developed and validated in this study. Then a porous media flow model is implemented. Transport equations for charge, mass and heat are solved in a time marching fashion using finite volume method. Material properties are calculated and updated as a function of time. The porous media model is coupled with the continuity equation and a separate diffusion equation for the liquid sodium in the melt. The total mass transport model is coupled with charge transport via Faraday's law. Results show that

  11. 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.

  12. 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.

  13. Thermodynamic properties of aqueous solutions with citrate ions. Compressibility studies in aqueous solutions of citric acid

    International Nuclear Information System (INIS)

    Apelblat, Alexander; Korin, Eli; Manzurola, Emanuel

    2013-01-01

    Highlights: • Over a wide range of concentrations and temperatures sound velocities were measured in aqueous solutions of citric acid. • Compressibility properties of citric acid solutions are thermodynamically characterized. • Changes in the structure of water when citric acid is dissolved are discussed. -- Abstract: Sound velocities in aqueous solutions of citric acid were measured from 15 °C to 50 °C in 5 °C intervals, within the 0.1 mol · kg −1 to 5.0 mol · kg −1 concentration range. These sound velocities served to evaluate the isentropic and isothermal compressibilities, the apparent molar compressibilities, the isochoric thermal pressure coefficients, changes of the cubic expansion coefficients with pressure at constant temperature, the changes of heat capacities with volume and hydration numbers of citric acid in aqueous solutions

  14. Comparative Genomics of Green Sulfur Bacteria

    DEFF Research Database (Denmark)

    Ussery, David; Davenport, C; Tümmler, B

    2010-01-01

    Eleven completely sequenced Chlorobi genomes were compared in oligonucleotide usage, gene contents, and synteny. The green sulfur bacteria (GSB) are equipped with a core genome that sustains their anoxygenic phototrophic lifestyle by photosynthesis, sulfur oxidation, and CO(2) fixation. Whole...... weight of 10(6), and are probably instrumental for the bacteria to generate their own intimate (micro)environment....

  15. 21 CFR 182.3862 - Sulfur dioxide.

    Science.gov (United States)

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Sulfur dioxide. 182.3862 Section 182.3862 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) FOOD FOR HUMAN CONSUMPTION (CONTINUED) SUBSTANCES GENERALLY RECOGNIZED AS SAFE Chemical Preservatives § 182.3862 Sulfur...

  16. Sulfur isotope fractionation between fluid and andesitic melt: An experimental study

    Science.gov (United States)

    Fiege, Adrian; Holtz, François; Shimizu, Nobumichi; Mandeville, Charles W.; Behrens, Harald; Knipping, Jaayke L.

    2014-01-01

    Glasses produced from decompression experiments conducted by Fiege et al. (2014a) were used to investigate the fractionation of sulfur isotopes between fluid and andesitic melt upon magma degassing. Starting materials were synthetic glasses with a composition close to a Krakatau dacitic andesite. The glasses contained 4.55–7.95 wt% H2O, ∼140 to 2700 ppm sulfur (S), and 0–1000 ppm chlorine (Cl). The experiments were carried out in internally heated pressure vessels (IHPV) at 1030 °C and oxygen fugacities (fO2) ranging from QFM+0.8 log units up to QFM+4.2 log units (QFM: quartz–fayalite–magnetite buffer). The decompression experiments were conducted by releasing pressure (P) continuously from ∼400 MPa to final P of 150, 100, 70 and 30 MPa. The decompression rate (r) ranged from 0.01 to 0.17 MPa/s. The samples were annealed for 0–72 h (annealing time, tA) at the final P and quenched rapidly from 1030 °C to room temperature (T).The decompression led to the formation of a S-bearing aqueous fluid phase due to the relatively large fluid–melt partitioning coefficients of S. Secondary ion mass spectrometry (SIMS) was used to determine the isotopic composition of the glasses before and after decompression. Mass balance calculations were applied to estimate the gas–melt S isotope fractionation factor αg-m.No detectable effect of r and tA on αg-m was observed. However, SIMS data revealed a remarkable increase of αg-m from ∼0.9985 ± 0.0007 at >QFM+3 to ∼1.0042 ± 0.0042 at ∼QFM+1. Noteworthy, the isotopic fractionation at reducing conditions was about an order of magnitude larger than predicted by previous works. Based on our experimental results and on previous findings for S speciation in fluid and silicate melt a new model predicting the effect of fO2 on αg-m (or Δ34Sg–m) in andesitic systems at 1030 °C is proposed. Our experimental results as well as our modeling are of high importance for the interpretation of S isotope

  17. Numerical simulation of condensation of sulfuric acid and water in a large two-stroke marine diesel engine

    DEFF Research Database (Denmark)

    Karvounis, Nikolas; Pang, Kar Mun; Mayer, Stefan

    2018-01-01

    correlation is found between the fuel sulfur content and the total condensed mass of sulfuric acid. The level of humidity of the scavenging air does not affect the condensation of sulfuric acid considerably, relative to the humidity increase, but it has a high impact on water condensation. The study...... of the scavenging pressure level reveals a counter intuitive behavior where the condensation rates decrease with higher scavenging pressures due to the flow regime and flame size. Next, increasing the cylinder liner temperature decreases significantly the water condensation contrary to the sulfuric acid...... condensation which is marginally affected. The increase in lubricant film thickness results in a decrease for both the sulfuric acid and water condensation with a more pronounced reduction for water. Finally, a comparison between the high and low load operating conditions reveals a small drop in the total...

  18. Sulfate- and Sulfur-Reducing Bacteria as Terrestrial Analogs for Microbial Life on Jupiter's Satellite Io

    Science.gov (United States)

    Pikuta, Elena V.; Hoover, Richard B.; Six, N. Frank (Technical Monitor)

    2001-01-01

    Observations from the Voyager and Galileo spacecraft have revealed Jupiter's moon Io to be the most volcanically active body of our Solar System. The Galileo Near Infrared Imaging Spectrometer (NIMS) detected extensive deposits of sulfur compounds, elemental sulfur and SO2 frost on the surface of Io. There are extreme temperature variations on Io's surface, ranging from -130 C to over 2000 C at the Pillan Patera volcanic vent. The active volcanoes, fumaroles, calderas, and lava lakes and vast sulfur deposits on this frozen moon indicate that analogs of sulfur- and sulfate-reducing bacteria might inhabit Io. Hence Io may have great significance to Astrobiology. Earth's life forms that depend on sulfur respiration are members of two domains: Bacteria and Archaea. Two basic links of the biogeochemical sulfur cycle of Earth have been studied: 1) the sulfur oxidizing process (occurring at aerobic conditions) and 2) the process of sulfur-reduction to hydrogen sulfide (anaerobic conditions). Sulfate-reducing bacteria (StRB) and sulfur-reducing bacteria (SrRB) are responsible for anaerobic reducing processes. At the present time the systematics of StRB include over 112 species distributed into 35 genera of Bacteria and Archaea. Moderately thermophilic and mesophilic SrRB belong to the Bacteria. The hyperthermophilic SrRB predominately belong to the domain Archaea and are included in the genera: Pyrodictium, Thermoproteus, Pyrobaculum, Thermophilum, Desulfurococcus, and Thermodiscus. The StRB and SrRB use a wide spectrum of substrates as electron donors for lithotrophic and heterotrophic type nutrition. The electron acceptors for the StRB include: sulfate, thiosulfate, sulfite, sulfur, arsenate, dithionite, tetrathionate, sulfur monoxide, iron, nitrite, selenite, fumarate, oxygen, carbon dioxide, and chlorine-containing phenol compounds. The Sulfate- and Sulfur-reducing bacteria are widely distributed in anaerobic ecosystems, including extreme environments like hot springs

  19. Aqueous solubility of zirconia

    International Nuclear Information System (INIS)

    Sunder, S.; Wren, S.

    2008-01-01

    Zirconia (zirconium dioxide) is being considered as a host matrix for the disposal of actinides in a geologic disposal vault, for the 'burning of actinides' in nuclear reactors and for the use of lanthanides as burnable-neutron absorbers to control the neutron flux in the reactors. These applications require knowledge of the stability of the zirconia in aqueous environment. Therefore, a literature review of the aqueous solubility of zirconia was carried out. The literature review was complemented by experiments on the dissolution of zirconia in aqueous solutions. The paper presents the results of the literature review and our experiments on the dissolution of zirconia in solutions of pH between 5.7 and 10.3. The low solubility of zirconia in the solutions investigated here supports the selection of zirconia for the above applications. (author)

  20. NOx Pollution Analysis for a Sulfur Recovery Unit Thermal Reactor

    Science.gov (United States)

    Yeh, Chun-Lang

    2017-12-01

    A sulfur recovery unit (SRU) thermal reactor is the most important equipment in a sulfur plant. It is negatively affected by high temperature operations. In this paper, NOx emissions from the SRU thermal reactors are simulated. Both the prototype thermal reactor and its modifications, including changing fuel mass fraction, changing inlet air quantity, changing inlet oxygen mole fraction, and changing burner geometry, are analyzed to investigate their influences on NOx emissions. In respect of the fuel mass fraction, the simulation results show that the highest NO emission occurs at a zone 1 fuel mass fraction of 0.375, around which the reactor maximum temperature and the zone 1 average temperature reach maximum values. Concerning the inlet air quantity, the highest NO emission occurs when the inlet air quantity is 2.4 times the designed inlet air quantity. This is very close to the inlet air quantity at which the maximum average temperature occurs. Regarding the inlet oxygen mole fraction, the NO emission increases as the inlet oxygen mole fraction increases. With regard to the burner geometry, the NO emission increases as the clearance of the burner acid gas tip increases. In addition, the NO emission increases as the swirling strength increases.

  1. Dynamics and mass accommodation of HCl molecules on sulfuric acid-water surfaces.

    Science.gov (United States)

    Behr, P; Scharfenort, U; Ataya, K; Zellner, R

    2009-09-28

    A molecular beam technique has been used to study the dynamics and mass accommodation of HCl molecules in collision with sulfuric acid-water surfaces. The experiments were performed by directing a nearly mono-energetic beam of HCl molecules onto a continuously renewed liquid film of 54-76 wt% sulfuric acid at temperatures between 213 K and 243 K. Deuterated sulfuric acid was used to separate sticking but non-reactive collisions from those that involved penetration through the phase boundary followed by dissociation and recombination with D+. The results indicate that the mass accommodation of HCl on sulfuric acid-water surfaces decreases sharply with increasing acidity over the concentration range 54-76 wt%. Using the capillary wave theory of mass accommodation this effect is explained by a change of the surface dynamics. Regarding the temperature dependence it is found that the mass accommodation of HCl increases with increasing temperature and is limited by the bulk phase viscosity and driven by the restoring forces of the surface tension. These findings imply that under atmospheric conditions the uptake of HCl from the gas phase depends crucially on the bulk phase parameters of the sulfuric acid aerosol.

  2. Modeling the condensation of sulfuric acid and water on the cylinder liner of a large two-stroke marine diesel engine

    DEFF Research Database (Denmark)

    Cordtz, Rasmus Faurskov; Mayer, Stefan; Eskildsen, Svend S.

    2018-01-01

    Corrosive wear of cylinder liners in large two-stroke marine diesel engines that burn heavy fuel oil containing sulfur is coupled to the formation of gaseous sulfur trioxide (SO3) and subsequent combined condensation of sulfuric acid (H2SO4) and water (H2O) vapor. The present work seeks to address...... vapor liquid equilibrium. By assuming homogenous cylinder gas mixtures condensation is modeled using a convective heat and mass transfer analogy combined with realistic liner temperature profiles. Condensation of water is significantly altered by the liner temperature and charge air humidity while...... how fuel sulfur content, charge air humidity and liner temperature variations affects the deposition of water and sulfuric acid at low load operation. A phenomenological engine model is applied to simulate the formation of cylinder/bulk gas combustion products and dew points comply with H2O–H2SO4...

  3. Sulfuric Acid Intercalated Graphite Oxide for Graphene Preparation

    Science.gov (United States)

    Hong, Yanzhong; Wang, Zhiyong; Jin, Xianbo

    2013-01-01

    Graphene has shown enormous potential for innovation in various research fields. The current chemical approaches based on exfoliation of graphite via graphite oxide (GO) are potential for large-scale synthesis of graphene but suffer from high cost, great operation difficulties, and serious waste discharge. We report a facile preparation of graphene by rapid reduction and expansion exfoliation of sulfuric acid intercalated graphite oxide (SIGO) at temperature just above 100°C in ambient atmosphere, noting that SIGO is easily available as the immediate oxidation descendent of graphite in sulfuric acid. The oxygenic and hydric groups in SIGO are mainly removed through dehydration as catalyzed by the intercalated sulfuric acid (ISA). The resultant consists of mostly single layer graphene sheets with a mean diameter of 1.07 μm after dispersion in DMF. This SIGO process is reductant free, easy operation, low-energy, environmental friendly and generates graphene with low oxygen content, less defect and high conductivity. The provided synthesis route from graphite to graphene via SIGO is compact and readily scalable. PMID:24310650

  4. DEVELOPMENT OF A CO2 SEQUESTRATION MODULE BY INTEGRATING MINERAL ACTIVATION AND AQUEOUS CARBONATION

    Energy Technology Data Exchange (ETDEWEB)

    M. Mercedes Maroto-Valer; John M. Andresen; George Alexander

    2004-11-15

    Mineral carbonation is a promising concept for permanent CO{sub 2} sequestration due to the vast natural abundance of the raw minerals, the permanent storage of CO{sub 2} in solid form as carbonates, and the overall reaction being exothermic. However, the primary drawback to mineral carbonation is the reaction kinetics. To accelerate the reaction, aqueous carbonation processes are preferred, where the minerals are firstly dissolved in solution. In aqueous carbonation, the key step is the dissolution rate of the mineral, where the mineral dissolution reaction is likely to be surface controlled. In order to accelerate the dissolution process, the serpentine can be ground to very fine particle size (<37 {micro}m), but this is a very energy intensive process. Alternatively, magnesium could be chemically extracted in aqueous solution. Phase I showed that chemical surface activation helps to dissolve the magnesium from the serpentine minerals (particle size {approx}100 {micro}m), and furthermore, the carbonation reaction can be conducted under mild conditions (20 C and 650 psig) compared to previous studies that required >185 C, >1850 psig and <37 {micro}m particle size. Phase I also showed that over 70% of the magnesium can be extracted at ambient temperature leaving amorphous SiO{sub 2} with surface areas {approx} 330m{sup 2}/g. The overall objective of Phase 2 of this research program is to optimize the active carbonation process developed in Phase I in order to design an integrated CO{sub 2} sequestration module. During the current reporting period, Task 1 ''Mineral activation'' was initiated and focused on a parametric study to optimize the operation conditions for the mineral activation, where serpentine and sulfuric acid were reacted, as following the results from Phase 1. Several experimental factors were outlined as having a potential influence on the mineral activation. This study has focused to date on the effects of varying the acid

  5. 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.

  6. Sulfur poisoning and regeneration of the Ag/γ-Al2O3 catalyst for H2-assisted SCR of NOx by ammonia

    DEFF Research Database (Denmark)

    Doronkin, Dmitry E.; Khan, Tuhin Suvra; Bligaard, Thomas

    2012-01-01

    Sulfur poisoning and regeneration mechanisms for a 2% Ag/γ-Al2O3 catalyst for the H2-assisted selective catalytic reduction of NOx by NH3 are investigated. The catalyst has medium sulfur tolerance at low temperatures, however a good capability of regeneration at 670°C under lean conditions when H2...

  7. Effects of adding aqueous extract of Tribulus terrestris to diet on productive performance, egg quality characteristics, and blood biochemical parameters of laying hens reared under low ambient temperature (6.8 ± 3 °C)

    Science.gov (United States)

    Akbari, Mohsen; Torki, Mehran

    2016-06-01

    A study was conducted using 144 laying hens to evaluate the effects of adding aqueous extract of Tribulus terrestris to diets on productive performance, egg quality traits, and some blood parameters of laying hens reared under cold stress condition (6.8 ± 3 °C). The birds were randomly assigned to each of four dietary treatments (C, T1, T2, and T3) with six replicate cages of six birds. Diet inclusion of aqueous extract of T. terrestris at the rate of 10, 20, and 30 ml/Lit offered to groups T1, T2, and T3, respectively, while group C served as the control diet with no addition. Feed intake (FI), feed conversion ratio (FCR), egg weight (EW), egg production (EP), and egg mass (EM) were evaluated during the 42-day trial period. The EP and EM increased, whereas FCR decreased ( P terrestris has beneficial effects on productive performance of laying hens reared under cold stress condition.

  8. 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

  9. Multiple sulfur isotopes fractionations associated with abiotic sulfur transformations in Yellowstone National Park geothermal springs.

    Science.gov (United States)

    Kamyshny, Alexey; Druschel, Gregory; Mansaray, Zahra F; Farquhar, James

    2014-01-01

    The paper presents a quantification of main (hydrogen sulfide and sulfate), as well as of intermediate sulfur species (zero-valent sulfur (ZVS), thiosulfate, sulfite, thiocyanate) in the Yellowstone National Park (YNP) hydrothermal springs and pools. We combined these measurements with the measurements of quadruple sulfur isotope composition of sulfate, hydrogen sulfide and zero-valent sulfur. The main goal of this research is to understand multiple sulfur isotope fractionation in the system, which is dominated by complex, mostly abiotic, sulfur cycling. Water samples from six springs and pools in the Yellowstone National Park were characterized by pH, chloride to sulfate ratios, sulfide and intermediate sulfur species concentrations. Concentrations of sulfate in pools indicate either oxidation of sulfide by mixing of deep parent water with shallow oxic water, or surface oxidation of sulfide with atmospheric oxygen. Thiosulfate concentrations are low (hot parent water body. In two pools δ(34)S values of sulfate varied significantly from the values calculated from this model. Sulfur isotope fractionation between ZVS and hydrogen sulfide was close to zero at pH < 4. At higher pH zero-valent sulfur is slightly heavier than hydrogen sulfide due to equilibration in the rhombic sulfur-polysulfide - hydrogen sulfide system. Triple sulfur isotope ((32)S, (33)S, (34)S) fractionation patterns in waters of hydrothermal pools are more consistent with redox processes involving intermediate sulfur species than with bacterial sulfate reduction. Small but resolved differences in ∆(33)S among species and between pools are observed. The variation of sulfate isotopic composition, the origin of differences in isotopic composition of sulfide and zero-valent sulfur, as well as differences in ∆(33)S of sulfide and sulfate are likely due to a complex network of abiotic redox reactions, including disproportionation pathways.

  10. Configuring the thermochemical hydrogen sulfuric acid process step for the Tandem Mirror Reactor

    International Nuclear Information System (INIS)

    Galloway, T.R.

    1981-01-01

    This paper identifies the sulfuric acid step as the critical part of the thermochemical cycle in dictating the thermal demands and temperature requirements of the heat source. The General Atomic Sulfur-Iodine Cycle is coupled to a Tandem Mirror. The sulfuric acid decomposition process step is focused on specifically since this step can use the high efficiency electrical power of the direct converter together with the other thermal-produced electricity to Joule-heat a non-catalytic SO 3 decomposer to approximately 1250 0 K. This approach uses concepts originally suggested by Dick Werner and Oscar Krikorian. The blanket temperature can be lowered to about 900 0 K, greatly alleviating materials problems, the level of technology required, safety problems, and costs. A moderate degree of heat has been integrated to keep the cycle efficiency around 48%, but the number of heat exchangers has been limited in order to keep hydrogen production costs within reasonable bounds

  11. 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.

  12. 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.

  13. Evolution of sulfur speciation in bitumen through hydrous pyrolysis induced thermal maturation of Jordanian Ghareb Formation oil shale

    Science.gov (United States)

    Birdwell, Justin E.; Lewan, Michael; Bake, Kyle D.; Bolin, Trudy B.; Craddock, Paul R.; Forsythe, Julia C.; Pomerantz, Andrew E.

    2018-01-01

    Previous studies on the distribution of bulk sulfur species in bitumen before and after artificial thermal maturation using various pyrolysis methods have indicated that the quantities of reactive (sulfide, sulfoxide) and thermally stable (thiophene) sulfur moieties change following consistent trends under increasing thermal stress. These trends show that sulfur distributions change during maturation in ways that are similar to those of carbon, most clearly illustrated by the increase in aromatic sulfur (thiophenic) as a function of thermal maturity. In this study, we have examined the sulfur moiety distributions of retained bitumen from a set of pre- and post-pyrolysis rock samples in an organic sulfur-rich, calcareous oil shale from the Upper Cretaceous Ghareb Formation. Samples collected from outcrop in Jordan were subjected to hydrous pyrolysis (HP). Sulfur speciation in extracted bitumens was examined using K-edge X-ray absorption near-edge structure (XANES) spectroscopy. The most substantial changes in sulfur distribution occurred at temperatures up to the point of maximum bitumen generation (∼300 °C) as determined from comparison of the total organic carbon content for samples before and after extraction. Organic sulfide in bitumen decreased with increasing temperature at relatively low thermal stress (200–300 °C) and was not detected in extracts from rocks subjected to HP at temperatures above around 300 °C. Sulfoxide content increased between 200 and 280 °C, but decreased at higher temperatures. The concentration of thiophenic sulfur increased up to 300 °C, and remained essentially stable under increasing thermal stress (mg-S/g-bitumen basis). The ratio of stable-to-reactive+stable sulfur moieties ([thiophene/(sulfide+sulfoxide+thiophene)], T/SST) followed a sigmoidal trend with HP temperature, increasing slightly up to 240 °C, followed by a substantial increase between 240 and 320 °C, and approaching a constant value (∼0.95) at

  14. Hysteresis Phenomena in Sulfur Dioxide Oxidation over Supported Vanadium Catalysts

    DEFF Research Database (Denmark)

    Masters, Stephen G.; Eriksen, Kim Michael; Fehrmann, Rasmus

    1997-01-01

    Catalyst deactivation and hysteresis behavior in industrial SO2-oxidation catalysts have been studied in the temperature region 350-480 C by combined in situ EPR spectroscopy and catalytic activity measurements. The feed gas composition simulated sulfuric acid synthesis gas and wet/dry deNOx'ed f......NOx'ed flue gas. The vanadium (IV) compound K4(VO)3(SO4)5 precipitated during all the investigated conditions hence causing catalyst deactivation. Hysteresis behavior of both the catalytic activity and the V(IV) content was observed during reheating....

  15. THE PERFORMANCE OF NATURAL SORBENTS IN THE SULFUR DIOXIDE ADSORPTION

    Directory of Open Access Journals (Sweden)

    Т. L. Rakyts’ka

    2015-02-01

    Full Text Available The performance of natural sorbents with different mineralogical makeup (zeolites, layered aluminosilicates, basalt tuffs, and dispersed silicas in the adsorption-desorption of sulfur dioxide at its contents in the gas-air mixture of 150 and 200 mg/m3 and at the temperature of 20 °C has been studied. The S02 adsorption has been found to be predominately the physical one. The adsorption capacity values obtained experimentally for the sorbents have been compared with the data presented in the literature.

  16. Uranium extraction from sulfuric acid solution using anion exchange resin

    International Nuclear Information System (INIS)

    Sheta, M. E.; Abdel Aal, M. M.; Kandil, A. T.

    2012-12-01

    Uranium is currently recovered from sulfuric acid leach liquor using anion exchange resin as Amberlite IRA 402 (CT). This technology is based on fact that, uranium exists as anionic complexes. This takes place by controlling the pH of the solution, agitation time, temperature and resin to solution ratio (R/S). In this work, batch stirrer tank used for uranium extraction from sulfate medium and after extraction, elution process was done using 1M NaCl solution. After extraction and elution process, the resin was separated from the system and uranium was determined in the solution. (Author)

  17. Sulfur (32S, 33S, 34S, 36S) and oxygen (16O, 17O, 18O) isotopi primary sulfate produced from combustion processes

    International Nuclear Information System (INIS)

    Lee, C.C.W.; Savarino, J.; Thiemens, M.H.; Cachier, H.

    2002-01-01

    The recent discovery of an anomalous enrichment in 17 O isotope in atmospheric sulfate has opened a new way to investigate the oxidation pathways of sulfur in the atmosphere. From laboratory investigations, it has been suggested that the wet oxidation of sulfur in rain droplets was responsible for the excess 17 O. In order to confirm this theory, sulfur and oxygen isotope ratios of different primary sulfates produced during fossil fuel combustion have been investigated and are reported. None of these samples exhibits any anomalous oxygen or sulfur isotopic content, as compared to urban sulfate aerosols. These results, in agreement with the laboratory investigations, reinforce the idea of an aqueous origin for the oxygen-17 anomaly found in tropospheric sulfates

  18. Use of probabilistic safety analysis for design of emergency mitigation systems in hydrogen producer plant with sulfur-iodine technology, Section II: sulfuric acid decomposition

    International Nuclear Information System (INIS)

    Mendoza A, A.; Nelson E, P. F.; Francois L, J. L.

    2009-10-01

    Over the last decades, the need to reduce emissions of greenhouse gases has prompted the development of technologies for the production of clean fuels through the use of primary energy resources of zero emissions, as the heat of nuclear reactors of high temperature. Within these technologies, one of the most promising is the hydrogen production by sulfur-iodine cycle coupled to a high temperature reactor initially proposed by General Atomics. By their nature and because it will be large-scale plants, the development of these technologies from its present phase to its procurement and construction, will have to incorporate emergency mitigation systems in all its parts and interconnections to prevent undesired events that could put threaten the plant integrity and the nearby area. For the particular case of sulfur-iodine thermochemical cycle, most analysis have focused on hydrogen explosions and failures in the primary cooling systems. While these events are the most catastrophic, is that there are also many other events that even taking less direct consequences, could jeopardize the plant operation, the people safety of nearby communities and carry the same economic consequences. In this study we analyzed one of these events, which is the formation of a toxic cloud prompted by uncontrolled leakage of concentrated sulfuric acid in the second section of sulfur-iodine process of General Atomics. In this section, the sulfuric acid concentration is near to 90% in conditions of high temperature and positive pressure. Under these conditions the sulfuric acid and sulfur oxides from the reactor will form a toxic cloud that the have contact with the plant personnel could cause fatalities, or to reach a town would cause suffocation, respiratory problems and eye irritation. The methodology used for this study is the supported design in probabilistic safety analysis. Mitigation systems were postulated based on the isolation of a possible leak, the neutralization of a pond of

  19. THIOGLYCOLIC ACID ESTERIFIED IN TO RICE STRAW FOR REMOVING LEAD FROM AQUEOUS SOLUTION

    Directory of Open Access Journals (Sweden)

    R. Gong

    2011-09-01

    Full Text Available Thiol rice straw (TRS was prepared by esterifying thioglycolic acid onto rice straw in the medium of acetic anhydride and acetic acid with sulfuric acid as catalyst. The sorption of lead (Pb on TRS from aqueous solution was subsequently investigated. The batch experiments showed that Pb removal was dependent on initial pH, sorbent dose, Pb concentration, contact time, and temperature. The maximum value of Pb removal appeared at pH 5. For 100 mg/L of Pb solution, a removal ratio of greater than 98% could be achieved with 2.0 g/L or more of TRS. The isothermal data of Pb sorption conformed well to the Langmuir model, and the maximum sorption capacity (Qm of TRS for Pb was 104.17 mg/g. The equilibrium of Pb removal was reached within 120 min. The Pb removal process could be described by the pseudo-first-order kinetic model. The thermodynamic study indicated that the Pb removal process was spontaneous and endothermic.

  20. 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.