Science.gov

Sample records for aqueous sulfuric acid

  1. Infrared titration of aqueous sulfuric acid

    SciTech Connect

    Max, J.J.; Menichelli, C.; Chapados, C.

    2000-03-30

    This paper presents the infrared (IR) titration of aqueous sulfuric acid solutions (0.50 M) obtained by the attenuated total reflection (ATR) sampling technique. After subtracting the water spectra, the spectra of the ionic species of H{sub 2}SO{sub 4} in the 0--14 pH range were separated by factor analysis (FA) which also gave their abundance. The results were in agreement with the theoretical calculation of the distribution of the species. Three sulfate species were found: HSO{sub 4}{sup {minus}}, SO{sub 4}{sup 2{minus}}, and HSO{sub 4}{sup {minus}}/HCl. The latter stands for the bisulfate--hydronium complex formed by the addition of HCl to obtain measurements in the 0--0.47 pH range. For 0.50 M sulfuric acid, the comparison between the experimentally IR-determined quantities and the theoretical values gave a mean activity coefficient of 0.12 {+-} 0.04, a value comparable to that from electrochemical measurements. Three types of water were quantitatively determined in the solutions: acidic water, basic water, and neutral water. The latter is always present while the two others are present in the low and high pH range, respectively. Another type of water strongly associated with the sulfates is also present. Moreover, knowledge of the behavior of the different types of water as the titration proceeded permitted us to give the details of the neutralization reactions of aqueous sulfuric acid by sodium hydroxide.

  2. Solubility of uranous sulfate in aqueous sulfuric acid solution

    NASA Astrophysics Data System (ADS)

    Suzuki, Shigeru; Hirono, Shuichiro; Awakura, Yasuhiro; Majima, Hiroshi

    1990-10-01

    To provide important thermodynamic data for use in uranium hydrometallurgy, solubilities of uranous sulfate were determined as a function of free acid concentration and temperature. Two sets of experiments were performed in this study. One set was the precipitation experiments of uranous sulfate crystals, in which concentrated uranous sulfate solution was mixed with sulfuric acid solution of suitable concentration. The other set was the dissolution experiments of uranous sulfate crystals in aqueous sulfuric acid solutions. It is noteworthy that good agreement exists between the solubilities determined by the two methods. At elevated temperatures, say, 363 K, the presence of free sulfuric acid is required to avoid precipitation of uranous hydroxide resulting from the hydrolysis of uranous sulfate. Generally speaking, however, an increase in free sulfuric acid concentration results in a slight decrease in uranous sulfate solubility. The elevation of solution temperature causes a decrease in solubility of uranous sulfate. It should be noted that the solid uranous sulfates equilibrated with saturated solutions at 298 K were U(SO4)2 2H2O in dilute sulfuric acid solution and U(SO4)2 4H2O in concentrated sulfuric acid solution, while those at 333 K and 363 K were mainly U(SO4)2 4H2O.

  3. Methanol Uptake By Low Temperature Aqueous Sulfuric Acid Solutions

    NASA Technical Reports Server (NTRS)

    Iraci, Laura T.; Essin, Andrew M.; Golden, David M.; Hipskind, R. Stephen (Technical Monitor)

    2001-01-01

    To evaluate the role of upper tropospheric and lower stratospheric aerosols in the global budget of methanol, the solubility and reactivity of CH3OH in aqueous sulfuric acid solutions are under investigation. Using standard uptake techniques in a Knudsen cell reactor, we have measured the effective Henry's law coefficient, H(*), for methanol dissolution into 45 to 70 percent by weight H2SO4. We find that methanol solubility ranges from 10(exp 5) to 10(exp 8) M/atm and increases with decreasing temperature and with increasing sulfuric acid content. These solubility measurements include uptake due to physical solvation and all rapid equilibria which are established in solution. Our data indicate that simple uptake by aqueous sulfuric acid particles will not be a significant sink for methanol in the UT/LS. These results differ from those recently reported in the literature, and an explanation of this disparity will be presented. In addition to solvation, reaction between primary alcohols and sulfuric acid does occur, leading to the production of alkyl sulfates. Literature values for the rate of this reaction suggest that formation of CH3OSO3H may proceed in the atmosphere but is not significant under our experimental conditions. Results obtained using a complementary equilibrium measurement technique confirm this directly. In addition, the extent of methanol sequestration via formation of mono- and dimethylsulfate will be evaluated under several atmospheric conditions.

  4. Methanol Uptake by Low Temperature Aqueous Sulfuric Acid Solutions

    NASA Technical Reports Server (NTRS)

    Iraci, L. T.; Essin, A. M.; Golden, D. M.; Hipskind, R. Stephen (Technical Monitor)

    2001-01-01

    The global methanol budget is currently unbalanced, with source terms significantly larger than the sinks terms. To evaluate possible losses of gaseous methanol to sulfate aerosols, the solubility and reactivity of methanol in aqueous sulfuric acid solutions representative of upper tropospheric and lower stratospheric aerosols is under investigation. Methanol will partition into sulfate aerosols according to its Henry's law solubility. Using standard uptake techniques in a Knudsen cell reactor, we have measured the effective Henry's law coefficient, H*, for cold (196 - 220 K) solutions ranging between 45 and 70 wt % H2SO4. We have found that methanol solubility ranges from approx. 10(exp 5) - 10(exp 7) M/atm for UT/LS conditions. Solubility increases with decreasing temperature and with increasing sulfuric acid content. Although methanol is slightly more soluble than are acetone and formaldehyde, current data indicate that uptake by clean aqueous sulfuric acid particles will not be a significant sink for methanol in the UT/LS. These solubility measurements include uptake due to physical solvation and any rapid equilibria which are established in solution. Reaction between primary alcohols and sulfuric acid does occur, leading to the production of alkyl sulfates. Literature values for the rate of this reaction suggest that formation of CH3OSO3H is not significant over our experimental time scale for solutions below 80 wt % H2SO4. To confirm this directly, results obtained using a complementary equilibrium measurement technique will also be presented.

  5. A critique of homogeneous freezing measurements of aqueous sulfuric acid

    NASA Astrophysics Data System (ADS)

    Alofs, Darryl J.; Vandike, John L.

    2000-08-01

    Two laboratory measurements of homogeneous freezing of aqueous sulfuric acid particles are critiqued: The first by Bertram et al., 1996, J. Phys. Chem., vol. 100, pp. 2376-2383: the second by Koop et al., 1998, J. Phys. Chem. A, vol. 102, pp. 8924-8931. Calculations for a proposed experimental artifact are inconclusive for Bertram et al. A proposed artifact for Koop et al. is shown to be insignificant.

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

    PubMed

    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.

  7. Photocatalytic Oxidation of Sulfurous Acid in an Aqueous Medium

    ERIC Educational Resources Information Center

    Romero, Alicia; Hernandez, Willie; Suarez, Marco F.

    2005-01-01

    The effect of some parameters on sulfurous acid and sulfur oxidation kinetics such as initial concentration of sulfurous acid, oxygen, TiO[2] crystalline concentration, the power of black light, and quantity of TiO[2] is investigated. The experiments can be performed in an undergraduate physical chemistry laboratory with an inexpensive…

  8. Photocatalytic Oxidation of Sulfurous Acid in an Aqueous Medium

    ERIC Educational Resources Information Center

    Romero, Alicia; Hernandez, Willie; Suarez, Marco F.

    2005-01-01

    The effect of some parameters on sulfurous acid and sulfur oxidation kinetics such as initial concentration of sulfurous acid, oxygen, TiO[2] crystalline concentration, the power of black light, and quantity of TiO[2] is investigated. The experiments can be performed in an undergraduate physical chemistry laboratory with an inexpensive…

  9. Thermodynamic Properties of the Aqueous Sulfuric Acid System to 350 K

    NASA Astrophysics Data System (ADS)

    Zeleznik, Frank J.

    1991-11-01

    Experimental measurements for aqueous sulfuric acid and its related pure, solid phases have been thermodynamically analyzed and correlated as a function of temperature and composition from pure water to pure acid. The pure phases included anhydrous sulfuric acid, five of its hydrates and ice. Experimental data which were used in the correlation included measurements of the enthalpy of dilution, both solution and pure phase heat capacities, electromotive force and solution freezing points. The correlation yielded mutually consistent expressions for the Gibbs energy of each phase and these functions generally reproduce the experimental data to ±0.75 percent. The Gibbs energy functions of the pure solid phases were used to generate tables of their thermodynamic properties from 0 K to the melting points. The Gibbs energy function for aqueous sulfuric acid was used to produce tables of both integral and partial molar solution properties as a function of sulfuric acid mole fraction every 50° from 200 to 350 K.

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

    NASA Technical Reports Server (NTRS)

    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.

  11. Solubility of methanol in low-temperature aqueous sulfuric acid and implications for atmospheric particle composition

    NASA Technical Reports Server (NTRS)

    Iraci, Laura T.; Essin, Andrew M.; Golden, David M.; Hipskind, R. Stephen (Technical Monitor)

    2001-01-01

    Using traditional Knudsen cell techniques, we find well-behaved Henry's law uptake of methanol in aqueous 45 - 70 wt% H2SO4 solutions at temperatures between 197 and 231 K. Solubility of methanol increases with decreasing temperature and increasing acidity, with an effective Henry's law coefficient ranging from 10(exp 5) - 10(exp 8) M/atm. Equilibrium uptake of methanol into sulfuric acid aerosol particles in the upper troposphere and lower stratosphere will not appreciably alter gas-phase concentrations of methanol. The observed room temperature reaction between methanol and sulfuric acid is too slow to provide a sink for gaseous methanol at the temperatures of the upper troposphere and lower stratosphere. It is also too slow to produce sufficient quantities of soluble reaction products to explain the large amount of unidentified organic material seen in particles of the upper troposphere.

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

    PubMed Central

    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

  13. The infrared optical constants of sulfuric acid at 250 K. [spectral reflectance measurement of aqueous solutions

    NASA Technical Reports Server (NTRS)

    Pinkley, L. W.; Williams, D.

    1976-01-01

    Results are presented for measurements of the IR spectral reflectance at near-normal incidence of aqueous solutions of sulfuric acid with acid concentrations of 75% and 95.6% by weight. Kramers-Kronig analyses of the reflectance data are employed to obtain values of the optical constants n(nu) and k(nu) in the spectral range from 400 to 6000 cm to the -1 power. The optical constants of these solutions at 250 K and 300 K are compared. It is found that in spectral regions remote from strong absorption bands, the values of the n(nu) indices obtained at 250 K agree with the values given by Lorentz-Lorenz correction of the same indices at 300 K. All absorption bands observed at 300 K are found to be present at 250 K with slight shifts in frequency and with significant differences in the k(nu) indices at the band maxima. Based on these results, it is concluded that the clouds of Venus probably consist of droplets of aqueous solutions of sulfuric acid with acid concentrations of about 75% by weight.

  14. Uptake of methacrolein into aqueous solutions of sulfuric acid and hydrogen peroxide.

    PubMed

    Liu, Ze; Wu, Ling-Yan; Wang, Tian-He; Ge, Mao-Fa; Wang, Wei-Gang

    2012-01-12

    Multiphase acid-catalyzed oxidation by hydrogen peroxide has been suggested to be a potential route to secondary organic aerosol (SOA) formation from isoprene and its gas-phase oxidation products, but the kinetics and chemical mechanism remain largely uncertain. Here we report the first measurement of uptake of methacrolein into aqueous solutions of sulfuric acid and hydrogen peroxide in the temperature range of 253-293 K. The steady-state uptake coefficients were acquired and increased quickly with increasing sulfuric acid concentration and decreasing temperature. Propyne, acetone, and 2,3-dihydroxymethacrylic acid were suggested as the products. The chemical mechanism is proposed to be the oxidation of carbonyl group and C═C double bonds by peroxide hydrogen in acidic environment, which could explain the large content of polyhydroxyl compounds in atmospheric fine particles. These results indicate that multiphase acid-catalyzed oxidation of methacrolein by hydrogen peroxide can contribute to SOA mass in the atmosphere, especially in the upper troposphere.

  15. Chemistry in the Venus clouds: Sulfuric acid reactions and freezing behavior of aqueous liquid droplets

    NASA Astrophysics Data System (ADS)

    Delitsky, M. L.; Baines, K. H.

    2015-11-01

    Venus has a thick cloud deck at 40-70 km altitude consisting of liquid droplets and solid particles surrounded by atmospheric gases. The liquid droplets are highly concentrated aqueous solutions of sulfuric acid ranging in concentration from 70-99 wt%. Weight percent drops off with altitude (Imamura and Hashimoto 2001). There will be uptake of atmospheric gases into the droplet solutions and the ratios of gas-phase to liquid-phase species will depend on the Henry’s Law constant for those solutions. Reactions of sulfuric acid with these gases will form products with differing solubilities. For example, uptake of HCl by H2SO4/H2O droplets yields chlorosulfonic acid, ClSO3H (Robinson et al 1998) in solution. This may eventually decompose to thionyl- or sulfuryl chlorides, which have UV absorbances. HF will also uptake, creating fluorosulfonic acid, FSO3H, which has a greater solubility than the chloro- acid. As uptake continues, there will be many dissolved species in the cloudwaters. Baines and Delitsky (2013) showed that uptake will have a maximum at ~62 km and this is very close to the reported altitude for the mystery UV absorber in the Venus atmosphere. In addition, at very strong concentrations in lower altitude clouds, sulfuric acid will form hydrates such as H2SO4.H2O and H2SO4.4H2O which will have very different freezing behavior than sulfuric acid, with much higher freezing temperatures (Carslaw et al, 1997). Using temperature data from Venus Express from Tellmann et al (2009), and changes in H2SO4 concentrations as a function of altitude (James et al 1997), we calculate that freezing out of sulfuric acid hydrates can be significant down to as low as 56 km altitude. As a result, balloons, aircraft or other probes in the Venus atmosphere may be limited to flying below certain altitudes. Any craft flying at altitudes above ~55 km may suffer icing on the wings, propellers, balloons and instruments which could cause possible detrimental effects (thermal

  16. Activity and osmotic coefficients of aqueous sulfuric acid at 298.15 K

    NASA Astrophysics Data System (ADS)

    Staples, Bert R.

    1981-07-01

    A critical evaluation of the mean activity coefficient, γ±, and osmotic coefficient, φ, of aqueous sulfuric acid at 298.15 K is presented for the molality range of 0 to 28 molṡkg-1. Osmotic coefficients were calculated from direct vapor pressure measurements, from isopietic measurements or from freezing point depression measurements. Activity coefficients were calculated from electromotive force measurements of galvanic cells. A least-squares program was used to fit data from all sources using both φ and ln γ± as functions of molality. A nine parameter equation describes the osmotic coefficient, the mean activity coefficient, and the excess. Gibbs energy as a function of the one-half power of molality. The scientific literature has been covered through January, 1979.

  17. Isolation and separation of transplutonium elements from other actinides on ion exchange resins from aqueous and aqueous ethanol solutions of sulfuric acid

    SciTech Connect

    Guseva, L.I.; Tikhomirova, G.S.; Stepushkina, V.V.

    1987-11-01

    The behavior of Am, Cm, Bk, Cf, Es, and other actinides, as well as Zr, on an anion exchange resin and a cation exchange resin in aqueous and aqueous alcohol solutions of sulfuric acid was investigated as a function of the concentration of various components of the solution. It was found that the presence of alcohol in sulfuric acid solutions leads to an increase in the distribution coefficients both on cation exchange resins and on anion exchange resins. The possibility of using ion exchange resins for the concentration and separation of transplutonium elements from U, Np, Pu, Zr, and other elements that form strong complexes with sulfate ions in a wide range of sulfuric acid concentrations was demonstrated.

  18. Uptake of isoprene, methacrylic acid and methyl methacrylate into aqueous solutions of sulfuric acid and hydrogen peroxide.

    PubMed

    Liu, Ze; Ge, Maofa; Wang, Weigang

    2012-01-01

    Multiphase acid-catalyzed oxidation by hydrogen peroxide has been suggested to be a potential route to secondary organic aerosol formation from isoprene and its gas-phase oxidation products, but the lack of kinetics data significantly limited the evaluation of this process in the atmosphere. Here we report the first measurement of the uptake of isoprene, methacrylic acid and methyl methacrylate into aqueous solutions of sulfuric acid and hydrogen peroxide. Isoprene cannot readily partition into the solution because of its high volatility and low solubility, which hinders its further liquid-phase oxidation. Both methacrylic acid and methyl methacrylate can enter the solutions and be oxidized by hydrogen peroxide, and steady-state uptake was observed with the acidity of solution above 30 wt.% and 70 wt.%, respectively. The steady-state uptake coefficient of methacrylic acid is much larger than that of methyl methacrylate for a solution with same acidity. These observations can be explained by the different reactivity of these two compounds caused by the different electron-withdrawing conjugation between carboxyl and ester groups. The atmospheric lifetimes were estimated based on the calculated steady-state uptake coefficients. These results demonstrate that the multiphase acid-catalyzed oxidation of methacrylic acid plays a role in secondary organic aerosol formation, but for isoprene and methyl methacrylate, this process is not important in the troposphere.

  19. Recovery of transplutonium elements from aqueous and water-ethanol solutions of sulfuric acid and their separation from other actinides

    SciTech Connect

    Guseva, L.I.; Tikhomirova, G.S.; Stepushkina, V.V.

    1988-05-01

    The behavior of Am, Cm, Bk, Cf, Es, and other actinides, as well as Zr, on anion and cation exchangers in aqueous and water-ethanol solutions of sulfuric acid as a function of the various components of the solution has been investigated. It has been discovered that the presence of ethanol in sulfuric acid solutions causes an increase in the distribution coefficients both on cation exchangers and on anion exchangers. The possibility of the use of ion exchangers for the preconcentration and separation of transplutonium elements from U, Np, Pu, Zr, and other elements which form strong complexes with sulfate ions over a broad range of concentrations of sulfuric acid has been demonstrated.

  20. Molecular Modeling of Ammonium, Calcium, Sulfur, and Sodium Lignosulphonates in Acid and Basic Aqueous Environments

    NASA Astrophysics Data System (ADS)

    Salazar Valencia, P. J.; Bolívar Marinez, L. E.; Pérez Merchancano, S. T.

    2015-12-01

    Lignosulphonates (LS), also known as lignin sulfonates or sulfite lignin, are lignins in sulfonated forms, obtained from the "sulfite liquors," a residue of the wood pulp extraction process. Their main utility lies in its wide range of properties, they can be used as additives, dispersants, binders, fluxing, binder agents, etc. in fields ranging from food to fertilizer manufacture and even as agents in the preparation of ion exchange membranes. Since they can be manufactured relatively easy and quickly, and that its molecular size can be manipulated to obtain fragments of very low molecular weight, they are used as transport agents in the food industry, cosmetics, pharmaceutical and drug development, and as molecular elements for the treatment of health problems. In this paper, we study the electronic structural and optical characteristics of LS incorporating ammonium, sulfur, calcium, and sodium ions in acidic and basic aqueous media in order to gain a better understanding of their behavior and the very interesting properties exhibit. The studies were performed using the molecular modeling program HyperChem 5 using the semiempirical method PM3 of the NDO Family (neglect of differential overlap), to calculate the structural properties. We calculated the electronic and optical properties using the semiempirical method ZINDO / CI.

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

    Treesearch

    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...

  2. 4-Carboxybenzophenone-sensitized photooxidation of sulfur-containing amino acids in alkaline aqueous solutions. Secondary photoreactions kinetics

    SciTech Connect

    Bobrowski, K.; Hug, G.L. ); Marciniak, B. A. Mickiewicz Univ., Poznan ); Kozubek, H. )

    1994-01-13

    Sulfur-containing amino acids and alanine were oxidized via photosensitization by 4-carboxybenzophenone (CB) in alkaline aqueous solutions. The mechanism of this reaction was examined using steady-state and laser flash photolysis techniques. The rate constants were determined for the quenching of the CB triplet state by five sulfur-containing amino acids and alanine and were found to be approximately 10[sup 9] and 1.8 x 10[sup 8] M[sup [minus]1] s[sup [minus]1], respectively. The observation of the (S therefore S)[sup +] radical cations of some of the amino acids showed that the quenching process involves an electron transfer from the sulfur atom to the triplet state of CB. A show process of formation of the ketyl radical anion occurring on the microsecond time scale was assigned to the one-electron reduction of CB by the [alpha]-aminoalkyl radicals that were formed earlier as a result of an intramolecular electron transfer from the carboxyl group to the sulfur-centered radical cation followed by decarboxylation. For thiaproline, the pseudo-first-order rate constant, k[prime][sub obs], which characterizes the slow process of secondary ketyl radical anion formation, is linearly dependent on the CB concentration over the pH region 9.4-13.4. A detailed mechanism for the primary and the secondary photoreduction of CB is proposed and discussed. 32 refs., 7 figs., 5 tabs.

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

    PubMed

    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. Pervaporation of Water from Aqueous Sulfuric Acid at Elevated Temperatures Using Nafion® Membranes

    SciTech Connect

    Christopher J. Orme; Frederick F. Stewart

    2009-01-01

    The concentration of sulfuric acid by pervaporation has been studied using Nafion-112® and Nafion-117® membranes, which have been characterized in terms of flux, permeability, and selectivity at 100 ºC and 120 ºC. Feed concentrations investigated ranged from 40 to over 80 weight percent. In general, water fluxes ranged from 100-8000 g/m2h, depending on feed acid concentration and separations factors as high as 104 were observed. Membrane stability was probed using Dynamic Mechanical Analysis that revealed some embrittlement of the membranes during use. Further studies showed that the embrittlement was due to an interaction with the acid and was not induced by the operating temperature.

  5. Oxygenation of methylarenes to benzaldehyde derivatives by a polyoxometalate mediated electron transfer-oxygen transfer reaction in aqueous sulfuric Acid.

    PubMed

    Sarma, Bidyut Bikash; Efremenko, Irena; Neumann, Ronny

    2015-05-13

    The synthesis of benzaldehyde derivatives by oxygenation of methylarenes is of significant conceptual and practical interest because these compounds are important chemical intermediates whose synthesis is still carried out by nonsustainable methods with very low atom economy and formation of copious amounts of waste. Now an oxygenation reaction with a 100% theoretical atom economy using a polyoxometalate oxygen donor has been found. The product yield is typically above 95% with no "overoxidation" to benzoic acids; H2 is released by electrolysis, enabling additional reaction cycles. An electrocatalytic cycle is also feasible. This reaction is possible through the use of an aqueous sulfuric acid solvent, in an aqueous biphasic reaction mode that also allows simple catalyst recycling and recovery. The solvent plays a key role in the reaction mechanism by protonating the polyoxometalate thereby enabling the activation of the methylarenes by an electron transfer process. After additional proton transfer and oxygen transfer steps, benzylic alcohols are formed that further react by an electron transfer-proton transfer sequence forming benzaldehyde derivatives.

  6. Sulfuric Acid on Europa

    NASA Image and Video Library

    1999-09-30

    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. http://photojournal.jpl.nasa.gov/catalog/PIA02500

  7. Sulfuric Acid and Water: Paradoxes of Dilution

    ERIC Educational Resources Information Center

    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…

  8. Sulfuric Acid and Water: Paradoxes of Dilution

    ERIC Educational Resources Information Center

    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…

  9. Sulfuric Acid on Europa

    NASA Technical Reports Server (NTRS)

    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.

  10. Sulfuric acid-sulfur heat storage cycle

    DOEpatents

    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.

  11. Are the clouds of Venus sulfuric acid.

    NASA Technical Reports Server (NTRS)

    Young, A. T.

    1973-01-01

    It is shown that strong aqueous sulfuric acid solutions have the right refractive index and freeze at Venusian cloud temperature, explain the dryness of the Venusian stratosphere, are consistent with some features of the Venusian IR spectrum, and do not absorb in highly reflecting areas of Venus. It is also indicated that such solutions should be produced by reactions between known atmospheric constituents and most sulfur-bearing rock at the Venusian surface temperature, and require only small amounts of sulfur consistent with its cosmic abundance and with the amounts of other volatile elements present in the atmosphere. It is believed therefore that the clouds of Venus consist of sulfuric acid solutions.

  12. Solubility of Sulfur Dioxide in Sulfuric Acid

    NASA Technical Reports Server (NTRS)

    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.

  13. Aqueous sulfuric acid as the mobile phase in cation ion chromatography for determination of histamine, putrescine, and cadaverine in fish samples.

    PubMed

    Liao, Benjamin S; Sram, Jackie; Cain, Teresa T; Halcrow, Kenneth R

    2011-01-01

    Aqueous sulfuric acid can be used as the mobile phase in cation ion chromatography to separate the three biogenic amines, putrescine, cadaverine, and histamine, from fish. Various concentrations of aqueous sulfuric acid were investigated to optimize the separation of these three biogenic amines. Aqueous sulfuric acid (5.0 mM) was found to be optimum for the separation and was used to determine the three biogenic amines in fish. The LOQ, defined as the lowest level of the standard calibration curve, was 0.055 ppm (equivalent to 0.55 microg/g sample) for putrescine, 0.05 ppm (equivalent to 0.5 microg/g sample) for cadaverine, and 1.0 ppm (equivalent to 10 microg/g sample) for histamine. From statistical analysis of the LOQ, the method detection limit was 0.003 ppm for putrescine, 0.009 ppm for cadaverine, and 0.16 ppm for histamine. For sample preparation, the fish was composited, homogenized in methanol-water (75 + 25, v/v), incubated for 15 min at 60 degrees C, and centrifuged. The sample solution was micron-filtered before injection. The mobile phase flow rate was 0.8 mL/min under isocratic conditions at room temperature (15-25 degrees C). The three biogenic amines were separated in the order of increasing retention time, i.e., putrescine, cadaverine, and histamine, within 30 min. The chromatograms showed complete peak separation of the three amines regardless of the difference in fish matrixes.

  14. Sulfuric acid on Europa and the radiolytic sulfur cycle.

    PubMed

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

    1999-10-01

    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.

  15. Sulfuric acid on Europa and the radiolytic sulfur cycle

    NASA Technical Reports Server (NTRS)

    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.

  16. Efficient catalytic hydration of cyanamides in aqueous medium and in the presence of Naringin sulfuric acid or green synthesized silver nanoparticles by using Gongronema latifolium leaf extract.

    PubMed

    Issaabadi, Zahra; Nasrollahzadeh, Mahmoud; Sajadi, S Mohammad

    2017-10-01

    In this paper, a novel, efficient and green method for the preparation of Naringin sulfuric acid (NSA) as a Brønsted acid organocatalyst and silver nanoparticles (Ag NPs) by using Gongronema latifolium leaf extract as a reducing and stabilizing agent is introduced. The catalysts were characterized using the powder XRD, SEM, EDS, TEM, UV-Vis and FT-IR spectroscopy. Afterward, the catalytic activity of synthesized NSA and Ag NPs were investigated for the synthesis of N-monosubstituted ureas via the hydration of cyanamides in aqueous medium. All products were obtained in good to excellent yields. These methods provided several advantages such as shorter reaction time, simpler work-up and higher yield. Copyright © 2017 Elsevier Inc. All rights reserved.

  17. Sulfuric acid thermoelectrochemical system and method

    DOEpatents

    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.

  18. Mass accommodation coefficient measurements for HNO3, HCl and N2O5 on water, ice and aqueous sulfuric acid droplet surfaces

    NASA Technical Reports Server (NTRS)

    Worsnop, Douglas; Zahniser, Mark; Kolb, Charles; Watson, Lyn; Vandoren, Jane; Jayne, John; Davidovits, Paul

    1988-01-01

    Preliminary results are reported of the direct measurement of accommodation coefficients for HNO3, N2O5 and HCl on water drops, aqueous sulfuric acid drops and ice particles. The heterogeneous chemistry of these species together with ClONO2 has been implicated in the ozone depletion observed in the Antarctic stratosphere during the spring in the last eight years. The most plausible chemical mechanism involves the removal of nitrogen oxide species via condensation on ice particles in polar stratospheric clouds resulting in a increase in the active chlorine species responsible for the ozone depletion. The observation of low NO2 and high ClO densities in the Antarctic stratosphere last summer appear to be consistent with such a mechanism.

  19. Process for forming sulfuric acid

    DOEpatents

    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.

  20. Sulfuric acid as autocatalyst in the formation of sulfuric acid.

    PubMed

    Torrent-Sucarrat, Miquel; Francisco, Joseph S; Anglada, Josep M

    2012-12-26

    Sulfuric acid can act as a catalyst of its own formation. We have carried out a computational investigation on the gas-phase formation of H(2)SO(4) by hydrolysis of SO(3) involving one and two water molecules, and also in the presence of sulfuric acid and its complexes with one and two water molecules. The hydrolysis of SO(3) requires the concurrence of two water molecules, one of them acting as a catalyzer, and our results predict an important catalytic effect, ranging between 3 and 11 kcal·mol(-1) when the catalytic water molecule is substituted by a sulfuric acid molecule or one of its hydrates. In these cases, the reaction products are either bare sulfuric acid dimer or sulfuric acid dimer complexed with a water molecule. There are broad implications from these new findings. The results of the present investigation show that the catalytic effect of sulfuric acid in the SO(3) hydrolysis can be important in the Earth's stratosphere, in the heterogeneous formation of sulfuric acid and in the formation of aerosols, in H(2)SO(4) formation by aircraft engines, and also in understanding the formation of sulfuric acid in the atmosphere of Venus.

  1. CHARACTERIZATION OF SULFUR CONTAINING ANALOGS OF MONOMETHYLARSONIC ACID IN AQUEOUS PHASE STANDARDS AND CARROT EXTRACTS BY IC-ICP-MS AND IC-ESI-MS/MS

    EPA Science Inventory

    Recently, sulfur analogs of well known arsenicals have been identified, generating a need for stable species-specific standards. This presentation will focus on the identification and characterization of a novel species, monomethylthioarsonic acid (MMTA), in carrots. A standard...

  2. CHARACTERIZATION OF SULFUR CONTAINING ANALOGS OF MONOMETHYLARSONIC ACID IN AQUEOUS PHASE STANDARDS AND CARROT EXTRACTS BY IC-ICP-MS AND IC-ESI-MS/MS

    EPA Science Inventory

    Recently, sulfur analogs of well known arsenicals have been identified, generating a need for stable species-specific standards. This presentation will focus on the identification and characterization of a novel species, monomethylthioarsonic acid (MMTA), in carrots. A standard...

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

    PubMed

    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).

  4. Solubility of sulfur dioxide in aqueous solutions of acetic acid, sodium acetate, and ammonium acetate in the temperature range from 313 to 393 K at pressures up to 3.3 MPa: Experimental results and comparison with correlations/predictions

    SciTech Connect

    Xia, J.; Rumpf, B.; Maurer, G.

    1999-03-01

    In many chemical plants, for example in coal gasification processes or desulfurization equipment, sour gas absorption columns and sour water strippers are used to remove weak electrolyte gases like sulfur dioxide, hydrogen cyanide, hydrogen sulfide or carbon dioxide from aqueous solutions. The basic design of such equipment requires physico-chemical models to describe the phase equilibrium as well as the caloric properties of such mixtures. New experimental results for the solubility of sulfur dioxide in aqueous solutions of single solutes acetic acid, sodium acetate and ammonium acetate at temperatures from 313 to 393 K and total pressures up to 3.3 MPa are reported. Similar to the system sulfur dioxide-water, also in such systems with acetic acid and sodium or ammonium acetate a second (sulfur dioxide rich) liquid phase is observed at high sulfur dioxide concentrations. A model to describe the phase equilibrium is presented and calculated (i.e., predicted as well as correlated) phase equilibria are compared to the new experimental data.

  5. Sulfuric Acid in the Venus Clouds

    NASA Technical Reports Server (NTRS)

    Sill, G. T.

    1972-01-01

    The visible and ultraviolet transmission features of a thin layer of elemental bromine and hydrobromic acid dissolved in sulfuric acid somewhat resemble the Venus spectrum, up to 14 microns. The chemical process postulated for forming sulfuric acid involves the oxidation of sulfur and its compounds to sulfuric acid through the agency of elemental bromine, produced by the photolytic decomposition of hydrogen bromide.

  6. An evaluation of possible mechanisms for conversion of sulfur dioxide to sulfuric acid and sulfate aerosols in the troposphere

    Treesearch

    Jack G. Calvert

    1976-01-01

    The mechanisms and rates of conversion of sulfur dioxide to sulfur trioxide, sulfuric acid, and other "sulfate" aerosol precursors are considered in view of current knowledge related to atmospheric reactions and chemical kinetics. Several heterogeneous pathways exist for SO2 oxidation promoted on solid catalyst particles and in aqueous...

  7. Hydrate sulfuric acid after sulfur implantation in water ice

    NASA Astrophysics Data System (ADS)

    Strazzulla, G.; Baratta, G. A.; Leto, G.; Gomis, O.

    2007-12-01

    For many years an ongoing research program performed at our laboratory has had the aim to investigate the implantation of reactive ions in ices relevant to planetology by using IR spectroscopy. We present new results obtained by implanting 200 keV sulfur ions into water ice at 80 K. We have looked at the formation of sulfur-bearing molecules such as sulfuric acid, sulfur dioxide and hydrogen sulfide. We find that hydrated sulfuric acid is formed with high yield ( 0.65±0.1 molecules/ion). An upper limit to the production yield of SO 2 ( Y⩽0.025 molecules/ion) has been estimated; no hydrogen sulfide has been detected. The formation of hydrogen peroxide is confirmed. Ozone is not detected. The results are discussed relevant to the inquiry on the radiolytic sulfur cycle considered responsible for the formation of sulfur-bearing molecules on the surfaces of the Galilean satellites. We demonstrate that sulfur implantation efficiently forms hydrated sulfuric acid whose observed abundance is explained as caused by an exogenic process. It is more difficult to say if the observed sulfur dioxide is quantitatively supported by only sulfur implantation; additional experimental studies are necessary along with direct observations, especially at UV wavelengths such as those that could be performed by instruments on board Hubble Space Telescope or by the forthcoming World Space Observatory (WSO/UV).

  8. 46 CFR 153.1046 - Sulfuric acid.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 5 2013-10-01 2013-10-01 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...

  9. 21 CFR 582.1095 - Sulfuric acid.

    Code of Federal Regulations, 2010 CFR

    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...

  10. 21 CFR 582.1095 - Sulfuric acid.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 6 2013-04-01 2013-04-01 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...

  11. 21 CFR 582.1095 - Sulfuric acid.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 6 2012-04-01 2012-04-01 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. 46 CFR 153.1046 - Sulfuric acid.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 5 2014-10-01 2014-10-01 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...

  13. 46 CFR 153.1046 - Sulfuric acid.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 5 2011-10-01 2011-10-01 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...

  14. 46 CFR 153.1046 - Sulfuric acid.

    Code of Federal Regulations, 2010 CFR

    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...

  15. 21 CFR 582.1095 - Sulfuric acid.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 6 2011-04-01 2011-04-01 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...

  16. 21 CFR 184.1095 - Sulfuric acid.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 3 2014-04-01 2014-04-01 false Sulfuric acid. 184.1095 Section 184.1095 Food and Drugs FOOD AND DRUG ADMINISTRATION, DEPARTMENT OF HEALTH AND HUMAN SERVICES (CONTINUED) DIRECT FOOD....1095 Sulfuric acid. (a) Sulfuric acid (H2SO4, CAS Reg. No. 7664-93-9), also known as oil of vitriol, is...

  17. 21 CFR 582.1095 - Sulfuric acid.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... 21 Food and Drugs 6 2014-04-01 2014-04-01 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...

  18. 46 CFR 153.1046 - Sulfuric acid.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 5 2012-10-01 2012-10-01 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...

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

    NASA Technical Reports Server (NTRS)

    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.

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

    NASA Technical Reports Server (NTRS)

    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. Heterogeneous Interactions of Acetaldehyde and Sulfuric Acid

    NASA Technical Reports Server (NTRS)

    Michelsen, R. R.; Ashbourn, S. F. M.; Iraci, L. T.

    2004-01-01

    The uptake of acetaldehyde [CH3CHO] by aqueous sulfuric acid has been studied via Knudsen cell experiments over ranges of temperature (210-250 K) and acid concentration (40-80 wt. %) representative of the upper troposphere. The Henry's law constants for acetaldehyde calculated from these data range from 6 x 10(exp 2) M/atm for 40 wt. % H2SO4 at 228 K to 2 x 10(exp 5) M/atm for 80 wt. % H2SO4 at 212 K. In some instances, acetaldehyde uptake exhibits apparent steady-state loss. The possible sources of this behavior, including polymerization, will be explored. Furthermore, the implications for heterogeneous reactions of aldehydes in sulfate aerosols in the upper troposphere will be discussed.

  2. 21 CFR 184.1095 - Sulfuric acid.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false 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...

  3. 21 CFR 184.1095 - Sulfuric acid.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... 21 Food and Drugs 3 2013-04-01 2013-04-01 false 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...

  4. 21 CFR 184.1095 - Sulfuric acid.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... 21 Food and Drugs 3 2012-04-01 2012-04-01 false 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...

  5. 21 CFR 184.1095 - Sulfuric acid.

    Code of Federal Regulations, 2010 CFR

    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...

  6. Charles H. Winston and Confederate Sulfuric Acid

    NASA Astrophysics Data System (ADS)

    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.

  7. Nitrosyl sulfuric acid and stratospheric aerosols

    NASA Astrophysics Data System (ADS)

    Burley, Joel D.; Johnston, H. S.

    1992-07-01

    It is proposed on the basis of information found in the atmospheric and chemical literature that nitrosyl sulfuric acid (NSA), NOHSO4 may play an important role in stratospheric chemistry. If the reaction probability of forming NSA per collision of NO with a sulfuric acid aerosol is 0.001, 1 percent of the sulfuric acid would be converted to NSA within 1 d at 20 km altitude. If NSA in the sulfate aerosols is 1 percent of the sulfuric acid and if the second order rate constant for (HCl + NOHSO4 = H2SO4 + ClNO) in sulfuric acid solution is greater than 10 exp -18 cu cm/molecule s under conditions at 20 km altitude, the rate of HCl + NSA is faster than the rate of HO + HCl. In this case, this heterogeneous catalysis is expected to affect the balance of No sub y, Cl sub y, and the ozone in the lower stratosphere.

  8. Heterogeneous Chemistry of HO2NO2 on Liquid Sulfuric Acid

    NASA Technical Reports Server (NTRS)

    Leu, Ming-Taun

    1995-01-01

    The interaction of HO2NO2 (peroxynitric acid, PNA) vapor with liquid sulfuric acid surfaces was investigated for the acid contents ranging from 50 to 70 wt % and over a temperature range from 205 to 230 K, using a fast flow-reactor coupled to a chemical ionization mass spectrometer. PNA was observed to be physically taken up by liquid sulfuric acid, without undergoing irreversible aqueous phase reactions.

  9. Dissolution, speciation, and reaction of acetaldehyde in cold sulfuric acid

    NASA Astrophysics Data System (ADS)

    Michelsen, Rebecca R.; Ashbourn, Samantha F. M.; Iraci, Laura T.

    2004-12-01

    The uptake of gas-phase acetaldehyde [CH3CHO, ethanal] by aqueous sulfuric acid solutions was studied under upper tropospheric/lower stratospheric (UT/LS) conditions. The solubility of acetaldehyde was found to be low, between 2 × 102 M atm-1 and 1.5 × 105 M atm-1 under the ranges of temperature (211-241 K) and acid composition (39-76 weight percent, wt%, H2SO4) studied. Under most conditions, acetaldehyde showed simple solubility behavior when exposed to sulfuric acid. Under moderately acidic conditions (usually 47 wt% H2SO4), evidence of reaction was observed. Enhancement of uptake at long times was occasionally detected in conjunction with reaction. The source of these behaviors and the effect of acetaldehyde speciation on solubility are discussed. Implications for the uptake of oxygenated organic compounds by tropospheric aerosols are considered.

  10. Linking neutral and charged sulfuric acid-ammonia and sulfuric acid-dimethylamine clusters

    NASA Astrophysics Data System (ADS)

    Ortega, Ismael K.; Kupiainen, Oona; Olenius, Tinja; Loukonen, Ville; Kurtén, Theo; Vehkamäki, Hanna

    2013-05-01

    We have used a quantum chemical method to calculate the formation free energies of negatively charged sulfuric acid - ammonia and sulfuric acid - dimethylamine clusters. Using the calculated formation free energies we have estimated the evaporation rates of the clusters. We have compared the evaporation rate of the charged clusters with the corresponding neutral clusters. We found that, although small clusters of sulfuric acid with ammonia and dimethylamine are stable and should be present in the atmosphere, they can not be detected using mass spectroscopy techniques. Charging the cluster will result in the fast evaporation of the base molecules, and they will be detected as pure sulfuric acid cluster.

  11. 46 CFR 151.50-21 - Sulfuric acid.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 5 2011-10-01 2011-10-01 false Sulfuric acid. 151.50-21 Section 151.50-21 Shipping... BULK LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-21 Sulfuric acid. (a) How sulfuric acid may be carried. (1) Sulfuric acid of concentration of 77.5 percent (1.7019 specific gravity) (59.8...

  12. 46 CFR 151.50-21 - Sulfuric acid.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 5 2014-10-01 2014-10-01 false Sulfuric acid. 151.50-21 Section 151.50-21 Shipping... BULK LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-21 Sulfuric acid. (a) How sulfuric acid may be carried. (1) Sulfuric acid of concentration of 77.5 percent (1.7019 specific gravity) (59.8...

  13. 46 CFR 151.50-21 - Sulfuric acid.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 5 2013-10-01 2013-10-01 false Sulfuric acid. 151.50-21 Section 151.50-21 Shipping... BULK LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-21 Sulfuric acid. (a) How sulfuric acid may be carried. (1) Sulfuric acid of concentration of 77.5 percent (1.7019 specific gravity) (59.8...

  14. 46 CFR 151.50-21 - Sulfuric acid.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

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

  15. 46 CFR 151.50-21 - Sulfuric acid.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 5 2012-10-01 2012-10-01 false Sulfuric acid. 151.50-21 Section 151.50-21 Shipping... BULK LIQUID HAZARDOUS MATERIAL CARGOES Special Requirements § 151.50-21 Sulfuric acid. (a) How sulfuric acid may be carried. (1) Sulfuric acid of concentration of 77.5 percent (1.7019 specific gravity) (59.8...

  16. Photochemistry of aqueous pyruvic acid

    PubMed Central

    Griffith, Elizabeth C.; Carpenter, Barry K.; Shoemaker, Richard K.; Vaida, Veronica

    2013-01-01

    The study of organic chemistry in atmospheric aerosols and cloud formation is of interest in predictions of air quality and climate change. It is now known that aqueous phase chemistry is important in the formation of secondary organic aerosols. Here, the photoreactivity of pyruvic acid (PA; CH3COCOOH) is investigated in aqueous environments characteristic of atmospheric aerosols. PA is currently used as a proxy for α-dicarbonyls in atmospheric models and is abundant in both the gas phase and the aqueous phase (atmospheric aerosols, fog, and clouds) in the atmosphere. The photoreactivity of PA in these phases, however, is very different, thus prompting the need for a mechanistic understanding of its reactivity in different environments. Although the decarboxylation of aqueous phase PA through UV excitation has been studied for many years, its mechanism and products remain controversial. In this work, photolysis of aqueous PA is shown to produce acetoin (CH3CHOHCOCH3), lactic acid (CH3CHOHCOOH), acetic acid (CH3COOH), and oligomers, illustrating the progression from a three-carbon molecule to four-carbon and even six-carbon molecules through direct photolysis. These products are detected using vibrational and electronic spectroscopy, NMR, and MS, and a reaction mechanism is presented accounting for all products detected. The relevance of sunlight-initiated PA chemistry in aqueous environments is then discussed in the context of processes occurring on atmospheric aerosols. PMID:23821751

  17. Photochemistry of aqueous pyruvic acid.

    PubMed

    Griffith, Elizabeth C; Carpenter, Barry K; Shoemaker, Richard K; Vaida, Veronica

    2013-07-16

    The study of organic chemistry in atmospheric aerosols and cloud formation is of interest in predictions of air quality and climate change. It is now known that aqueous phase chemistry is important in the formation of secondary organic aerosols. Here, the photoreactivity of pyruvic acid (PA; CH3COCOOH) is investigated in aqueous environments characteristic of atmospheric aerosols. PA is currently used as a proxy for α-dicarbonyls in atmospheric models and is abundant in both the gas phase and the aqueous phase (atmospheric aerosols, fog, and clouds) in the atmosphere. The photoreactivity of PA in these phases, however, is very different, thus prompting the need for a mechanistic understanding of its reactivity in different environments. Although the decarboxylation of aqueous phase PA through UV excitation has been studied for many years, its mechanism and products remain controversial. In this work, photolysis of aqueous PA is shown to produce acetoin (CH3CHOHCOCH3), lactic acid (CH3CHOHCOOH), acetic acid (CH3COOH), and oligomers, illustrating the progression from a three-carbon molecule to four-carbon and even six-carbon molecules through direct photolysis. These products are detected using vibrational and electronic spectroscopy, NMR, and MS, and a reaction mechanism is presented accounting for all products detected. The relevance of sunlight-initiated PA chemistry in aqueous environments is then discussed in the context of processes occurring on atmospheric aerosols.

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

    NASA Astrophysics Data System (ADS)

    Beaver, M. R.; Elrod, M. J.; Garland, R. M.; Tolbert, M. A.

    2006-08-01

    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.

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

    NASA Astrophysics Data System (ADS)

    Beaver, M. R.; Elrod, M. J.; Garland, R. M.; Tolbert, M. A.

    2006-03-01

    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 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.

  20. Sulfuric acid spills in marine accidents

    SciTech Connect

    Tang, I N; Wong, W T; Munkelwitz, H R; Flessner, M F

    1980-07-01

    Concentrated sulfuric acid and oleum are among the most potentially hazardous chemicals routinely transported in bulk quantities on US and international waterways. Conceivably, during a marine mishap, tons of sulfuric acid could be abruptly released into the water, and the consequences of such a spill could be detrimental to man and the environment. Several acid spill scenarios are briefly described, and the results from laboratory experiments designed to simulate two different types of acid spill accidents are reported. It is shown that the convective mixing of concentrated sulfuric acid with water can adequately be described by a mathematical model which takes into account the variation of the buoyancy force arising from changes in acid concentration and released heat of dilution. A value of 0.21 is determined to be the entrainment parameter for the mixing of sulfuric acid with water. For oleum spills in which acid aerosol formation is a potential safety hazard, a conservative estimate of less than one-tenth of a percent is obtained for the amount of airborne acid under most accident conditions. The fraction of airborne acid, however, decreases very rapidly with increasing release depth below water surfaces. The acid aerosols exhibit a well-defined log-normal particle-size distribution with peak diameter varying from 0.1 to 0.6 ..mu..m (at 70% R.H.) depending upon release depth. This is well within the respirable particle size range.

  1. Methane activation and oxidation in sulfuric acid.

    PubMed

    Goeppert, Alain; Dinér, Peter; Ahlberg, Per; Sommer, Jean

    2002-07-15

    The H/D exchange observed when methane is contacted with D(2)SO(4) at 270-330 degrees C shows that the alkane behaves as a sigma base and undergoes rapid and reversible protonation at this temperature. DFT studies of the hydrogen exchange between a monomer and a dimer of sulfuric acid and methane show that the transition states involved in the exchange are bifunctional, that is one hydrogen atom is transferred from a hydroxy group in sulfuric acid to methane, while one hydrogen atom is abstracted from methane by a non-hydroxy oxygen atom in sulfuric acid. All the transition states include a CH(5) moiety, which shows similarities to the methanium ion CH(5) (+). The calculated potential activation energy of the hydrogen exchange for the monomer is 174 kJ mol(-1), which is close to the experimental value (176 kJ mol(-1)). Solvation of the monomer and the transition state of the monomer with an extra sulfuric acid molecule, decrease the potential activation energy by 6 kJ mol(-1). The acid-base process is in competition, however, with an oxidative process involving methane and sulfuric acid which leads to CO(2), SO(2), and water, and thus to a decrease of acidity and loss of reactivity of the medium.

  2. [Investigation on formation mechanism of secologanic acid sulfonates in sulfur-fumigated buds of Lonicera japonica].

    PubMed

    Guo, Ai-Li; Gao, Hui-Min; Chen, Liang-Mian; Zhang, Qi-Wei; Wang, Zhi-Min

    2014-05-01

    To investigate formation mechanism of secologanic acid sulfonates in sulfur-fumigated buds of Lonicera japonica, secologanic acid was enriched and purified from the sun-dried buds of L. japonica by various column chromatography on macroporus resin HPD-100, silica gel and ODS. The stimulation experiments of sulfur-fumigation process were carried out using secologanic acid reacted with SO2 in the aqueous solution. The reaction mechanism could be involved in the esterification or addition reaction. The present investigation provides substantial evidences for interpreting formation pathway of secologanic acid sulfonates in sulfur-fumigated buds of L. japonica.

  3. Sulfuric acid in the Venus clouds.

    NASA Technical Reports Server (NTRS)

    Sill, G. T.

    1972-01-01

    The extremely dry nature of the Venus upper atmosphere appears to demand the presence of an efficient desiccating agent as the chief constituent of the clouds of Venus. On the basis of polarization measures it is to be expected that this substance is present as spherical droplets, 1 to 2 microns in diameter, with a refractive index n of 1.46 plus or minus 0.02 at 3500A in the observed region of the atmosphere, with T about equal to 235 K. This substance must have ultraviolet, visible, and infrared reflection properties not inconsistent with the observed spectrum of Venus. Sulfuric acid, of about 86% by weight composition, roughly fulfills the first of these properties. The visible and ultraviolet transmission features of a thin layer of elemental bromine and hydrobromic acid dissolved in sulfuric acid somewhat resemble the Venus spectrum, up to 14 microns. The chemical process postulated for forming sulfuric acid involves the oxidation of sulfur and its compounds to sulfuric acid through the agency of elemental bromine produced by the photolytic decomposition of hydrogen bromide.

  4. Sulfuric acid in the Venus clouds.

    NASA Technical Reports Server (NTRS)

    Sill, G. T.

    1972-01-01

    The extremely dry nature of the Venus upper atmosphere appears to demand the presence of an efficient desiccating agent as the chief constituent of the clouds of Venus. On the basis of polarization measures it is to be expected that this substance is present as spherical droplets, 1 to 2 microns in diameter, with a refractive index n of 1.46 plus or minus 0.02 at 3500A in the observed region of the atmosphere, with T about equal to 235 K. This substance must have ultraviolet, visible, and infrared reflection properties not inconsistent with the observed spectrum of Venus. Sulfuric acid, of about 86% by weight composition, roughly fulfills the first of these properties. The visible and ultraviolet transmission features of a thin layer of elemental bromine and hydrobromic acid dissolved in sulfuric acid somewhat resemble the Venus spectrum, up to 14 microns. The chemical process postulated for forming sulfuric acid involves the oxidation of sulfur and its compounds to sulfuric acid through the agency of elemental bromine produced by the photolytic decomposition of hydrogen bromide.

  5. Growth of nitric acid hydrates on thin sulfuric acid films

    NASA Technical Reports Server (NTRS)

    Iraci, Laura T.; Middlebrook, Ann M.; Wilson, Margaret A.; Tolbert, Margaret A.

    1994-01-01

    Type I polar stratospheric clouds (PSCs) are thought to nucleate and grow on stratospheric sulfate aerosols (SSAs). To model this system, thin sulfuric acid films were exposed to water and nitric acid vapors (1-3 x 10(exp -4) Torr H2O and 1-2.5 x 10(exp -6) Torr HNO3) and subjected to cooling and heating cycles. Fourier Transform Infrared (FTIR) spectroscopy was used to probe the phase of the sulfuric acid and to identify the HNO3/H2O films that condensed. Nitric acid trihydrate (NAT) was observed to grow on crystalline sulfuric acid tetrahydrate (SAT) films. NAT also condensed in/on supercooled H2SO4 films without causing crystallization of the sulfuric acid. This growth is consistent with NAT nucleation from ternary solutions as the first step in PSC formation.

  6. Sulfur

    USGS Publications Warehouse

    Apodaca, L.E.

    2012-01-01

    In 2011, elemental sulfur and the byproduct sulfuric acid were produced at 109 operations in 29 states and the U.S. Virgin Islands. Total shipments were valued at about $1.6 billion. Elemental sulfur production was 8.2 Mt (9 million st); Louisiana and Texas accounted for about 53 percent of domestic production.

  7. Comparative uptake of sulfur in sulfur dioxide and acid rain by corn (Zea mays L. )

    SciTech Connect

    Simon, J.E.

    1984-01-01

    This study has compared and evaluated the absorption and accumulation of sulfur from the two major forms of sulfur pollution (sulfur dioxide and sulfur containing acid rain), by seedlings of corn (Zea mays L.). Plants were exposed to matched treatments containing equivalent ..mu..moles S/treatment in sulfur dioxide or simulated acid rain containing sulfuric acid. Pollution levels were chosen to represent low, medium and high ambient pollutant concentrations (0.13, 1.3 and 130.0 ..mu..moles S/treatment). The uptake and distribution of sulfur by plants was followed by using radioactively labelled sulfur (35-S) in both pollutants. Plants were exposed to the pollutants via a single injection of sulfur dioxide or by rainfall simulators with acid rain treatments. From the sulfur dioxide concentrations evaluated (0.67; 1.00; 2.60; 6.70; and 16 ppm), maximum absorption occurred at the highest concentration while sulfur was more efficiently absorbed at lower concentrations. Absorption of sulfur by plants exposed to acid rain (pH 5.4; 4.4; 3.4; and 2.6) was higher with high sulfur/low pH treatments. pH per se, was not responsible for increased sulfur absorption at low pH treatments. Of the total sulfur associated with the plant following exposure to sulfur dioxide and acid rain, 55% and 97%, respectively was not absorbed, and could be released after one minute of a foliar wash. At each equivalent concentration of sulfur, corn seedlings absorbed significantly greater amounts of sulfur from sulfur dioxide than from acid rain.

  8. Sulfur Reduction in Acid Rock Drainage Environments.

    PubMed

    Florentino, Anna P; Weijma, Jan; Stams, Alfons J M; Sánchez-Andrea, Irene

    2015-10-06

    Microbiological suitability of acidophilic sulfur reduction for metal recovery was explored by enriching sulfur reducers from acidic sediments at low pH (from 2 to 5) with hydrogen, glycerol, methanol and acetate as electron donors at 30 °C. The highest levels of sulfide in the enrichments were detected at pH 3 with hydrogen and pH 4 with acetate. Cloning and sequencing of the 16S rRNA gene showed dominance of the deltaproteobacterial sulfur-reducing genus Desulfurella in all the enrichments and subsequently an acidophilic strain (TR1) was isolated. Strain TR1 grew at a broad range of pH (3-7) and temperature (20-50 °C) and showed good metal tolerance (Pb(2+), Zn(2+), Cu(2+), Ni(2+)), especially for Ni(2+) and Pb(2+), with maximal tolerated concentrations of 0.09 and 0.03 mM, respectively. Different sources of sulfur were tested in the enrichments, from which biosulfur showed fastest growth (doubling time of 1.9 days), followed by colloidal, chemical and sublimated sulfur (doubling times of 2.2, 2.5, and 3.6 days, respectively). Strain TR1's physiological traits make it a good candidate to cope with low pH and high metal concentration in biotechnological processes for treatment of metal-laden acidic streams at low and moderately high temperature.

  9. Intestinal metabolism of sulfur amino acids

    USDA-ARS?s Scientific Manuscript database

    The gastrointestinal tract (GIT) is a metabolically significant site of sulfur amino acid (SAA) metabolism in the body and metabolizes approx. 20% of the dietary methionine intake that is mainly transmethylated to homocysteine and transsulfurated to cysteine. The GIT accounts for approx. 25% of the ...

  10. Charles H. Winston and Confederate Sulfuric Acid.

    ERIC Educational Resources Information Center

    Riethmiller, Steven

    1995-01-01

    Describes the invention and use of a sulfuric acid chamber by Charles Henry Winston during the Civil War. This invention helped supply munitions for the South. Winston, who was President of the Richmond Female Institute in Virginia, constructed the chamber at his farm and was granted a patent by the Confederate Patent Office in 1863. (PVD)

  11. Charles H. Winston and Confederate Sulfuric Acid.

    ERIC Educational Resources Information Center

    Riethmiller, Steven

    1995-01-01

    Describes the invention and use of a sulfuric acid chamber by Charles Henry Winston during the Civil War. This invention helped supply munitions for the South. Winston, who was President of the Richmond Female Institute in Virginia, constructed the chamber at his farm and was granted a patent by the Confederate Patent Office in 1863. (PVD)

  12. Heterogeneous Interaction of Peroxyacetyl Nitrate on Liquid Sulfuric Acid

    NASA Technical Reports Server (NTRS)

    Zhang, Renyi; Leu, Ming-Taun

    1996-01-01

    The uptake of peroxyacetyl nitrate (PAN) on liquid sulfuric acid surfaces has been investigated using a fast-flow reactor coupled to a chemical ionization mass spectrometer. PAN was observed to be reversibly adsorbed on sulfuric acid.

  13. Uptake and Dissolution of Gaseous Ethanol in Sulfuric Acid

    NASA Technical Reports Server (NTRS)

    Michelsen, Rebecca R.; Staton, Sarah J. R.; Iraci, Laura T.

    2006-01-01

    The solubility of gas-phase ethanol (ethyl alcohol, CH3CH2OH, EtOH) in aqueous sulfuric acid solutions was measured in a Knudsen cell reactor over ranges of temperature (209-237 K) and acid composition (39-76 wt % H2SO4). Ethanol is very soluble under these conditions: effective Henry's law coefficients, H*, range from 4 x 10(exp 4) M/atm in the 227 K, 39 wt % acid to greater than 10(exp 7) M/atm in the 76 wt % acid. In 76 wt % sulfuric acid, ethanol solubility exceeds that which can be precisely determined using the Knudsen cell technique but falls in the range of 10(exp 7)-10(exp 10) M/atm. The equilibrium concentration of ethanol in upper tropospheric/lower stratospheric (UT/LS) sulfate particles is calculated from these measurements and compared to other small oxygenated organic compounds. Even if ethanol is a minor component in the gas phase, it may be a major constituent of the organic fraction in the particle phase. No evidence for the formation of ethyl hydrogen sulfate was found under our experimental conditions. While the protonation of ethanol does augment solubility at higher acidity, the primary reason H* increases with acidity is an increase in the solubility of molecular (i.e., neutral) ethanol.

  14. Uptake and Dissolution of Gaseous Ethanol in Sulfuric Acid

    NASA Technical Reports Server (NTRS)

    Michelsen, Rebecca R.; Staton, Sarah J. R.; Iraci, Laura T.

    2006-01-01

    The solubility of gas-phase ethanol (ethyl alcohol, CH3CH2OH, EtOH) in aqueous sulfuric acid solutions was measured in a Knudsen cell reactor over ranges of temperature (209-237 K) and acid composition (39-76 wt % H2SO4). Ethanol is very soluble under these conditions: effective Henry's law coefficients, H*, range from 4 x 10(exp 4) M/atm in the 227 K, 39 wt % acid to greater than 10(exp 7) M/atm in the 76 wt % acid. In 76 wt % sulfuric acid, ethanol solubility exceeds that which can be precisely determined using the Knudsen cell technique but falls in the range of 10(exp 7)-10(exp 10) M/atm. The equilibrium concentration of ethanol in upper tropospheric/lower stratospheric (UT/LS) sulfate particles is calculated from these measurements and compared to other small oxygenated organic compounds. Even if ethanol is a minor component in the gas phase, it may be a major constituent of the organic fraction in the particle phase. No evidence for the formation of ethyl hydrogen sulfate was found under our experimental conditions. While the protonation of ethanol does augment solubility at higher acidity, the primary reason H* increases with acidity is an increase in the solubility of molecular (i.e., neutral) ethanol.

  15. Boric/sulfuric acid anodize - Alternative to chromic acid anodize

    NASA Astrophysics Data System (ADS)

    Koop, Rodney; Moji, Yukimori

    1992-04-01

    The suitability of boric acid/sulfuric acid anodizing (BSAA) solution as a more environmentally acceptable replacement of the chromic acid anodizing (CAA) solution was investigated. Results include data on the BSAA process optimization, the corrosion protection performance, and the compatibility with aircraft finishing. It is shown that the BSSA implementation as a substitude for CAA was successful.

  16. A comparison of chromic acid and sulfuric acid anodizing

    NASA Technical Reports Server (NTRS)

    Danford, M. D.

    1992-01-01

    Because of federal and state mandates restricting the use of hexavalent chromium, it was deemed worthwhile to compare the corrosion protection afforded 2219-T87 aluminum alloy by both Type I chromic acid and Type II sulfuric acid anodizing per MIL-A-8625. Corrosion measurements were made on large, flat 2219-T87 aluminum alloy sheet material with an area of 1 cm(exp 2) exposed to a corrosive medium of 3.5-percent sodium chloride at pH 5.5. Both ac electrochemical impedance spectroscopy and the dc polarization resistance techniques were employed. The results clearly indicate that the corrosion protection obtained by Type II sulfuric acid anodizing is superior, and no problems should result by substituting Type II sulfuric acid anodizing for Type I chromic acid anodizing.

  17. Exposure to sulfuric acid in zinc production.

    PubMed

    Bråtveit, Magne; Haaland, Inger Margrethe; Moen, Bente E; Målsnes, Agnar

    2004-03-01

    This study characterized workers' exposure to sulfuric acid in two cell houses of a zinc production plant. We also aimed at estimating previous exposure to sulfuric acid by simulating the process conditions from before 1975 to produce exposure data for an epidemiological study on cancer in this industry. Further, we compared different sampling methods for aerosols in the cell houses. Personal sampling with a 37 mm Millipore cassette showed that the geometric means of the exposure levels for the workers in the two cell houses were 0.07 mg/m3 (range 0.01-0.48 mg/m3) and 0.04 mg/m3 (range 0.01-0.15 mg/m3). Norway's newly revised limit value of 0.1 mg/m3 was exceeded in 39.0 and 12.9% of the samples in the two cell houses. After the foam layer was removed from the electrolyte surface to simulate the production process from before 1975, the concentration of sulfuric acid increased from 0.11 to 6.04 mg/m3 in stationary measurement by the Millipore sampler. Stationary sampling showed that the Millipore sampler and the inhalable fraction of the Respicon impactor underestimated the sulfuric acid concentration by factors of 1.5 and 2.1 compared with the Institute of Occupational Medicine (IOM) sampler. Sampling with the Respicon impactor showed that the respirable, tracheobronchial and extrathoracic fractions constituted 3.0, 18.7 and 71.7% of the inhalable sulfuric acid aerosol, respectively. Today's exposure levels are lower than those reported to be associated with an increased prevalence of laryngeal cancer in other industries, but the levels prior to 1975 seem to have been much higher. By mass, most of the inhalable aerosol was in the size fractions considered to be highly relevant for the effects of sulfuric acid on the respiratory system. The risk of cancer among the cell house workers should be investigated in an epidemiological study.

  18. Uptake of Small Organic Compounds by Sulfuric Acid Aerosols: Dissolution and Reaction

    NASA Technical Reports Server (NTRS)

    Iraci, L. T.; Michelsen, R. R.; Ashbourn, S. F. M.; Staton, S. J. R.

    2003-01-01

    To assess the role of oxygenated volatile organic compounds in the upper troposphere and lower stratosphere, the interactions of a series of small organic compounds with low-temperature aqueous sulfuric acid will be evaluated. The total amount of organic material which may be taken up from the gas phase by dissolution, surface layer formation, and reaction during the particle lifetime will be quantified. Our current results for acetaldehyde uptake on 40 - 80 wt% sulfuric acid solutions will be compared to those of methanol, formaldehyde, and acetone to investigate the relationships between chemical functionality and heterogeneous activity. Where possible, equilibrium uptake will be ascribed to component pathways (hydration, protonation, etc.) to facilitate evaluation of other species not yet studied in low temperature aqueous sulfuric acid.

  19. Uptake of Small Organic Compounds by Sulfuric Acid Aerosols: Dissolution and Reaction

    NASA Technical Reports Server (NTRS)

    Iraci, L. T.; Michelsen, R. R.; Ashbourn, S. F. M.; Staton, S. J. R.

    2003-01-01

    To assess the role of oxygenated volatile organic compounds in the upper troposphere and lower stratosphere, the interactions of a series of small organic compounds with low-temperature aqueous sulfuric acid will be evaluated. The total amount of organic material which may be taken up from the gas phase by dissolution, surface layer formation, and reaction during the particle lifetime will be quantified. Our current results for acetaldehyde uptake on 40 - 80 wt% sulfuric acid solutions will be compared to those of methanol, formaldehyde, and acetone to investigate the relationships between chemical functionality and heterogeneous activity. Where possible, equilibrium uptake will be ascribed to component pathways (hydration, protonation, etc.) to facilitate evaluation of other species not yet studied in low temperature aqueous sulfuric acid.

  20. Np(V) reduction by humic acid: contribution of reduced sulfur functionalities to the redox behavior of humic acid.

    PubMed

    Schmeide, K; Sachs, S; Bernhard, G

    2012-03-01

    The role of sulfur-containing functional groups in humic acids for the Np(V) reduction in aqueous solution has been studied with the objective to specify individual processes contributing to the overall redox activity of humic substances. For this, humic acid model substances type M1-S containing different amounts of sulfur (1.9, 3.9, 6.9 wt.%) were applied. The sulfur functionalities in these humic acids are dominated by reduced-sulfur species, such as thiols, dialkylsulfides and/or disulfides. The Np(V) reduction behavior of these humic acids has been studied in comparison to that of the sulfur-free humic acid type M1 at pH 5.0, 7.0 and 9.0 under anaerobic conditions by means of batch experiments. For Np redox speciation in solution, solvent extraction and ultrafiltration were applied. In addition, redox potentials of the sample solutions were monitored. At pH 5.0, both rate and extent of Np(V) to Np(IV) reduction were found to increase with increasing sulfur content of the humic acids. At pH 7.0 and 9.0, sulfur functional groups had only a slight influence on the reduction behavior of humic acid toward Np(V). Thus, in addition to quinoid moieties and non-quinoid phenolic OH groups, generally acknowledged as main redox-active sites in humic substances, sulfur functional groups have been identified as further redox-active moieties of humic substances being active especially in the slightly acidic pH range as shown for Np(V). Due to the low sulfur content of up to 2 wt.% in natural humic substances, their contribution to the total reducing capacity is smaller than that of the other redox-active functional groups. Copyright © 2012 Elsevier B.V. All rights reserved.

  1. Electrochemical behavior of silver in concentrated sulfuric acid solutions

    SciTech Connect

    Gordeeva, T.V.; Krasikov, B.S.

    1985-04-20

    The authors use stationary and rotating silver disk electrodes for studying the electrochemical behavior of silver in sulfuric acid solutions. Charts present data gathered on potential of the silver electrode in absence of current in sulfate solutions; on calculated curves and experimental points for anodic dissolution of a rotating silver disk electrode in sulfuric acid solution; and on influence of the average activity of sulfuric acid on the equilibrium potential of the silver electrode. The authors conclude that the rates of electrodeposition and dissolution of silver in concentrated sulfuric acid solutions, whether containing silver ions or not, are determined only by the rates of diffusion of silver ions and their sulfate complexes.

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

    PubMed

    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.

  3. Aqueous leaching on high sulfur sub-bituminous coals, in Assam, India

    SciTech Connect

    Bimala P. Baruah; Binoy K. Saikia; Prabhat Kotoky; P. Gangadhar Rao

    2006-08-15

    Aqueous leaching of high sulfur sub-bituminous coals from Ledo and Baragolai collieries of Makum coal fields, in Assam, India, has been investigated with respect to time at different temperatures. Leaching at 25{sup o}C up to 120 h showed that the physicochemical characteristics viz., conductivity, acidity, TDS, and SO{sub 4}-2 ions, increase with the increase in time of leaching. The generation of highly acidic leachates at 1-1.5 h (pH 2.5) and 2 h (pH 3.1) for Ledo and Baragolai coals was observed, respectively. However, it remains stable up to 120 h. The concentration of major, minor, and trace elements and their mobility along with the loss of pyritic sulfur or depyritization were also reported. The release of metals (Fe, Mg, Bi, Al, V, Cu, Cd, Ni, Pb, and Mn) above the regulatory levels during leaching was evidenced. Depyritization was found to be 79.8, 82.9, 84.7, and 89.7% for Ledo and 70.49, 73.77, 75.41, and 77.05% for Baragolai coal at 15, 25, 35, and 45 {sup o}C, respectively. A pseudo-first-order kinetic relationship with activation energies (E) of 8.1477 and 5.2378 kJ mol{sup -1} with frequency factors (A) of 8.8405 x 10{sup -4} and 2.6494 x 10{sup -4} dm{sup 3} mol{sup -1} s{sup -1} was attributed to aqueous oxidation of pyrites in Ledo and Baragolai coals, respectively. The X-ray diffraction analysis and Fourier transform infrared spectroscopy patterns indicate the presence of illite, {alpha}-quartz, hematite, chlorite, rutile, calcite, and albite as mineral phases. This investigation justifies the formation of acid mine drainage by weathering of pyrites from coal during the mining of high sulfur Makum coal fields, in Assam, India, and demonstrates one of the possible routes for its formation. 39 refs., 3 figs. 9 tabs.

  4. Solubility of HCL in sulfuric acid at stratospheric temperatures

    NASA Technical Reports Server (NTRS)

    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.

  5. Solubility of HCL in sulfuric acid at stratospheric temperatures

    NASA Astrophysics Data System (ADS)

    Williams, Leah R.; Golden, David M.

    1993-10-01

    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.

  6. A novel non-aqueous aluminum sulfur battery

    NASA Astrophysics Data System (ADS)

    Cohn, Gil; Ma, Lin; Archer, Lynden A.

    2015-06-01

    An aluminum-sulfur battery comprised of a composite sulfur cathode, aluminum anode and an ionic liquid electrolyte of AlCl3/1-ethyl-3-methylimidazolium chloride is described. The electrochemical reduction of elemental sulfur has been studied in different molar ratios of the electrolyte, and aluminum tetrachloride ions have been identified at the electroactive ionic species. The Al/S battery exhibits a discharge voltage plateau of 1.1-1.2 V, with extremely high charge storage capacity of more than 1500 mAh g-1, relative to the mass of sulfur in the cathode. The energy density of the Al/S cell is estimated to be 1700 Wh kg-1 sulfur, which is competitive with the most attractive battery chemistries targeted for high-energy electrochemical storage. Characterization by means of SEM, XRD and XPS of the battery components reveal complete dissolution of sulfur-based discharge products to the electrolyte. The low cost, natural abundance and high volumetric energy density of both anode and cathode materials define a research path for new materials and cell designs for next-generation Al/S battery systems.

  7. Atmospheric sulfur as related to acid precipitation and soil fertility

    SciTech Connect

    Suarez, E.L.; Jones, U.S.

    1982-09-01

    Conductivity, pH, and ionic components were determined in the rainfall and particulate matter at Clemson, S.C., Experiment, Ga., and Franklin, N.C., using a wet/dry collector. Sulfur in the air was collected at Clemson on a 30-d interval in a standard lead peroxide sampler. Soil samples were taken from 15 locations in South Carolina and analyzed for sulfur. It was observed that the average loading concentration of anions in rainwater increased during the spring-summer months and decreased during the fall-winter months. Sulfuric and nitric acids were found to be the major components of acid rainfall. Rainfall and air deposition contributed approximately 10.7 and 1.8 kg/ha of sulfur per year, respectively, at Clemson. Atmospheric deposition from the particulate matter contributed an estimated 3.0 kg/ha of sulfur during the year. Increases in corn grain and silage yields were obtained with the application of 18 kg/ha of sulfur at Darlington, S.C. A relationship between applied sulfur and crop response for the other crops considered could not be established. A need for reevaluating the findings and recommendations for sulfur fertilizers was apparent because of the contribution of atmospheric-deposited sulfur to the soil and plant sulfur supply.

  8. The x-ray absorption spectroscopy model of solvation about sulfur in aqueous L-cysteine.

    PubMed

    Sarangi, Ritimukta; Frank, Patrick; Benfatto, Maurizio; Morante, Silvia; Minicozzi, Velia; Hedman, Britt; Hodgson, Keith O

    2012-11-28

    The environment of sulfur in dissolved aqueous L-cysteine has been examined using K-edge x-ray absorption spectroscopy (XAS), extended continuum multiple scattering (ECMS) theory, and density functional theory (DFT). For the first time, bound-state and continuum transitions representing the entire XAS spectrum of L-cysteine sulfur are accurately reproduced by theory. Sulfur K-edge absorption features at 2473.3 eV and 2474.2 eV represent transitions to LUMOs that are mixtures of S-C and S-H σ∗ orbitals significantly delocalized over the entire L-cysteine molecule. Continuum features at 2479, 2489, and 2530 eV were successfully reproduced using extended continuum theory. The full L-cysteine sulfur K-edge XAS spectrum could not be reproduced without addition of a water-sulfur hydrogen bond. Density functional theory analysis shows that although the Cys(H)S⋯H-OH hydrogen bond is weak (∼2 kcal) the atomic charge on sulfur is significantly affected by this water. MXAN analysis of hydrogen-bonding structures for L-cysteine and water yielded a best fit model featuring a tandem of two water molecules, 2.9 Å and 5.8 Å from sulfur. The model included a S(cys)⋯H-O(w1)H hydrogen-bond of 2.19 Å and of 2.16 Å for H(2)O(w1)⋯H-O(w2)H. One hydrogen-bonding water-sulfur interaction alone was insufficient to fully describe the continuum XAS spectrum. However, density functional theoretical results are convincing that the water-sulfur interaction is weak and should be only transient in water solution. The durable water-sulfur hydrogen bond in aqueous L-cysteine reported here therefore represents a break with theoretical studies indicating its absence. Reconciling the apparent disparity between theory and result remains the continuing challenge.

  9. Nitric acid uptake by sulfuric acid solutions under stratospheric conditions - Determination of Henry's Law solubility

    NASA Technical Reports Server (NTRS)

    Reihs, Christa M.; Golden, David M.; Tolbert, Margaret A.

    1990-01-01

    The uptake of nitric acid by sulfuric acid solutions representative of stratospheric particulate at low temperatures was measured to determine the solubility of nitric acid in sulfuric acid solutions as a function of H2SO4 concentration and solution temperature. Solubilities are reported for sulfuric acid solutions ranging from 58 to 87 wt pct H2SO4 over a temperature range from 188 to 240 K, showing that, in general, the solubility of nitric acid increases with decreasing sulfuric acid concentration and with decreasing temperature. The measured solubilities indicate that nitric acid in the global stratosphere will be found predominantly in the gas phase.

  10. Aqueous process for recovering sulfur from hydrogen sulfide-bearing gas

    SciTech Connect

    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.

  11. Hydrolysis of Sulfur Dioxide in Small Clusters of Sulfuric Acid: Mechanistic and Kinetic Study.

    PubMed

    Liu, Jingjing; Fang, Sheng; Wang, Zhixiu; Yi, Wencai; Tao, Fu-Ming; Liu, Jing-Yao

    2015-11-17

    The deposition and hydrolysis reaction of SO2 + H2O in small clusters of sulfuric acid and water are studied by theoretical calculations of the molecular clusters SO2-(H2SO4)n-(H2O)m (m = 1,2; n = 1,2). Sulfuric acid exhibits a dramatic catalytic effect on the hydrolysis reaction of SO2 as it lowers the energy barrier by over 20 kcal/mol. The reaction with monohydrated sulfuric acid (SO2 + H2O + H2SO4 - H2O) has the lowest energy barrier of 3.83 kcal/mol, in which the cluster H2SO4-(H2O)2 forms initially at the entrance channel. The energy barriers for the three hydrolysis reactions are in the order SO2 + (H2SO4)-H2O > SO2 + (H2SO4)2-H2O > SO2 + H2SO4-H2O. Furthermore, sulfurous acid is more strongly bonded to the hydrated sulfuric acid (or dimer) clusters than the corresponding reactant (monohydrated SO2). Consequently, sulfuric acid promotes the hydrolysis of SO2 both kinetically and thermodynamically. Kinetics simulations have been performed to study the importance of these reactions in the reduction of atmospheric SO2. The results will give a new insight on how the pre-existing aerosols catalyze the hydrolysis of SO2, leading to the formation and growth of new particles.

  12. Sulfur and Hydrogen Isotope Anomalies in Meteorite Sulfonic Acids

    NASA Technical Reports Server (NTRS)

    Cooper, George W.; Thiemens, Mark H.; Jackson, Teresa L.; Chang, Sherwood

    1997-01-01

    Intramolecular carbon, hydrogen, and sulfur isotope ratios were measured on a homologous series of organic sulfonic acids discovered in the Murchison meteorite. Mass-independent sulfur isotope fractionations were observed along with high deuterium/hydrogen ratios. The deuterium enrichments indicate formation of the hydrocarbon portion of these compounds in a low-temperature environment that is consistent with that of interstellar clouds. Sulfur-33 enrichments observed in methanesulfonic acid could have resulted from gas-phase ultraviolet irradiation of a precursor, carbon disulfide. The source of the sulfonic acid precursors may have been the reactive interstellar molecule carbon monosulfide.

  13. Integrated boiler, superheater, and decomposer for sulfuric acid decomposition

    DOEpatents

    Moore, Robert; Pickard, Paul S.; Parma, Jr., Edward J.; Vernon, Milton E.; Gelbard, Fred; Lenard, Roger X.

    2010-01-12

    A method and apparatus, constructed of ceramics and other corrosion resistant materials, for decomposing sulfuric acid into sulfur dioxide, oxygen and water using an integrated boiler, superheater, and decomposer unit comprising a bayonet-type, dual-tube, counter-flow heat exchanger with a catalytic insert and a central baffle to increase recuperation efficiency.

  14. Temperature dependency of single-bubble sonoluminescence in sulfuric acid

    NASA Astrophysics Data System (ADS)

    Moshaii, A.; Tajik-Nezhad, S.; Faraji, M.

    2011-10-01

    Using a hydrochemical simulation, temperature dependency of single-bubble sonoluminescence (SL) in a concentrated solution of sulfuric acid has theoretically been studied. With calculating the phase diagrams of an SL bubble in the solution of 85% acid, maximum acquirable SL emissions at different ambient temperatures were calculated. The results show that the SL emission in sulfuric acid increases with increment in the ambient temperature. This temperature dependency is in opposition to that observed in experiments for SL in water. The difference originates from different instability mechanisms determining the ultimate phase parameters of SL in water and sulfuric acid. In water, due to the smallness of viscosity, the ultimate phase parameters are determined by the shape instability. However, in sulfuric acid the phase parameters are restricted by positional instability due to the largeness of the liquid viscosity.

  15. Focused electron beam induced etching of copper in sulfuric acid solutions

    NASA Astrophysics Data System (ADS)

    Boehme, Lindsay; Bresin, Matthew; Botman, Aurélien; Ranney, James; Hastings, J. Todd

    2015-12-01

    We show here that copper can be locally etched by an electron-beam induced reaction in a liquid. Aqueous sulfuric acid (H2SO4) is utilized as the etchant and all experiments are conducted in an environmental scanning electron microscope. The extent of etch increases with liquid thickness and dose, and etch resolution improves with H2SO4 concentration. This approach shows the feasibility of liquid phase etching for material selectivity and has the potential for circuit editing.

  16. Sulfuric acid aerosols in the atmospheres of the terrestrial planets

    NASA Astrophysics Data System (ADS)

    McGouldrick, Kevin; Toon, Owen B.; Grinspoon, David H.

    2011-08-01

    Clouds and hazes composed of sulfuric acid are observed to exist or postulated to have once existed on each of the terrestrial planets with atmospheres in our solar system. Venus today maintains a global cover of clouds composed of a sulfuric acid/water solution that extends in altitude from roughly 50 km to roughly 80 km. Terrestrial polar stratospheric clouds (PSCs) form on stratospheric sulfuric acid aerosols, and both PSCs and stratospheric aerosols play a critical role in the formation of the ozone hole. Stratospheric aerosols can modify the climate when they are enhanced following volcanic eruptions, and are a current focus for geoengineering studies. Rain is made more acidic by sulfuric acid originating from sulfur dioxide generated by industry on Earth. Analysis of the sulfur content of Martian rocks has led to the hypothesis that an early Martian atmosphere, rich in SO 2 and H 2O, could support a sulfur-infused hydrological cycle. Here we consider the plausibility of frozen sulfuric acid in the upper clouds of Venus, which could lead to lightning generation, with implications for observations by the European Space Agency's Venus Express and the Japan Aerospace Exploration Agency's Venus Climate Orbiter (also known as Akatsuki). We also present simulations of a sulfur-rich early Martian atmosphere. We find that about 40 cm/yr of precipitation having a pH of about 2.0 could fall in an early Martian atmosphere, assuming a surface temperature of 273 K, and SO 2 generation rates consistent with the formation of Tharsis. This modeled acid rain is a powerful sink for SO 2, quickly removing it and preventing it from having a significant greenhouse effect.

  17. Investigation of the thermal decomposition of sulfuric acid containing inorganic impurities

    SciTech Connect

    Kogtev, S.E.; Nikandrov, I.S.; Borisenko, A.S.; Peretrutov, A.A.

    1986-09-20

    Oleum is recovered by thermal decomposition of sulfuric acid wastes to sulfur dioxide with conversion of the sulfur dioxide to oleum. The organic substances in sulfuric acid wastes can affect the thermal-decomposition indexes of sulfuric acid wastes. They studied the effect of toluene, nitrotoluene, benzoic acid, and carbon on the yield of sulfur dioxide and also the possibility of reduction of acid vapors by products of pyrolysis and incomplete combustion of hydrocarbons. It is shown that the yield of sulfur dioxide in thermal decomposition of hydrocarbon-containing sulfuric acid wastes can be increased if the process assumes the nature of reductive decomposition.

  18. Quantitative Chromatographic Determination of Dissolved Elemental Sulfur in the Non-aqueous Electrolyte for Lithium-Sulfur Batteries

    DOE PAGES

    Zheng, Dong; Yang, Xiao-Qing; Zhang, Xuran; ...

    2014-12-02

    A fast and reliable analytical method is reported for the quantitative determination of dissolved elemental sulfur in non-aqueous electrolytes for Li-S batteries. By using high performance liquid chromatography with a UV detector, the solubility of S in 12 different pure solvents and in 22 different electrolytes was determined. It was found that the solubility of elemental sulfur is dependent on the Lewis basicity, the polarity of solvents and the salt concentration in the electrolytes. In addition, the S content in the electrolyte recovered from a discharged Li-S battery was successfully determined by the proposed HPLC/UV method. Thus, the feasibility ofmore » the method to the online analysis for a Li-S battery is demonstrated. Interestingly, the S was found super-saturated in the electrolyte recovered from a discharged Li-S cell.« less

  19. Quantitative Chromatographic Determination of Dissolved Elemental Sulfur in the Non-aqueous Electrolyte for Lithium-Sulfur Batteries

    SciTech Connect

    Zheng, Dong; Yang, Xiao-Qing; Zhang, Xuran; Li, Chao; McKinnon, Meaghan E.; Sadok, Rachel G.; Qu, Deyu; Yu, Xiqian; Lee, Hung-Sui; Qu, Deyang

    2014-12-02

    A fast and reliable analytical method is reported for the quantitative determination of dissolved elemental sulfur in non-aqueous electrolytes for Li-S batteries. By using high performance liquid chromatography with a UV detector, the solubility of S in 12 different pure solvents and in 22 different electrolytes was determined. It was found that the solubility of elemental sulfur is dependent on the Lewis basicity, the polarity of solvents and the salt concentration in the electrolytes. In addition, the S content in the electrolyte recovered from a discharged Li-S battery was successfully determined by the proposed HPLC/UV method. Thus, the feasibility of the method to the online analysis for a Li-S battery is demonstrated. Interestingly, the S was found super-saturated in the electrolyte recovered from a discharged Li-S cell.

  20. Protein and sulfur amino acid requirements of broiler breeder hens.

    PubMed

    Harms, R H; Wilson, H R

    1980-02-01

    Two experiments were conducted with Cobb color-sexed broiler breeder hens to determine their protein and sulfur amino acid requirement. A daily intake between 400 and 478 mg of methionine and between 722 and 839 mg of total sulfur amino acids was necessary for maximum egg production, the latter in a diet of 13.07% protein. Slightly lower levels supported maximum body weights. Hens laying at the highest rate consumed 23.4 g of protein per day.

  1. The corrosion protection of several aluminum alloys by chromic acid and sulfuric acid anodizing

    NASA Technical Reports Server (NTRS)

    Danford, M. D.

    1994-01-01

    The corrosion protection afforded 7075-T6, 7075-T3, 6061-T6, and 2024-T3 aluminum alloys by chromic acid and sulfuric acid anodizing was examined using electrochemical techniques. From these studies, it is concluded that sulfuric acid anodizing provides superior corrosion protection compared to chromic acid anodizing.

  2. Sulfuric Acid All Over Early Mars?

    NASA Astrophysics Data System (ADS)

    Wänke, H.; Boynton, W. V.; Brückner, J.; Dreibus, G.; Taylor, G. J.; Evans, L.; James, B.; Keller, J.; Kerry, K.; Starr, R.; GRS Team

    2005-03-01

    The Gamma-Ray Spectrometer of the 2001 Mars Odyssey Mission yielded concentration maps for several elements in the mid-latitude regions of Mars. The role of sulfur and other elements on the surface are discussed.

  3. Characterization of sulfur oxidizing bacteria related to biogenic sulfuric acid corrosion in sludge digesters.

    PubMed

    Huber, Bettina; Herzog, Bastian; Drewes, Jörg E; Koch, Konrad; Müller, Elisabeth

    2016-07-18

    Biogenic sulfuric acid (BSA) corrosion damages sewerage and wastewater treatment facilities but is not well investigated in sludge digesters. Sulfur/sulfide oxidizing bacteria (SOB) oxidize sulfur compounds to sulfuric acid, inducing BSA corrosion. To obtain more information on BSA corrosion in sludge digesters, microbial communities from six different, BSA-damaged, digesters were analyzed using culture dependent methods and subsequent polymerase chain reaction denaturing gradient gel electrophoresis (PCR-DGGE). BSA production was determined in laboratory scale systems with mixed and pure cultures, and in-situ with concrete specimens from the digester headspace and sludge zones. The SOB Acidithiobacillus thiooxidans, Thiomonas intermedia, and Thiomonas perometabolis were cultivated and compared to PCR-DGGE results, revealing the presence of additional acidophilic and neutrophilic SOB. Sulfate concentrations of 10-87 mmol/L after 6-21 days of incubation (final pH 1.0-2.0) in mixed cultures, and up to 433 mmol/L after 42 days (final pH <1.0) in pure A. thiooxidans cultures showed huge sulfuric acid production potentials. Additionally, elevated sulfate concentrations in the corroded concrete of the digester headspace in contrast to the concrete of the sludge zone indicated biological sulfur/sulfide oxidation. The presence of SOB and confirmation of their sulfuric acid production under laboratory conditions reveal that these organisms might contribute to BSA corrosion within sludge digesters. Elevated sulfate concentrations on the corroded concrete wall in the digester headspace (compared to the sludge zone) further indicate biological sulfur/sulfide oxidation in-situ. For the first time, SOB presence and activity is directly relatable to BSA corrosion in sludge digesters.

  4. Kinetics of the reduction of nitrite oil by sulfur dioxide in aqueous solution

    SciTech Connect

    Oblath, S.B.

    1981-08-01

    Reactions between nitrite and bisulfite ions in aqueous solutions were studied in which sulfur (IV) species are oxidized to sulfate ions and nitrogen (III) species are reduced. The dependence on temperature, ionic strength, acidity, and solution composition was determined. The actual products formed depend primarily on the concentration of bisulfite ion. The importance of these reactions to atmospheric aerosol formation processes is discussed. Under most conditions, the nitrogen product is hydroxylamine-N, N-disulfonate. Two processes are responsible for its formation. The first process (when the bisulfite concentration is greater than 0.1 M) is first order in nitrite ion, second order in bisulfite ion, and independent of acidity and temperature. It has a strong dependence on the ionic strength. The second and dominant process contributes to the product formation under all conditions and is first order in nitrite, bisulfite, and hydrogen ions. This process is independent of ionic strength and has a 12 kcal/mole activation energy. Both processes are insensitive to the choice of buffer. Whenever the hydrogen ion concentraion is nearly equal to that of the bisulfite ion, nitrous oxide is also a product. A mechanism is proposed to account for these results. It consists of a direct reaction of nitrite ion with metabisulfite ion to form hydroxylamine disulfonate, in parallel with a reaction between nitrous acid and bisulfite ion to form nitrososulfonic acid. This rapidly adds a bisulfite ion to form hydroxylamine disulfonate or undergoes hydrolysis to form nitrous oxide. The reaction between nitrite ion and hydroxylamine-N-sulfonate to produce nitrous oxide was also investigated. The reaction is first order in nitrite ion, second order in hydrogen ion, and between zero and first order in hydroxylamine monosulfonate, depending on the concentration.

  5. Sulfur amino acids in methionine-restricted rats: hyperhomocysteinemia.

    PubMed

    Elshorbagy, Amany K; Valdivia-Garcia, Maria; Refsum, Helga; Smith, A David; Mattocks, Dwight A L; Perrone, Carmen E

    2010-01-01

    Dietary methionine restriction in Fischer-344 rats favorably influences visceral fat mass, insulin sensitivity, metabolic parameters, and longevity. However, little is known about the effects of methionine restriction on serum methionine and its downstream sulfur amino acids. We investigated the serum sulfur amino acid profile of male Fischer-344 rats fed a methionine-restricted diet for 3 mo. Using tandem mass spectrometry, we observed marked reduction in serum concentrations of methionine, cystathionine, cysteine, and taurine in methionine-restricted rats compared with control (P<0.001) and a 2.5-fold elevation of homocysteine (P<0.001). This suggests that homocysteine trans-sulfuration may be inhibited by methionine restriction, and that some of the effects of methionine restriction may be mediated by changes in sulfur amino acids downstream of methionine. Published by Elsevier Inc.

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

    SciTech Connect

    Grompone, M.A.; Tancredi, N.A. )

    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.

  7. Tested Demonstrations: Color Oscillations in the Formic Acid-Nitric Acid-Sulfuric Acid System.

    ERIC Educational Resources Information Center

    Raw, C. J. G.; And Others

    1983-01-01

    Presented are procedures for demonstrating the production of color oscillations when nitric acid is added to a formic acid/concentrated sulfuric acid mixture. Because of safety considerations, "Super-8" home movie of the color changes was found to be satisfactory for demonstration purposes. (JN)

  8. Tested Demonstrations: Color Oscillations in the Formic Acid-Nitric Acid-Sulfuric Acid System.

    ERIC Educational Resources Information Center

    Raw, C. J. G.; And Others

    1983-01-01

    Presented are procedures for demonstrating the production of color oscillations when nitric acid is added to a formic acid/concentrated sulfuric acid mixture. Because of safety considerations, "Super-8" home movie of the color changes was found to be satisfactory for demonstration purposes. (JN)

  9. Sulfur isotope effects associated with oxidation of sulfide by O2 in aqueous solution

    NASA Technical Reports Server (NTRS)

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

    1988-01-01

    Normal sulfur isotope effects averaging epsilon = -5.2 +/- 1.4% (s.d.) were consistently observed for the oxidation of sulfide in aqueous solution. Reaction products were sulfate, thiosulfate and sulfite at pH 10.8-11 in distilled water; S0 was formed in two experiments with synthetic seawater at pH 8-9.5. Because the -5.2% normal isotope effect differs significantly from the previously measured +2% inverse effect associated with anaerobic oxidation of sulfide by photosynthetic bacteria, stable sulfur isotopic measurements are potentially useful for distinguishing aerobic vs. anaerobic sulfide oxidation in marine and freshwater sulfureta.

  10. Sulfur isotope effects associated with oxidation of sulfide by O2 in aqueous solution

    NASA Technical Reports Server (NTRS)

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

    1988-01-01

    Normal sulfur isotope effects averaging epsilon = -5.2 +/- 1.4% (s.d.) were consistently observed for the oxidation of sulfide in aqueous solution. Reaction products were sulfate, thiosulfate and sulfite at pH 10.8-11 in distilled water; S0 was formed in two experiments with synthetic seawater at pH 8-9.5. Because the -5.2% normal isotope effect differs significantly from the previously measured +2% inverse effect associated with anaerobic oxidation of sulfide by photosynthetic bacteria, stable sulfur isotopic measurements are potentially useful for distinguishing aerobic vs. anaerobic sulfide oxidation in marine and freshwater sulfureta.

  11. Unusual hydrophobic interactions in acidic aqueous solutions.

    PubMed

    Chen, Hanning; Xu, Jianqing; Voth, Gregory A

    2009-05-21

    Hydrophobic interaction, which is believed to be a primary driving force for many fundamental chemical and biological processes such as nanostructure self-assembly, micelle formation, and protein folding, is different in acidic aqueous solutions compared to salt solutions. In this study, the aggregation/dispersion behavior of nonpolar hydrophobic molecules in aqueous solutions with varying acid (HCl) concentrations is investigated using novel molecular dynamics simulations and compared to the hydrophobic behavior in corresponding salt (NaCl) solutions. The formation of unusual weakly bound hydrophobe-hydrated proton solvation structures is observed and can be attributed to the unique "amphiphilic" characteristic of hydrated protons. This molecular-level mechanism for the acid-enhanced dissolution of hydrophobic particles also provides a novel interpretation for the apparent anomaly of the hydronium cation in the Hofmeister series.

  12. 40 CFR 417.140 - Applicability; description of the neutralization of sulfuric acid esters and sulfonic acids...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... neutralization of sulfuric acid esters and sulfonic acids subcategory. 417.140 Section 417.140 Protection of... MANUFACTURING POINT SOURCE CATEGORY Neutralization of Sulfuric Acid Esters and Sulfonic Acids Subcategory § 417.140 Applicability; description of the neutralization of sulfuric acid esters and sulfonic acids...

  13. 40 CFR 417.140 - Applicability; description of the neutralization of sulfuric acid esters and sulfonic acids...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... neutralization of sulfuric acid esters and sulfonic acids subcategory. 417.140 Section 417.140 Protection of... MANUFACTURING POINT SOURCE CATEGORY Neutralization of Sulfuric Acid Esters and Sulfonic Acids Subcategory § 417.140 Applicability; description of the neutralization of sulfuric acid esters and sulfonic acids...

  14. 40 CFR 417.140 - Applicability; description of the neutralization of sulfuric acid esters and sulfonic acids...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... neutralization of sulfuric acid esters and sulfonic acids subcategory. 417.140 Section 417.140 Protection of... MANUFACTURING POINT SOURCE CATEGORY Neutralization of Sulfuric Acid Esters and Sulfonic Acids Subcategory § 417.140 Applicability; description of the neutralization of sulfuric acid esters and sulfonic acids...

  15. 40 CFR 417.140 - Applicability; description of the neutralization of sulfuric acid esters and sulfonic acids...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... neutralization of sulfuric acid esters and sulfonic acids subcategory. 417.140 Section 417.140 Protection of... MANUFACTURING POINT SOURCE CATEGORY Neutralization of Sulfuric Acid Esters and Sulfonic Acids Subcategory § 417.140 Applicability; description of the neutralization of sulfuric acid esters and sulfonic acids...

  16. 40 CFR 417.140 - Applicability; description of the neutralization of sulfuric acid esters and sulfonic acids...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... neutralization of sulfuric acid esters and sulfonic acids subcategory. 417.140 Section 417.140 Protection of... MANUFACTURING POINT SOURCE CATEGORY Neutralization of Sulfuric Acid Esters and Sulfonic Acids Subcategory § 417.140 Applicability; description of the neutralization of sulfuric acid esters and sulfonic acids...

  17. Commercial Alloys for Sulfuric Acid Vaporization in Thermochemical Hydrogen Cycles

    SciTech Connect

    Thomas M. Lillo; Karen M. Delezene-Briggs

    2005-10-01

    Most thermochemical cycles being considered for producing hydrogen include a processing stream in which dilute sulfuric acid is concentrated, vaporized and then decomposed over a catalyst. The sulfuric acid vaporizer is exposed to highly aggressive conditions. Liquid sulfuric acid will be present at a concentration of >96 wt% (>90 mol %) H2SO4 and temperatures exceeding 400oC [Brown, et. al, 2003]. The system will also be pressurized, 0.7-3.5 MPa, to keep the sulfuric acid in the liquid state at this temperature and acid concentration. These conditions far exceed those found in the commercial sulfuric acid generation, regeneration and handling industries. Exotic materials, e.g. ceramics, precious metals, clad materials, etc., have been proposed for this application [Wong, et. al., 2005]. However, development time, costs, reliability, safety concerns and/or certification issues plague such solutions and should be considered as relatively long-term, optimum solutions. A more cost-effective (and relatively near-term) solution would be to use commercially-available metallic alloys to demonstrate the cycle and study process variables. However, the corrosion behavior of commercial alloys in sulfuric acid is rarely characterized above the natural boiling point of concentrated sulfuric acid (~250oC at 1 atm). Therefore a screening study was undertaken to evaluate the suitability of various commercial alloys for concentration and vaporization of high-temperature sulfuric acid. Initially alloys were subjected to static corrosion tests in concentrated sulfuric acid (~95-97% H2SO4) at temperatures and exposure times up to 200oC and 480 hours, respectively. Alloys with a corrosion rate of less than 5 mm/year were then subjected to static corrosion tests at a pressure of 1.4 MPa and temperatures up to 375oC. Exposure times were shorter due to safety concerns and ranged from as short as 5 hours up to 144 hours. The materials evaluated included nickel-, iron- and cobalt

  18. Aqueous thermal degradation of gallic acid

    SciTech Connect

    Boles, J.S.; Crerar, D.A.; Grissom, G.; Key, T.C.

    1988-02-01

    Aqueous thermal degradation experiments show gallic acid, a naturally occurring aromatic carboxylic compound, decomposes rapidly at temperatures between 105/sup 0/ and 150/sup 0/C, with an activation energy of 22.9 or 27.8 kcal/mole, depending on pH of the starting solution. Pyrogallol is the primary product identified, indicating degradation via decarboxylation and a carbanion transition state. Relatively rapid degradation of vanillic, phthalic, ellagic and tannic acids has also been observed,suggesting that these and perhaps other aromatic acids could be short-lived in deep formation waters.

  19. Aqueous thermal degradation of gallic acid

    NASA Astrophysics Data System (ADS)

    Snow Boles, Jennifer; Crerar, David A.; Grissom, Grady; Key, Tonalee C.

    1988-02-01

    Aqueous thermal degradation experiments show gallic acid, a naturally occurring aromatic carboxylic compound, decomposes rapidly at temperatures between 105° and 150°C, with an activation energy of 22.9 or 27.8 kcal/ mole, depending on pH of the starting solution. Pyrogallol is the primary product identified, indicating degradation via decarboxylation and a carbanion transition state. Relatively rapid degradation of vanillic, phthalic, ellagic and tannic acids has also been observed, suggesting that these and perhaps other aromatic acids could be short-lived in deep formation waters.

  20. Oxaldihydroxamic acid as a new reagent for the fixation of atmospheric sulfur dioxide

    NASA Astrophysics Data System (ADS)

    Paul, Khana Rani; Gupta, V. K.

    In the present investigation 0.01 M aqueous oxaldihydroxamic acid has been used to stabilize the atmospheric sulfur dioxide. The collection efficiency of the reagent was found to be ~ 100% and the sulfite solution was stable for ⩾ 30 days at room temperature. The sulfite ion was estimated colorimetrically using acidified p-aminoazobenzene and formaldehyde. The pink coloured dye, λmax 505 nm, obeys Beer's law in the range of 0.1-1 ppm. The procedure has been optimized with respect to the acidity, time and reagent concentration. The method is simple, free from pH dependence and several commonly present air pollutants do not interfere.

  1. Connection of sulfuric acid to atmospheric nucleation in boreal forest.

    PubMed

    Nieminen, T; Manninen, H E; Sihto, S L; Yli-Juuti, T; Mauldin, R L; Petäjä, T; Riipinen, I; Kerminen, V M; Kulmala, M

    2009-07-01

    Gas to particle conversion in the boundary layer occurs worldwide. Sulfuric acid is considered to be one of the key components in these new particle formation events. In this study we explore the connection between measured sulfuric acid and observed formation rate of both charged 2 nm as well as neutral clusters in a boreal forest environment A very short time delay of the order of ten minutes between these two parameters was detected. On average the event days were clearly associated with higher sulfuric acid concentrations and lower condensation sink (CS) values than the nonevent days. Although there was not a clear sharp boundary between the nucleation and no-nucleation days in sulfuric acid-CS plane, at our measurement site a typical threshold concentration of 3.10(5) molecules cm(-3) of sulfuric acid was needed to initiate the new particle formation. Two proposed nucleation mechanisms were tested. Our results are somewhat more in favor of activation type nucleation than of kinetic type nucleation, even though our data set is too limited to omit either of these two mechanisms. In line with earlier studies, the atmospheric nucleation seems to start from sizes very close to 2 nm.

  2. Potential heat exchange fluids for use in sulfuric acid vaporizers

    NASA Technical Reports Server (NTRS)

    Lawson, D. D.; Petersen, G. R.

    1979-01-01

    A series of perhalocarbons are proposed as candidate heat exchange fluids for service in thermochemical cycles for hydrogen production that involve direct contact of the fluid with sulfuric acid and vaporization of the acid. The required chemical and physical criteria of the liquids are described and the results of some preliminary high temperature test data are presented.

  3. Molecular interaction of pinic acid with sulfuric acid: exploring the thermodynamic landscape of cluster growth.

    PubMed

    Elm, Jonas; Kurtén, Theo; Bilde, Merete; Mikkelsen, Kurt V

    2014-09-11

    We investigate the molecular interactions between the semivolatile α-pinene oxidation product pinic acid and sulfuric acid using computational methods. The stepwise Gibbs free energies of formation have been calculated utilizing the M06-2X functional, and the stability of the clusters is evaluated from the corresponding ΔG values. The first two additions of sulfuric acid to pinic acid are found to be favorable with ΔG values of -9.06 and -10.41 kcal/mol. Addition of a third sulfuric acid molecule is less favorable and leads to a structural rearrangement forming a bridged sulfuric acid-pinic acid cluster. The involvement of more than one pinic acid molecule in a single cluster is observed to lead to the formation of favorable (pinic acid)2(H2SO4) and (pinic acid)2(H2SO4)2 clusters. The identified most favorable growth paths starting from a single pinic acid molecule lead to closed structures without the further possibility for attachment of either sulfuric acid or pinic acid. This suggests that pinic acid cannot be a key species in the first steps in nucleation, but the favorable interactions between sulfuric acid and pinic acid imply that pinic acid can contribute to the subsequent growth of an existing nucleus by condensation.

  4. NIR spectroscopic properties of aqueous acids solutions.

    PubMed

    Omar, Ahmad Fairuz; Atan, Hanafi; Matjafri, Mohd Zubir

    2012-06-15

    Acid content is one of the important quality attributes in determining the maturity index of agricultural product, particularly fruits. Despite the fact that much research on the measurement of acidity in fruits through non-destructive spectroscopy analysis at NIR wavelengths between 700 to 1,000 nm has been conducted, the same response towards individual acids is not well known. This paper presents NIR spectroscopy analysis on aqueous citric, tartaric, malic and oxalic solutions through quantitative analysis by selecting a set of wavelengths that can best be used to measure the pH of the solutions. The aquaphotomics study of the acid solutions has generated R² above 0.9 for the measurement of all acids. The most important wavelengths for pH are located at 918-925 nm and 990-996 nm, while at 975 nm for water.

  5. High pressure sulfuric acid decomposition experiments for the sulfur-iodine thermochemical cycle.

    SciTech Connect

    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.

  6. Production of furfural from xylose at atmospheric pressure by dilute sulfuric acid and inorganic salts.

    PubMed

    Rong, Chunguang; Ding, Xuefeng; Zhu, Yanchao; Li, Ying; Wang, Lili; Qu, Yuning; Ma, Xiaoyu; Wang, Zichen

    2012-03-01

    In this paper, the dehydration of xylose to furfural was carried out under atmospheric pressure and at the boiling temperature of a biphasic mixture of toluene and an aqueous solution of xylose, with sulfuric acid as catalyst plus an inorganic salt (NaCl or FeCl(3)) as promoter. The best yield of furfural was 83% under the following conditions: 150 mL of toluene and 10 mL of aqueous solution of 10% xylose (w/w), 10% H(2)SO(4) (w/w), 2.4g NaCl , and heating for 5h. FeCl(3) as promoter was found to be more efficient than NaCl. The addition of DMSO to the aqueous phase in the absence of an inorganic salt was shown to improve the yield of furfural.

  7. Adsorption of ammonia by sulfuric acid treated zirconium hydroxide.

    PubMed

    Glover, T Grant; Peterson, Gregory W; DeCoste, Jared B; Browe, Matthew A

    2012-07-17

    The adsorption of ammonia on Zr(OH)(4), as well as Zr(OH)(4) treated with sulfuric acid, were examined. The results show that treating Zr(OH)(4) with sulfuric acid leads to the formation of a sulfate on the surface of the material, and that the sulfate contributes to the ammonia adsorption capacity through the formation of an ammonium sulfates species. Calcination of Zr(OH)(4) decreases the ammonia adsorption capacity of the material and limits the formation of sulfate species. NMR and FTIR spectroscopy results are presented that show the presence of two distinct ammonium species on the surface of the material. The adsorption capacity of the materials is shown to be a complex phenomenon that is impacted by the surface area, the sulfur content, and the pH of the material. The results illustrate that Zr(OH)(4), which is known to adsorb acidic gases, can be modified and used to adsorb basic gases.

  8. Air pollution and asthma: clinical studies with sulfuric acid aerosols

    SciTech Connect

    Utell, M.J.; Frampton, M.W.; Morrow, P.E. )

    1991-11-01

    Until recently, acid deposition has been widely considered a serious ecological problem but not a threat to human health. The controlled clinical study is an important approach in linking acidic aerosol inhalation with respiratory effects. Asthmatic patients represent a subpopulation most responsive to sulfuric acid aerosols. In a series of studies with asthmatic volunteers, several factors have been identified that may modulate the intensity of the bronchoconstrictor response to inhaled acidic aerosols. We found (1) enhancement of the bronchoconstrictor response during exercise, (2) the more acidic aerosols provoke the greatest changes in lung function, and (3) mitigation of airway responses during sulfuric acid aerosol inhalation caused by high respiratory ammonia concentrations. Additional factors influencing responsiveness await identification.

  9. FURNACE INJECTION OF ALKALINE SORBENTS FOR SULFURIC ACID CONTROL

    SciTech Connect

    Gary M. Blythe

    2000-12-01

    This document summarizes progress on the Cooperative Agreement DE-FC26-99FT40718, Furnace Injection of Alkaline Sorbents for Sulfuric Acid Control, during the time period April 1, 2000 through September 30, 2000. The objective of this project is to demonstrate the use of alkaline reagents injected into the furnace of coal-fired boilers as a means of controlling sulfuric acid emissions. The coincident removal of hydrochloric acid and hydrofluoric acid will also be determined, as will the removal of arsenic, a known poison for NOX selective catalytic reduction (SCR) catalysts. EPRI, the Tennessee Valley Authority (TVA), First Energy Corporation, and the Dravo Lime Company are project co-funders. URS Corporation is the prime contractor. This is the second reporting period for the subject Cooperative Agreement. During this period, the first of four short-term sorbent injection tests were conducted at the First Energy Bruce Mansfield Plant. This test determined the effectiveness of dolomite injection through out-of-service burners as a means of controlling sulfuric acid emissions from this unit. The tests showed that dolomite injection could achieve up to 95% sulfuric acid removal. Balance of plant impacts on furnace slagging and fouling, air heater fouling, ash loss-on-ignition, and the flue gas desulfurization system were also determined. These results are presented and discussed in this report.

  10. Energy efficiency of iron–boron–silicon metallic glasses in sulfuric acid solutions

    NASA Astrophysics Data System (ADS)

    Habib, K.; Jiang, W.; Rahman, B. M. A.; Grattan, K. T. V.

    2017-03-01

    A criterion of the energy efficiency of iron–boron–silicon metallic glasses in sulfuric acid solutions is proposed for the first time. The criterion has been derived based on calculating the limit of the ratio value of the conductivity of a metallic glass in aqueous solution to the conductivity of the metallic glass in air. In other words, the conductivity ratio of a metallic glass in aqueous solution to the conductivity of the metallic glass in air  = 1, was applied to determine the energy efficiency of the metallic glass in the aqueous solution when the conductivity of a metallic glass in air became equal (decreased) to the steady conductivity of the metallic glass in aqueous solution as a function of time of the exposure of the metallic glass to the aqueous solution. This criterion was not only used to determine the energy efficiency of different metallic glasses, but also, the criterion was used to determine the energy efficiency of metallic glasses exposed to a wide range of sulfuric acid concentrations. These conductivity values were determined by the electrochemical impedance spectroscopy (EIS). In addition, the criterion can be applied under diverse test conditions with a predetermined period of the operational life of the metallic glasses as functional materials. Furthermore, variations of the energy efficiency of the metallic glasses as a function of the acid concentration and time were produced by fitting the experimental data to a numerical model using a nonlinear regression method. The profiles of the metallic glasses exhibit a less conservative behavior of the energy efficiency than the proposed analytical criterion.

  11. Sulfuric acid measurements in the exhaust plume of a jet aircraft in flight: Implications for the sulfuric acid formation efficiency

    NASA Astrophysics Data System (ADS)

    Curtius, J.; Arnold, F.; Schulte, P.

    2002-04-01

    Sulfuric acid concentrations were measured in the exhaust plume of a B737-300 aircraft in flight. The measurements were made onboard of the German research aircraft Falcon using the Volatile Aerosol Component Analyzer (VACA). The VACA measures total H2SO4, which is the sum of gaseous H2SO4 and aerosol H2SO4. Measurements took place at distances of 25-200 m behind the B737 corresponding to plume ages of about 0.1-1 seconds. The fuel sulfur content (FSC) of the fuel burned by the B737 engines was alternatively 2.6 and 56 mg sulfur per kilogram fuel (ppmm). H2SO4 concentrations measured in the plume for the 56 ppmm sulfur case were up to ~600 pptv. The average concentration of H2SO4 measured in the ambient atmosphere outside the aircraft plume was 88 pptv, the maximum ambient atmospheric H2SO4 was ~300 pptv. Average efficiencies ɛΔCO2 = 3.3 +/- 1.8% and ɛΔT = 2.9 +/- 1.6% for fuel sulfur conversion to sulfuric acid were inferred when relating the H2SO4 data to measurements of the plume tracers ΔCO2 and ΔT.

  12. 46 CFR 153.556 - Special requirements for sulfuric acid and oleum.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... 46 Shipping 5 2011-10-01 2011-10-01 false Special requirements for sulfuric acid and oleum. 153... and Equipment Special Requirements § 153.556 Special requirements for sulfuric acid and oleum. (a... acid, oleum, or contaminated sulfuric acid are approved by the Commandant (CG-522) on a case by case...

  13. 46 CFR 153.556 - Special requirements for sulfuric acid and oleum.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... 46 Shipping 5 2014-10-01 2014-10-01 false Special requirements for sulfuric acid and oleum. 153... and Equipment Special Requirements § 153.556 Special requirements for sulfuric acid and oleum. (a... acid, oleum, or contaminated sulfuric acid are approved by the Commandant (CG-ENG) on a case by case...

  14. 46 CFR 153.556 - Special requirements for sulfuric acid and oleum.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... 46 Shipping 5 2013-10-01 2013-10-01 false Special requirements for sulfuric acid and oleum. 153... and Equipment Special Requirements § 153.556 Special requirements for sulfuric acid and oleum. (a... acid, oleum, or contaminated sulfuric acid are approved by the Commandant (CG-ENG) on a case by case...

  15. 46 CFR 153.556 - Special requirements for sulfuric acid and oleum.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... 46 Shipping 5 2012-10-01 2012-10-01 false Special requirements for sulfuric acid and oleum. 153... and Equipment Special Requirements § 153.556 Special requirements for sulfuric acid and oleum. (a... acid, oleum, or contaminated sulfuric acid are approved by the Commandant (CG-ENG) on a case by case...

  16. Sulfur and Sulfuric Acid Microphysics in the Venus Atmosphere: Implications for the Unknown UV Absorber

    NASA Astrophysics Data System (ADS)

    Gao, P.; Carlson, R. W.; Robinson, T. D.; Crisp, D.; Lyons, J. R.; Yung, Y. L.

    2016-12-01

    A mystery that has continued to plague our sister planet, Venus, for nearly a century is the nature of the brightness contrasts observed crisscrossing its disk in near-ultraviolet wavelength images. These contrasts - specifically the dark regions - have been attributed to the actions of an unknown UV absorber, knowing the identity of which is integral to understanding the Venus atmosphere due to the high rates of mesospheric heating attributed to the absorption of solar UV. One possible candidate for the UV absorber is polysulfur, which form from polymerization of elemental sulfur arising from SO2 photolysis at the Venus cloud tops under low O2 conditions. In this work we investigate the microphysics of condensed polysulfur and its interaction with the sulfuric acid clouds. We consider the "gumdrop model", where sulfur is allowed to condense onto sulfuric acid cloud particles. We explore the possibility that S2 vapor may condense faster than its loss to gas phase reactions that produce higher allotropes, leading to solid state polymerization to S8. This process may explain the ephemeral and variable nature of the UV absorption.

  17. ELEMENTAL MERCURY ADSORPTION BY ACTIVATED CARBON TREATED WITH SULFURIC ACID

    EPA Science Inventory

    The paper gives results of a study of the adsorption of elemental mercury at 125 C by a sulfuric-acid (H2S04, 50% w/w/ solution)-treated carbon for the removal of mercury from flue gas. The pore structure of the sample was characterized by nitrogen (N2) at -196 C and the t-plot m...

  18. Heat-Exchange Fluids for Sulfuric Acid Vaporizers

    NASA Technical Reports Server (NTRS)

    Lawson, D. D.; Petersen, G. R.

    1982-01-01

    Some fluorine-substituted organic materials meet criteria for heat-exchange fluids in contact with sulfuric acid. Most promising of these are perfluoropropylene oxide polymers with degree of polymerization (DP) between 10 and 50. It is desirable to have DP in high range because vapor pressure of material decreases as DP increases, and high-DP liquids have lower loss due to vaporization.

  19. Potential heat exchange fluids for use in sulfuric acid vaporizers

    NASA Technical Reports Server (NTRS)

    Lawson, D. D.; Petersen, G. R.

    1981-01-01

    A series of liquids have been screened as candidate heat exchange fluids for service in thermochemical cycles that involve the vaporization of sulfuric acid. The required chemical and physical criteria of the liquids is described with the results of some preliminary high temperature test data presented.

  20. ELEMENTAL MERCURY ADSORPTION BY ACTIVATED CARBON TREATED WITH SULFURIC ACID

    EPA Science Inventory

    The paper gives results of a study of the adsorption of elemental mercury at 125 C by a sulfuric-acid (H2S04, 50% w/w/ solution)-treated carbon for the removal of mercury from flue gas. The pore structure of the sample was characterized by nitrogen (N2) at -196 C and the t-plot m...

  1. Microbial Sulfur Cycling in an Acid Mine Lake

    NASA Astrophysics Data System (ADS)

    Bernier, L.; Warren, L. A.

    2004-12-01

    Geochemical dynamics of a tailings impacted lake in Northern Ontario were investigated over a three-year period, in which active pyrrhotite slurry disposal was initiated in year two. A strong seasonal trend of decreasing epilimnetic pH with significant diurnal acid production, pre-, during and post slurry deposition was observed with high rates observed compared to pre-slurry. Slurry deposition occurred at the surface of the lake and acted as a reaction stimulant for acid generation. Over the diurnal timescale investigated, the highest rates of acid production occurred not at the lake surface but within the metaliminetic region of the lake. This region was exemplified by strong decreasing oxygen gradients, and thus observed high rates of acid generation are more consistent with microbial pathways of sulfur oxidation than with abiotic, oxygen catalyzed pathways. Consistent with microbial catalysis, metalimnetic rates of acid generation were highest during June and July when microbial populations and metabolic rates were maximal. These results indicate that microbial oxidation of sulfur species play a major role in acid generation in this system. Further, observed rates of acid generation exceed those predicted by published abiotic rates of pyrrhotite oxidation, but are consistent with literature estimates of acid generation catalyzed by microbial activity. Acidithiobacilli accounted for up to 50% of the microbial community pre slurry, but were absent post slurry deposition. These results are the first to demonstrate quantitatively that microbial sulfur oxidation can play a predominant role in acid generation within mine tailings impacted systems. They further highlight the need to evaluate the more complex pathways by which microorganisms process sulfur as the conditions, controls and process rates differ from those observed for abiotic reactions.

  2. The Reaction of CIONO_2 with Submicrometer Sulfuric Acid Aerosol

    NASA Astrophysics Data System (ADS)

    Hanson, D. R.; Lovejoy, E. R.

    1995-03-01

    The measured reaction probability, γ, for the reaction of chlorine nitrate (CIONO_2) with 60 percent (by weight) sulfuric acid aerosol increases monotonically with particle size at 250 kelvin. The reacto-diffusive length (l, the effective liquid depth over which reaction occurs) derived from these experiments is 0.037 ± 0.007 micrometer (95 percent confidence level for precision). The reaction probability for the reaction of CIONO_2 with 60 percent sulfuric acid aerosol doped with ~7 x 10-4 M hydrochloric acid at 250 kelvin is larger by about a factor of 4 than in the absence of hydrochloric acid and varies less with particle size (l = 0.009 ± 0.005 micrometer). These results provide a test of the theory for gas-particle reactions and further insight into the reactivity of atmospheric aerosol.

  3. The Reaction of CIONO2 with Submicrometer Sulfuric Acid Aerosol.

    PubMed

    Hanson, D R; Lovejoy, E R

    1995-03-03

    The measured reaction probability, gamma for the reaction of chlorine nitrate (CIONa(2)) with 60 percent (by weight) sulfuric acid aerosol increases monotonically with particle size at 250 kelvin. The reacto-diffusive length (l, the effective liquid depth over which reaction occurs) derived from these experiments is 0.037 +/- 0.007 micrometer (95 percent confidence level for precision). The reaction probability for the reaction of CIONO(2) with 60 percent sulfuric acid aerosol doped with approximately 7 x 10(-4) M hydrochloric acid at 250 kelvin is larger by about a factor of 4 than in the absence of hydrochloric acid and varies less with particle size (l = 0.009 +/- 0.005 micrometer). These results provide a test of the theory for gas-particle reactions and further insight into the reactivity of atmospheric aerosol.

  4. Thermodynamics of Aqueous Organic Sulfur Compounds: A Key to the Organic Geochemistry of Hydrothermal Systems?

    NASA Technical Reports Server (NTRS)

    Schulte, Mitchell; Rogers, Karyn L.; DeVincenzi, Donald L. (Technical Monitor)

    2000-01-01

    Hydrothermal environments are locations of varied geochemistry due to the disequilibrium between vent fluids and seawater. The disequilibrium geochemistry has been hypothesized to include reactions to synthesize organic compounds. Observations of the organic geochemistry of hydrothermal vent sites has received little attention. Experimental simulations of these environments, however, indicate that organic compounds may have difficulty forming in a purely aqueous environment. On the other hand, thiols. thioesters and disulfides have been implicated as reaction intermediates between CO or CO2 in experiments of carbon reduction in hydrothermal environments as well as in a variety of biological processes and other abiotic reactions (Wachtershauser, 1990, OLEB 20, 173; Heinen and Lauwers, 1996, OLEB 26, 13 1, Huber and Wachtershauser, 1997, Science 276, 245; Russell et al., 1998, in Thermophiles: The keys to molecular evolution and the origin of life?). The reduction of CO2 to thiols, for example, is observed using the FeS-H2S/FeS2 couple to provide the reducing power (see Schoonen et al., 1999, OLEB 29, 5). In addition, the enzyme involved in final stage of methanogenesis, coenzyme-M, is itself a thiol. Thus, organic sulfur compounds may hold the key to the organic chemistry leading to the origin of life at high temperatures. Understanding the biochemical processes of microorganisms that can live to temperatures at least as high as 113 C (Blochl et al., 1996, Extremophiles 1, 14) requires knowledge of the properties of the chemical reactions involved. In order to assess the role of aqueous organic sulfur compounds in hydrothermal organic geochemistry, we have been attempting to determine their thermodynamic properties. We have culled the literature to obtain the properties of organic sulfur compounds. We are able to calculate a number of essential properties, such as free energies of formation, from solubility data available in the literature together with standard

  5. Thermodynamics of Aqueous Organic Sulfur Compounds: A Key to the Organic Geochemistry of Hydrothermal Systems?

    NASA Technical Reports Server (NTRS)

    Schulte, Mitchell; Rogers, Karyn L.; DeVincenzi, Donald L. (Technical Monitor)

    2000-01-01

    Hydrothermal environments are locations of varied geochemistry due to the disequilibrium between vent fluids and seawater. The disequilibrium geochemistry has been hypothesized to include reactions to synthesize organic compounds. Observations of the organic geochemistry of hydrothermal vent sites has received little attention. Experimental simulations of these environments, however, indicate that organic compounds may have difficulty forming in a purely aqueous environment. On the other hand, thiols. thioesters and disulfides have been implicated as reaction intermediates between CO or CO2 in experiments of carbon reduction in hydrothermal environments as well as in a variety of biological processes and other abiotic reactions (Wachtershauser, 1990, OLEB 20, 173; Heinen and Lauwers, 1996, OLEB 26, 13 1, Huber and Wachtershauser, 1997, Science 276, 245; Russell et al., 1998, in Thermophiles: The keys to molecular evolution and the origin of life?). The reduction of CO2 to thiols, for example, is observed using the FeS-H2S/FeS2 couple to provide the reducing power (see Schoonen et al., 1999, OLEB 29, 5). In addition, the enzyme involved in final stage of methanogenesis, coenzyme-M, is itself a thiol. Thus, organic sulfur compounds may hold the key to the organic chemistry leading to the origin of life at high temperatures. Understanding the biochemical processes of microorganisms that can live to temperatures at least as high as 113 C (Blochl et al., 1996, Extremophiles 1, 14) requires knowledge of the properties of the chemical reactions involved. In order to assess the role of aqueous organic sulfur compounds in hydrothermal organic geochemistry, we have been attempting to determine their thermodynamic properties. We have culled the literature to obtain the properties of organic sulfur compounds. We are able to calculate a number of essential properties, such as free energies of formation, from solubility data available in the literature together with standard

  6. Color Change of Sudan III against Concentrated Sulfuric Acid in Acetonitrile and Quantification for a Small Amount of Concentrated Sulfuric Acid.

    PubMed

    Sakurai, Takao; Kurata, Shoji; Ogino, Kenji

    2016-01-01

    The color-changing phenomenon of hydrophobic bisazo dye, Sudan III in an acetonitrile solution against the addition of concentrated sulfuric acid has been discovered and the chromic properties investigated. Based on observations, a novel quantification method of concentrated sulfuric acid has been developed. Sudan III changes its color from orange to blue against a small volume of sulfuric acid, and the acetonitrile solution of Sudan III is the most suitable for observing the color-change phenomenon. (1)H-NMR and UV-Vis spectroscopic studies showed that the color-change mechanism of Sudan III against sulfuric acid is due to the protonation of the dye by sulfuric acid. This phenomenon is applicable to the quantification of concentrated sulfuric acid by introducing the Hammett acidity function. The proposed method requires only a small amount of the sample, 0.04 mL, and enables rapid quantification.

  7. Recovery of high purity sulfuric acid from the waste acid in toluene nitration process by rectification.

    PubMed

    Song, Kai; Meng, Qingqiang; Shu, Fan; Ye, Zhengfang

    2013-01-01

    Waste sulfuric acid is a byproduct generated from numerous industrial chemical processes. It is essential to remove the impurities and recover the sulfuric acid from the waste acid. In this study the rectification method was introduced to recover high purity sulfuric acid from the waste acid generated in toluene nitration process by using rectification column. The waste acid quality before and after rectification were evaluated using UV-Vis spectroscopy, GC/MS, HPLC and other physical and chemical analysis. It was shown that five nitro aromatic compounds in the waste acid were substantially removed and high purity sulfuric acid was also recovered in the rectification process at the same time. The COD was removed by 94% and the chrominance was reduced from 1000° to 1°. The recovered sulfuric acid with the concentration reaching 98.2 wt% had a comparable quality with commercial sulfuric acid and could be recycled back into the toluene nitration process, which could avoid waste of resources and reduce the environmental impact and pollution. Copyright © 2012 Elsevier Ltd. All rights reserved.

  8. Reactive uptake of organic compounds by liquid sulfuric acid.

    NASA Astrophysics Data System (ADS)

    Roberts, J.; Michelsen, R.

    2003-04-01

    The uptake of several organic compounds by laboratory surrogates for tropospheric sulfuric acid particles were investigated by mass spectrometry and infrared reflection-absorption spectroscopy. Among the compounds studied were acetone [(CH_3)_2CO], 2,4-hexanedione [CH_3CO(CH_2)_2COCH_3, MBO], and 2-methyl-3-buten-2-ol [CH_2CHC(CH_3)_2OH]. Experiments were carried out on ultrathin sulfuric acid films (ca. 10-100 monolayer equivalents thick) as functions of organic partial pressure, temperature, and acid composition. Acetone uptake is irreversible for acids that contain >70 weight percent (wt. %) H_2SO4, with kinetics that are second-order in concentration of dissolved acetone. Hexanedione and MBO are irreversibly taken for all acid compositions investigated (60-96 wt. %), with first-order uptake kinetics. In all cases, the irreversible uptake is a consequence of sulfuric acid catalyzed reactions that lead to the formation of new C-C bonds. Implications of these results for heterogeneous tropospheric chemistry will be discussed.

  9. Kinetics and mechanism of hydration of o-thioquinone methide in aqueous solution. Rate-determining protonation of sulfur.

    PubMed

    Chiang, Yvonne; Kresge, A Jerry; Sadovski, Oleg; Zhan, Hao-Qiang

    2005-03-04

    o-Thioquinone methide, 2, was generated in aqueous solution by flash photolysis of benzothiete, 1, and rates of hydration of this quinone methide to o-mercaptobenzyl alcohol, 3, were measured in perchloric acid solutions, using H2O and D2O as the solvent, and also in acetic acid and tris(hydroxymethyl)methylammonium ion buffers, using H2O as the solvent. The rate profiles constructed from these data show hydronium-ion-catalyzed and uncatalyzed hydration reaction regions, just like the rate profiles based on literature data for hydration of the oxygen analogue, o-quinone methide, of the presently examined substrate. Solvent isotope effects on hydronium-ion catalysis of hydration for the two substrates, however, are quite different: k(H)/k(D) = 0.42 for the oxygen quinone methide, whereas k(H)/k(D) = 1.66 for the sulfur substrate. The inverse nature (k(H)/k(D) < 1) of the isotope effect in the oxygen system indicates that this reaction occurs by a preequilibrium proton-transfer reaction mechanism, with protonation of the substrate on its oxygen atom being fast and reversible and capture of the benzyl-type carbocationic intermediate so formed being rate-determining. The normal direction (k(H)/k(D) > 1) of the isotope effect in the sulfur system, on the other hand, suggests that protonation of the substrate on its sulfur atom is in this case rate-determining, with carbocation capture a fast following step. A semiquantitative argument supporting this hypothesis is presented.

  10. 40 CFR 180.1019 - Sulfuric acid; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 25 2013-07-01 2013-07-01 false Sulfuric acid; exemption from the... Exemptions From Tolerances § 180.1019 Sulfuric acid; exemption from the requirement of a tolerance. (a) Residues of sulfuric acid are exempted from the requirement of a tolerance when used in accordance with...

  11. 40 CFR 180.1019 - Sulfuric acid; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 24 2011-07-01 2011-07-01 false Sulfuric acid; exemption from the... Exemptions From Tolerances § 180.1019 Sulfuric acid; exemption from the requirement of a tolerance. (a) Residues of sulfuric acid are exempted from the requirement of a tolerance when used in accordance with...

  12. 40 CFR 180.1019 - Sulfuric acid; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 23 2010-07-01 2010-07-01 false Sulfuric acid; exemption from the... Exemptions From Tolerances § 180.1019 Sulfuric acid; exemption from the requirement of a tolerance. (a) Residues of sulfuric acid are exempted from the requirement of a tolerance when used in accordance with...

  13. 40 CFR 180.1019 - Sulfuric acid; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 24 2014-07-01 2014-07-01 false Sulfuric acid; exemption from the... Exemptions From Tolerances § 180.1019 Sulfuric acid; exemption from the requirement of a tolerance. (a) Residues of sulfuric acid are exempted from the requirement of a tolerance when used in accordance with...

  14. 40 CFR 180.1019 - Sulfuric acid; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 25 2012-07-01 2012-07-01 false Sulfuric acid; exemption from the... Exemptions From Tolerances § 180.1019 Sulfuric acid; exemption from the requirement of a tolerance. (a) Residues of sulfuric acid are exempted from the requirement of a tolerance when used in accordance with...

  15. 46 CFR 153.556 - Special requirements for sulfuric acid and oleum.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ...) Except as prescribed in paragraphs (b) and (c) of this section, containment systems carrying sulfuric acid, oleum, or contaminated sulfuric acid are approved by the Commandant (CG-522) on a case by case basis. (b) A containment system carrying sulfuric acid may be: (1) Made of unlined steel if the cargo...

  16. Sulfur amino acids and severe childhood undernutrition

    PubMed Central

    Jahoor, Farook

    2011-01-01

    In studies of glutathione (GSH) metabolism in children with severe childhood undernutrition (SCU), we found that slower erythrocyte GSH synthesis in those with edema was associated with lower concentrations of cysteine, the rate-limiting precursor of GSH synthesis. This finding suggested a shortage in cysteine availability for GSH synthesis in children with edematous SCU. The plasma concentration of methionine, the sulfur donor for cysteine synthesis, was also lower in children with edematous SCU, suggesting decreased methionine availability for cysteine synthesis. It is also possible that reduced methionine availability will result in decreased formation of S-adenosylmethionine, which could lead to an overall defect in methylation reactions. This review focuses on (i) the relationship between cysteine availability and GSH synthesis in children SCU (ii) whether there is an inadequate supply of cysteine in those with edematous SCU and, if so, (ii) whether this is due to a shortage of methionine or to decreased release from a protein breakdown. Finally, (iii) if there is a shortage of methionine, does this result in decreased synthesis of the universal methyl donor S-adenosylmethionine? PMID:22364160

  17. FURNACE INJECTION OF ALKALINE SORBENTS FOR SULFURIC ACID CONTROL

    SciTech Connect

    Gary M. Blythe

    2000-12-01

    A test program is being sponsored by the US Department of Energy (DOE), EPRI, FirstEnergy, and TVA to investigate furnace injection of alkaline sorbents as a means of reducing sulfuric acid concentrations in the flue gas from coal-fired boilers. This test program is being conducted at the FirstEnergy Bruce Mansfield Plant (BMP), although later testing will be conducted at a TVA plant. A sorbent injection test was conducted the week of April 18, 2000. The test was the first of several short-term (one- to two-week duration) tests to investigate the effectiveness of various alkaline sorbents for sulfuric acid control and the effects of these sorbents on boiler equipment performance. This first short-term test investigated the effect of injecting dry dolomite powder (CaCO{sub 3} {center_dot} MgCO{sub 3}), a mineral similar to limestone, into the furnace of Unit 2. During the test program, various analytical techniques were used to assess the effects of sorbent injection. These primarily included sampling with the controlled condensation system (CCS) for determining flue gas SO{sub 3} content and an acid dew-point (ADP) meter for determining the sulfuric acid dew point (and, indirectly, the concentration of sulfuric acid) of the flue gas. EPA Reference Method 26a was used for determining hydrochloric acid (HCl) and hydrofluoric acid (HF), as well and chlorine (Cl{sub 2}) and fluorine (F{sub 2}) concentrations in the flue gas. Fly ash resistivity was measured using a Southern Research Institute (SRI) point-to-plane resistivity probe, and unburned carbon in fly ash was determined by loss on ignition (LOI). Coal samples were also collected and analyzed for a variety of parameters. Finally, visual observations were made of boiler furnace and convective pass surfaces prior to and during sorbent injection.

  18. Speciation in aqueous solutions of nitric acid.

    PubMed

    Hlushak, S; Simonin, J P; De Sio, S; Bernard, O; Ruas, A; Pochon, P; Jan, S; Moisy, P

    2013-02-28

    In this study, speciation in aqueous solutions of nitric acid at 25 °C was assessed in two independent ways. First, Raman experiments were carried out and interpreted in terms of free nitrate ions, ion pairs and neutral HNO(3) molecules. In parallel, a model was developed to account for the formation of these two kinds of pairs. It was based on an extension of the binding mean spherical approximation (BiMSA), or associative MSA (AMSA), in which the size and the charge of the ions in the chemical pair may differ from those of the free ions. A simultaneous fit of the osmotic coefficient and of the proportion of free ions (obtained from Raman spectroscopy experiments) led to an estimation of the speciation in nitric acid solutions. The result obtained using this procedure was compared with the estimation obtained from the Raman experiments.

  19. Metabolism of sulfur amino acids in Saccharomyces cerevisiae.

    PubMed Central

    Thomas, D; Surdin-Kerjan, Y

    1997-01-01

    Sulfur amino acid biosynthesis in Saccharomyces cerevisiae involves a large number of enzymes required for the de novo biosynthesis of methionine and cysteine and the recycling of organic sulfur metabolites. This review summarizes the details of these processes and analyzes the molecular data which have been acquired in this metabolic area. Sulfur biochemistry appears not to be unique through terrestrial life, and S. cerevisiae is one of the species of sulfate-assimilatory organisms possessing a larger set of enzymes for sulfur metabolism. The review also deals with several enzyme deficiencies that lead to a nutritional requirement for organic sulfur, although they do not correspond to defects within the biosynthetic pathway. In S. cerevisiae, the sulfur amino acid biosynthetic pathway is tightly controlled: in response to an increase in the amount of intracellular S-adenosylmethionine (AdoMet), transcription of the coregulated genes is turned off. The second part of the review is devoted to the molecular mechanisms underlying this regulation. The coordinated response to AdoMet requires two cis-acting promoter elements. One centers on the sequence TCACGTG, which also constitutes a component of all S. cerevisiae centromeres. Situated upstream of the sulfur genes, this element is the binding site of a transcription activation complex consisting of a basic helix-loop-helix factor, Cbf1p, and two basic leucine zipper factors, Met4p and Met28p. Molecular studies have unraveled the specific functions for each subunit of the Cbf1p-Met4p-Met28p complex as well as the modalities of its assembly on the DNA. The Cbf1p-Met4p-Met28p complex contains only one transcription activation module, the Met4p subunit. Detailed mutational analysis of Met4p has elucidated its functional organization. In addition to its activation and bZIP domains, Met4p contains two regulatory domains, called the inhibitory region and the auxiliary domain. When the level of intracellular AdoMet increases

  20. Sulfur dynamics in an impoundment receiving acid mine drainage

    SciTech Connect

    Herlihy, A.T.

    1987-01-01

    To quantify the importance of bacterial sulfate reduction (SR) in an acidified system, a sulfate influx-efflux budget was constructed for Lake Anna, an impoundment receiving acid mine drainage. Forty eight percent of the entering sulfate was removed from the water column within the 2 km arm of the lake that receives the pollution. Directly measured SR equaled 200% of the sulfate removal calculated in the budget. Thus, sulfide oxidation must be an important process in these sediments. The calculated alkalinity generated by sulfate removal was more than twice that necessary to account for the observed pH increase in the impoundment. Inorganic sulfur concentrations in the sediments of the impacted arm of Lake Anna were significantly greater than those in unpolluted sections of the lake. Label experiments showed that FeS and elemental sulfur (S{degree}) were the major products of SR in the impacted sediments. Inorganic sulfur (FeS, S{degree}, and pyrite) made up to 60% to 100% of the total sediment sulfur concentration. Pyrite concentrations were high and decreased exponentially with distance from the AMD source, indicating that the pyrite is stream detrius. FeS and S{degree} concentrations were highest at a station 1 km away from the AMD inflow, indicating in situ formation. There was no evidence for the formation of organic sulfur species.

  1. Aqueous solutions of acidic ionic liquids for enhanced stability of polyoxometalate-carbon supercapacitor electrodes

    NASA Astrophysics Data System (ADS)

    Hu, Chenchen; Zhao, Enbo; Nitta, Naoki; Magasinski, Alexandre; Berdichevsky, Gene; Yushin, Gleb

    2016-09-01

    Nanocomposites based on polyoxometalates (POMs) nanoconfined in microporous carbons have been synthesized and used as electrodes for supercapacitors. The addition of the pseudocapacitance from highly reversible redox reaction of POMs to the electric double-layer capacitance of carbon lead to an increase in specific capacitance of ∼90% at 1 mV s-1. However, high solubility of POM in traditional aqueous electrolytes leads to rapid capacity fading. Here we demonstrate that the use of aqueous solutions of protic ionic liquids (P-IL) as electrolyte instead of aqueous sulfuric acid solutions offers an opportunity to significantly improve POM cycling stability. Virtually no degradation in capacitance was observed in POM-based positive electrode after 10,000 cycles in an asymmetric capacitor with P-IL aqueous electrolyte. As such, POM-based carbon composites may now present a viable solution for enhancing energy density of electrical double layer capacitors (EDLC) based on pure carbon electrodes.

  2. Recovery and separation of sulfuric acid and iron from dilute acidic sulfate effluent and waste sulfuric acid by solvent extraction and stripping.

    PubMed

    Qifeng, Wei; Xiulian, Ren; Jingjing, Guo; Yongxing, Chen

    2016-03-05

    The recovery and simultaneous separation of sulfuric acid and iron from dilute acidic sulfate effluent (DASE) and waste sulfuric acid (WSA) have been an earnest wish for researchers and the entire sulfate process-based titanium pigment industry. To reduce the pollution of the waste acid and make a comprehensive use of the iron and sulfuric acid in it, a new environmentally friendly recovery and separation process for the DASE and the WSA is proposed. This process is based on the reactive extraction of sulfuric acid and Fe(III) from the DASE. Simultaneously, stripping of Fe(III) is carried out in the loaded organic phase with the WSA. Compared to the conventional ways, this innovative method allows the effective extraction of sulfuric acid and iron from the DASE, and the stripping of Fe(III) from the loaded organic phase with the WSA. Trioctylamine (TOA) and tributyl phosphate (TBP) in kerosene (10-50%) were used as organic phases for solvent extraction. Under the optimal conditions, about 98% of Fe(III) and sulfuric acid were removed from the DASE, and about 99.9% of Fe(III) in the organic phase was stripped with the WSA. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. Interaction of sulfuric acid corrosion and mechanical wear of iron

    NASA Technical Reports Server (NTRS)

    Rengstorff, G. W. P.; Miyoshi, K.; Buckley, D. H.

    1986-01-01

    Friction and wear experiment were conducted with elemental iron sliding on aluminum oxide in aerated sulfuric acid at concentrations ranging from very dilute (0.00007 N; i.e., 4 ppm) to very concentrated (96 percent acid). Load and reciprocating sliding speed were kept constant. With the most dilute acid concentration of 0.00007 to 0.0002 N, a complex corrosion product formed that was friable and often increased friction and wear. At slightly higher concentrations of 0.001 N, metal losses were essentially by wear alone. Because no buildup of corrosion products occurred, this acid concentration became the standard from which to separate metal loss from direct corrosion and mechanical wear losses. When the acid concentration was increased to 5 percent (1 N), the well-established high corrosion rate of iron in sulfuric acid strongly dominated the total wear loss. This strong corrosion increased to 30 percent acid and decreased somewhat to 50 percent acid in accordance with expectations. However, the low corrosion of iron expected at acid concentrations of 65 to 96 percent was not observed in the wear area. It was apparent that the normal passivating film was being worn away and a galvanic cell established that rapidly attacked the wear area. Under the conditions where direct corrosion losses were highest, the coefficient of friction was the lowest.

  4. Interaction of sulfuric acid corrosion and mechanical wear of iron

    NASA Technical Reports Server (NTRS)

    Rengstorff, G. W. P.; Miyoshi, K.; Buckley, D. H.

    1984-01-01

    Friction and wear experiments were conducted with elemental iron sliding on aluminum oxide in aerated sulfuric acid at concentrations ranging from very dilute (0.00007 N; i.e., 4 ppm) to very concentrated (96 percent acid). Load and reciprocating sliding speed were kept constant. With the most dilute acid concentration of 0.00007 to 0.0002 N, a complex corrosion product formed that was friable and often increased friction and wear. At slightly higher concentrations of 0.001 N, metal losses were essentially by wear alone. Because no buildup of corrosion products occurred, this acid concentration became the standard from which to separate metal loss from direct corrosion and mechanical wear losses. When the acid concentration was increased to 5 percent (1 N), the well-established high corrosion rate of iron in sulfuric acid strongly dominated the total wear loss. This strong corrosion increased to 30 percent acid and decreased somewhat to 50 percent acid in accordance with expectations. However, the low corrosion of iron expected at acid concentrations of 65 to 96 percent was not observed in the wear area. It was apparent that the normal passivating film was being worn away and a galvanic cell established that rapidly attacked the wear area. Under the conditions where direct corrosion losses were highest, the coefficient of friction was the lowest.

  5. Free energy barrier in the growth of sulfuric acid-ammonia and sulfuric acid-dimethylamine clusters.

    PubMed

    Olenius, T; Kupiainen-Määttä, O; Ortega, I K; Kurtén, T; Vehkamäki, H

    2013-08-28

    The first step in atmospheric new particle formation involves the aggregation of gas phase molecules into small molecular clusters that can grow by colliding with gas molecules and each other. In this work we used first principles quantum chemistry combined with a dynamic model to study the steady-state kinetics of sets of small clusters consisting of sulfuric acid and ammonia or sulfuric acid and dimethylamine molecules. Both sets were studied with and without electrically charged clusters. We show the main clustering pathways in the simulated systems together with the quantum chemical Gibbs free energies of formation of the growing clusters. In the sulfuric acid-ammonia system, the major growth pathways exhibit free energy barriers, whereas in the acid-dimethylamine system the growth occurs mainly via barrierless condensation. When ions are present, charged clusters contribute significantly to the growth in the acid-ammonia system. For dimethylamine the role of ions is minor, except at very low acid concentration, and the growing clusters are electrically neutral.

  6. Free energy barrier in the growth of sulfuric acid-ammonia and sulfuric acid-dimethylamine clusters

    NASA Astrophysics Data System (ADS)

    Olenius, T.; Kupiainen-Määttä, O.; Ortega, I. K.; Kurtén, T.; Vehkamäki, H.

    2013-08-01

    The first step in atmospheric new particle formation involves the aggregation of gas phase molecules into small molecular clusters that can grow by colliding with gas molecules and each other. In this work we used first principles quantum chemistry combined with a dynamic model to study the steady-state kinetics of sets of small clusters consisting of sulfuric acid and ammonia or sulfuric acid and dimethylamine molecules. Both sets were studied with and without electrically charged clusters. We show the main clustering pathways in the simulated systems together with the quantum chemical Gibbs free energies of formation of the growing clusters. In the sulfuric acid-ammonia system, the major growth pathways exhibit free energy barriers, whereas in the acid-dimethylamine system the growth occurs mainly via barrierless condensation. When ions are present, charged clusters contribute significantly to the growth in the acid-ammonia system. For dimethylamine the role of ions is minor, except at very low acid concentration, and the growing clusters are electrically neutral.

  7. Friction and wear of iron in sulfuric acid

    NASA Technical Reports Server (NTRS)

    Rengstorff, G. W. P.; Miyoshi, K.; Buckley, D. H.

    1983-01-01

    Elemental iron sliding on aluminum oxide in aerated sulfuric acid concentrations ranging from very dilute (0.000007 N; i.e., 4 ppm) to very concentrated (96 percent acid) was studied. Load and reciprocating sliding speeds were kept constant. With the most dilute acid of 0.7 to 0.0002 N, a complex corrosion product formed that was friable and often increased friction and wear. At concentrations of 0.001 N, metal losses were essentially by wear alone. Because no buildup of corrosion products occurred, this acid concentration became the standard from which to separate metal loss from direct corrosion and mechanical wear losses. When the acid concentration was increased to 5 percent, the high corrosion rate of iron in sulfuric acid strongly dominated the total wear loss. This strong corrosion increased to 30 percent acid, and decreased somewhat at 50 percent in accordance with expectations. However, the low corrosion of iron expected at acid concentrations of 65 to 96 percent was not observed in the wear area. It is apparent that the normal passivating film was being worn away and a galvanic cell established which rapidly attached to the wear area.

  8. RECOVERY OF ACTINIDES FROM AQUEOUS NITRIC ACID SOLUTIONS

    DOEpatents

    Ader, M.

    1963-11-19

    A process of recovering actinides is presented. Tetravalent actinides are extracted from rare earths in an aqueous nitric acid solution with a ketone and back-extracted from the ketone into an aqueous medium. The aqueous actinide solution thus obtained, prior to concentration by boiling, is sparged with steam to reduce its ketone to a maximum content of 3 grams per liter. (AEC)

  9. Dilute-sulfuric acid pretreatment of cattails for cellulose conversion.

    PubMed

    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.

  10. Sulfuric acid-induced corrosion of aluminum surfaces

    SciTech Connect

    Dai, Q.; Freedman, A.; Robinson, G.N.

    1995-12-01

    The sulfuric acid-induced corrosion of smooth (2 nm average roughness) aluminum surfaces has been studied in real times using an in situ Fourier transform infrared reflection absorption spectrometer and a quartz crystal microbalance. Submicron thick, 35 to 55 weight percent (5 to 12 molal), sulfuric acid films were formed on room temperature metal surfaces by the reaction of gas-phase SO{sub 3} and H{sub 2}O vapor in a flowing gas system at a total pressure of {approximately}200 Torr. The deposition of the acid films and subsequent changes in their chemical composition resulting from corrosion of the aluminum substrate could be monitored using characteristic infrared absorption features. The corrosion process always significantly perturbed the spectral signature of the films from that which was observed on inert gold surfaces. Using changes in spectral features that are linked to the production of Al{sup 3+} as indicators of corrosion, the authors conclude the rate of corrosion of the metal is strongly enhanced by both higher relative humidities and increased rates of sulfuric acid deposition.

  11. Sulfuric Acid Regeneration Waste Disposal Technology.

    DTIC Science & Technology

    1986-11-01

    overflow. Newport AAP Newport, IN Storage lagoon; Combined with other lagoon overflow wastewaters; dis - to river, charged to river. Radford AAP Radford...VA Vacuvim filtered; Combined with other $ landfilled. wastewaters; dis - charged to river. Volunteer AAP Chattanooga, TN Vacuum filtered; Double ion...Volpicelli, G., Caprio , V. and Santoro, L. (1982), "Development of a Process for Neutralizing Acid Wastewaters by Powdered Limestone," Enviro Technology

  12. Multidimensional Polycation β-Cyclodextrin Polymer as an Effective Aqueous Binder for High Sulfur Loading Cathode in Lithium-Sulfur Batteries.

    PubMed

    Zeng, Fanglei; Wang, Weikun; Wang, Anbang; Yuan, Keguo; Jin, Zhaoqing; Yang, Yu-sheng

    2015-12-02

    Although the lithium-sulfur battery has attracted significant attention because of its high theoretical energy density and low cost of elemental sulfur, its real application is still hindered by multiple challenges, especially the polysulfides shuttled between the cathode and anode electrodes. By originating from β-cyclodextrin and introducing a quaternary ammonium cation into β-cyclodextrin polymer, a new multifunctional aqueous polycation binder (β-CDp-N(+)) for the sulfur cathode is obtained. The unique hyperbranched network structure of the new binder β-CDp-N(+) as well as its multidimensional noncovalent interactions and the introduced cations endowed β-CDp-N(+) with some new abilities: a sulfur-electrode-stabilized ability, a polysulfides-immobilized ability, and a volume-accommodated ability, which help to ease the primary problems of the lithium-sulfur battery, i.e., the shuttle of polysulfides and the volume change of the sulfur during charge and discharge. It is demonstrated that cycling performance and rate capability of the cathodes can be the improved by using β-CDp-N(+) as the binder compared to other well-known binders. Even with high sulfur loading of 5.5 mg cm(-2), the cathode with β-CDp-N(+) still can deliver an areal capacity of 4.4 mAh cm(-2) at 50 mA g(-1) after 45 cycles, which is much higher than that achieved using the cathode with the conventional binder (0.9 mAh cm(-2)).

  13. Computational study of the hydration of sulfuric acid dimers: implications for acid dissociation and aerosol formation.

    PubMed

    Temelso, Berhane; Phan, Thuong Ngoc; Shields, George C

    2012-10-04

    We have investigated the thermodynamics of sulfuric acid dimer hydration using ab initio quantum mechanical methods. For (H(2)SO(4))(2)(H(2)O)(n) where n = 0-6, we employed high-level ab initio calculations to locate the most stable minima for each cluster size. The results presented herein yield a detailed understanding of the first deprotonation of sulfuric acid as a function of temperature for a system consisting of two sulfuric acid molecules and up to six waters. At 0 K, a cluster of two sulfuric acid molecules and one water remains undissociated. Addition of a second water begins the deprotonation of the first sulfuric acid leading to the di-ionic species (the bisulfate anion HSO(4)(-), the hydronium cation H(3)O(+), an undissociated sulfuric acid molecule, and a water). Upon the addition of a third water molecule, the second sulfuric acid molecule begins to dissociate. For the (H(2)SO(4))(2)(H(2)O)(3) cluster, the di-ionic cluster is a few kcal mol(-1) more stable than the neutral cluster, which is just slightly more stable than the tetra-ionic cluster (two bisulfate anions, two hydronium cations, and one water). With four water molecules, the tetra-ionic cluster, (HSO(4)(-))(2)(H(3)O(+))(2)(H(2)O)(2), becomes as favorable as the di-ionic cluster H(2)SO(4)(HSO(4)(-))(H(3)O(+))(H(2)O)(3) at 0 K. Increasing the temperature favors the undissociated clusters, and at room temperature we predict that the di-ionic species is slightly more favorable than the neutral cluster once three waters have been added to the cluster. The tetra-ionic species competes with the di-ionic species once five waters have been added to the cluster. The thermodynamics of stepwise hydration of sulfuric acid dimer is similar to that of the monomer; it is favorable up to n = 4-5 at 298 K. A much more thermodynamically favorable pathway forming sulfuric acid dimer hydrates is through the combination of sulfuric acid monomer hydrates, but the low concentration of sulfuric acid relative to

  14. Uranyl fluoride luminescence in acidic aqueous solutions

    SciTech Connect

    Beitz, J.V.; Williams, C.W.

    1996-08-01

    Luminescence emission spectra and decay rates are reported for uranyl species in acidic aqueous solutions containing HF or added NaF. The longest luminescence lifetime, 0.269 {+-} 0.006 ms, was observed from uranyl in 1 M HF + 1 M HClO{sub 4} at 296 K and decreased with increasing temperature. Based on a luminescence dynamics model that assumes equilibrium among electronically excited uranyl fluoride species and free fluoride ion, this long lived uranyl luminescence in aqueous solution is attributed primarily to UO{sub 2}F{sub 2}. Studies on the effect of added LiNO{sub 3} or Na{sub 2}WO{sub 4}{center_dot}2H{sub 2}O showed relatively weak quenching of uranyl fluoride luminescence which suggests that high sensitivity determination of the UF{sub 6} content of WF{sub 6} gas should be feasible via uranyl luminescence analysis of hydrolyzed gas samples of impure WF{sub 6}.

  15. Thermal Regeneration of Sulfuric Acid Hydrates after Irradiation

    NASA Technical Reports Server (NTRS)

    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.

  16. Infrared spectroscopy of sulfuric acid/water aerosols: Freezing characteristics

    NASA Astrophysics Data System (ADS)

    Clapp, M. L.; Niedziela, R. F.; Richwine, L. J.; Dransfield, T.; Miller, R. E.; Worsnop, D. R.

    1997-04-01

    A low-temperature flow cell has been used in conjunction with a Fourier transform infrared (FT-IR) spectrometer to study sulfuric acid/water aerosols. The aerosols were generated with a wide range of composition (28 to 85 wt%), including those characteristic of stratospheric sulfate aerosols, and studied over the temperature range from 240 K to 160 K. The particles exhibited deep supercooling, by as much as 100 K below the freezing point in some cases. Freezing of water ice was observed in the more dilute (<40 wt% sulfuric acid) particles, in agreement with the predictions of Jensen et al. and recent observations by Bertram et al. In contrast with theoretical predictions, however, the entire particle often does not immediately freeze, at least on the timescale of the present experiments (seconds to minutes). Freezing of the entire particle is observed at lower temperatures, well below that characteristic of the polar stratosphere.

  17. FURNACE INJECTION OF ALKALINE SORBENTS FOR SULFURIC ACID CONTROL

    SciTech Connect

    Gary M. Blythe

    2001-11-06

    This document summarizes progress on Cooperative Agreement DE-FC26-99FT40718, Furnace Injection of Alkaline Sorbents for Sulfuric Acid Control, during the time period April 1, 2001 through September 30, 2001. The objective of this project is to demonstrate the use of alkaline reagents injected into the furnace of coal-fired boilers as a means of controlling sulfuric acid emissions. The coincident removal of hydrochloric acid and hydrofluoric acid is also being determined, as is the removal of arsenic, a known poison for NO{sub x} selective catalytic reduction (SCR) catalysts. EPRI, the Tennessee Valley Authority (TVA), FirstEnergy Corporation, and the Dravo Lime Company are project co-funders. URS Corporation is the prime contractor. During the current period, American Electric Power (AEP) joined the project as an additional co-funder and as a provider of a host site for testing. This is the fourth reporting period for the subject Cooperative Agreement. During this period, two long-term sorbent injection tests were conducted, one on Unit 3 at FirstEnergy's Bruce Mansfield Plant (BMP) and one on Unit 1 at AEP's Gavin Station. These tests determined the effectiveness of injecting alkaline slurries into the upper furnace of the boiler as a means of controlling sulfuric acid emissions from these units. The alkaline slurries tested included commercially available magnesium hydroxide slurry (Gavin Station), and a byproduct magnesium hydroxide slurry (both Gavin Station and BMP). The tests showed that injecting either the commercial or the byproduct magnesium hydroxide slurry could achieve up to 70 to 75% sulfuric acid removal. At BMP, the overall removal was limited by the need to maintain acceptable electrostatic precipitator (ESP) particulate control performance. At Gavin Station, the overall sulfuric acid removal was limited because the furnace injected sorbent was less effective at removing SO{sub 3} formed across the SCR system installed on the unit for NO{sub x

  18. Recovery of rhenium from sulfuric acid solutions with activated coals

    SciTech Connect

    Troshkina, I.D.; Naing, K.Z.; Ushanova, O.N.; P'o, V.; Abdusalomov, A.A.

    2006-09-15

    Equilibrium and kinetic characteristics of rhenium sorption from sulfuric acid solutions (pH 2) by activated coals produced from coal raw materials (China) were studied. Constants of the Henry equation describing isotherms of rhenium sorption by activated coals were calculated. The effective diffusion coefficients of rhenium in the coals were determined. The dynamic characteristics of rhenium sorption and desorption were determined for the activated coal with the best capacity and kinetic characteristics.

  19. COS in the stratosphere. [sulfuric acid aerosol precursor

    NASA Technical Reports Server (NTRS)

    Inn, E. C. Y.; Vedder, J. F.; Tyson, B. J.; Ohara, D.

    1979-01-01

    Carbonyl sulfide (COS) has been detected in the stratosphere, and mixing ratio measurements are reported for altitudes of 15.2 to 31.2 km. A large volume, cryogenic sampling system mounted on board a U-2 aircraft has been used for lower stratosphere measurements and a balloon platform for measurement at 31.2 km. These observations and measurements strongly support the concept that stratospheric COS is an important precursor in the formation of sulfuric acid aerosols.

  20. Sulfuric Acid Intercalated Graphite Oxide for Graphene Preparation

    PubMed Central

    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

  1. Laryngeal cancer and occupational exposure to sulfuric acid

    SciTech Connect

    Soskolne, C.L.; Zeighami, E.A.; Hanis, N.M.; Kupper, L.L.; Herrmann, N.; Amsel, J.; Mausner, J.S.; Stellman, J.M.

    1984-09-01

    Workers on an ethanol unit which used sulfuric acid in strong concentrations at a large refinery and chemical plant in Baton Rouge, Louisiana were reported in 1979, at excess risk for upper respiratory cancer. The carcinogen implicated by indirect evidence was diethyl sulfate. However, with the continued use of sulfuric acid in the same plant, and with additional cases not attributable to the ethanol process, the hypothesis of an association between sulfuric acid exposure and upper respiratory cancer was tested. Each of 50 confirmed cases of upper respiratory cancer diagnosed between 1944 and 1980, was matched to at least three controls on sex, race, age, date of initial employment, and duration of employment. Thrity-four of the 50 cases were laryngeal cancers. Data were obtained from existing plant records. Retrospective estimates of exposure were made without regard to case or control status. Findings from conditional logistic regression techniques were supported by other statistical methods. Among workers classified as potentially highly exposed, four-fold relative risks for all upper respiratory cancer sites combined were exceeded by the relative risk for laryngeal cancer specifically. Exposure-response and consistency across various comparisons after controlling statistically for tobacco-use, alcoholism and other previously implicated risk factors, suggest increased cancer risk with higher exposure.

  2. Sulfuric acid intercalated graphite oxide for graphene preparation.

    PubMed

    Hong, Yanzhong; Wang, Zhiyong; Jin, Xianbo

    2013-12-06

    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.

  3. Adsorption of cadmium from aqueous solutions on sulfurized activated carbon prepared from nut shells.

    PubMed

    Fouladi Tajar, Amir; Kaghazchi, Tahereh; Soleimani, Mansooreh

    2009-06-15

    Low-cost activated carbon, derived from nut shells, and its modified sample have been used as replacements for the current expensive methods of removing cadmium from aqueous solutions and waste waters. Adsorption of cadmium onto four kinds of activated carbons has been studied; prepared activated carbon (PAC), commercial activated carbon (CAC), and the sulfurized ones (SPAC & SCAC). The activated carbon has been derived, characterized, treated with sulfur and then utilized for the removal of Cd(2+). Sulfurizing agent (SO(2) gas) was successfully used in adsorbents' modification process at the ambient temperature. Samples were then characterized and tested as adsorbents of cadmium. Effect of some parameters such as contact time, initial concentration and pH were examined. With increasing pH, the adsorption of cadmium ions was increased and maximum removal, 92.4% for SPAC, was observed in pH>8.0 (C(0)=100mg/L). The H-type adsorption isotherms, obtained for the adsorbents, indicated a favorable process. Adsorption data on both prepared and commercial activated carbon, before and after sulfurization, followed both the Frendlich and Langmuir models. They were better fitted by Frendlich isotherm as compared to Langmuir. The maximum adsorption capacities were 90.09, 104.17, 126.58 and 142.86 mg/g for CAC, PAC, SCAC and SPAC, respectively. Accordingly, surface modification of activated carbons using SO(2) greatly enhanced cadmium removal. The reversibility of the process has been studied in a qualitative manner and it shows that the spent SPAC can be effectively regenerated for further use easily.

  4. 40 CFR 721.7770 - Alkylphenoxypoly(oxyethylene) sulfuric acid ester, substituted amine salt.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... Significant New Uses for Specific Chemical Substances § 721.7770 Alkylphenoxypoly(oxyethylene) sulfuric acid...) The chemical substance identified as alkyl phenoxypoly(oxyethylene) sulfuric acid ester, substituted... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alkylphenoxypoly(oxyethylene) sulfuric...

  5. 40 CFR 721.7770 - Alkylphenoxypoly(oxyethylene) sulfuric acid ester, substituted amine salt.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... Significant New Uses for Specific Chemical Substances § 721.7770 Alkylphenoxypoly(oxyethylene) sulfuric acid...) The chemical substance identified as alkyl phenoxypoly(oxyethylene) sulfuric acid ester, substituted... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alkylphenoxypoly(oxyethylene) sulfuric...

  6. 40 CFR 721.7770 - Alkylphenoxypoly(oxyethylene) sulfuric acid ester, substituted amine salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... Significant New Uses for Specific Chemical Substances § 721.7770 Alkylphenoxypoly(oxyethylene) sulfuric acid...) The chemical substance identified as alkyl phenoxypoly(oxyethylene) sulfuric acid ester, substituted... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alkylphenoxypoly(oxyethylene) sulfuric...

  7. 40 CFR 721.7770 - Alkylphenoxypoly(oxyethylene) sulfuric acid ester, substituted amine salt.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... Significant New Uses for Specific Chemical Substances § 721.7770 Alkylphenoxypoly(oxyethylene) sulfuric acid...) The chemical substance identified as alkyl phenoxypoly(oxyethylene) sulfuric acid ester, substituted... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alkylphenoxypoly(oxyethylene) sulfuric...

  8. Sulfuric Acid Speleogenesis: Microbial Karst and Microbial Crust

    NASA Astrophysics Data System (ADS)

    Engel, A. S.; Bennett, P. C.; Stern, L. A.

    2001-12-01

    Sulfuric acid speleogenesis is a fundamental mechanism of karst formation, and is potentially responsible for the formation of some of the most extensive cave systems yet discovered. Speleogenesis occurs from the rapid dissolution of the host limestone by sulfuric acid produced from biotic and abiotic sulfide oxidation, and with the release of carbon dioxide, secondary gypsum crusts form. This crust develops predominately on the cave walls, often preserving original bedding indicators, until it finally collapses under its own weight to expose fresh limestone for dissolution. While this general speleogenetic process can be inferred from secondary residues in some caves, directly observing this process is difficult, and involves entry into an extreme environment with toxic atmospheres and low pH solutions. Kane Cave, Big Horn County, WY, offers the unique opportunity to study microbe-rock interactions directly. Kane Cave presently contains 3 springs that discharge hydrogen sulfide-rich waters, supporting thick subaqueous mats of diverse microbial communities in the stream passage. Condensation droplets and elemental sulfur form on subaerially exposed gypsum surfaces. Droplets have an average pH of 1.7, and are dominated by dissolved sulfate, Ca, Mg, Al, and Si, with minor Sr and Fe, and trace Mn and U. SEM and EDS examination of the crusts reveal the presence of C, O, and S, as well as authigenic, doubly-terminated quartz crystals. An average δ 13C value of -36 ‰ suggests that the crusts are biogenic and are composed of chemoautotrophic microorganisms. Enrichment cultures of biofilms and acid droplets rapidly produce sulfuric acid, demonstrating the dominance of sulfur-oxidizing bacteria. Colonization of gypsum surfaces by acidophilic microorganisms enhances acid dissolution of the limestone, and hence the growth of the cave itself. Limestone dissolution also results in mineralized crusts and biofilms that accumulate insoluble residues, which serve as sources of

  9. Rapid determination of organic matter in spent sulfuric acid

    SciTech Connect

    Petrenko, V.G.; Takhtaeva, A.Ya.; Frolova, R.P.

    1981-01-01

    Ammonium sulfate is produced with the aid of spent sulfuric acid which averages 0.3 to 0.7% (and sometimes up to 2.5%) of carbon in the form of organic impurities. In the saturator, the latter upset the processing conditions and lower the quality (size analysis, etc.) of the ammonium sulfate. A rapid quality control procedure is essential to obtain timely warning of increased organic matter contents in the acid. On the other hand, the standard procedure in current use (TU38-2-3-1-68), based on the oxidation of organic substances with potassium bichromate in an acid medium, takes 3 hr to complete. Observations have revealed a correlation between the color of the acid and its organic impurity contents. On this basis, we have developed a rapid photocolorimetric procedure for determining the organic impurity contents of sulfuric acid, based on the known proportionality between optical density (light absorption) and solute (dye) content. A calibration curve is used to convert optical density readings to organic impurity contents. It should be pointed out that in contrast to the standard procedure, our procedure only determines the concentration of organic matter in solution in the acid. However, the amounts of insoluble organic matter are negligible compared with the amounts in solution and therefore do not affect the final results.

  10. PROCESS FOR RECOVERING URANIUM FROM AQUEOUS PHOSPHORIC ACID LIQUORS

    DOEpatents

    Schmitt, J.M.

    1962-09-01

    A liquid-liquid extraction method is given for recovering uranium values from aqueous solutions. An acidic aqueous solution containing uranium values is contacted with an organic phase comprising an organic diluent and the reaction product of phosphorous pentoxide and a substantially pure dialkylphosphoric acid. The uranium values are transferred to the organic phase even from aqueous solutions containing a high concentration of strong uranium complexing agents such as phosphate ions. (AEC)

  11. Proton defect solvation and dynamics in aqueous acid and base.

    PubMed

    Kale, Seyit; Herzfeld, Judith

    2012-10-29

    Easy come, easy go: LEWIS, a new model of reactive and polarizable water that enables the simulation of a statistically reliable number of proton hopping events in aqueous acid and base at concentrations of practical interest, is used to evaluate proton transfer intermediates in aqueous acid and base (picture, left and right, respectively).

  12. Acidities of Water and Methanol in Aqueous Solution and DMSO

    ERIC Educational Resources Information Center

    Gao, Daqing

    2009-01-01

    The relative acidities of water and methanol have been a nagging issue. In gas phase, methanol is more acidic than water by 36.0 kJ/mol; however, in aqueous solution, the acidities of methanol and water are almost identical. The acidity of an acid in solution is determined by both the intrinsic gas-phase ionization Gibbs energy and the solvent…

  13. Acidities of Water and Methanol in Aqueous Solution and DMSO

    ERIC Educational Resources Information Center

    Gao, Daqing

    2009-01-01

    The relative acidities of water and methanol have been a nagging issue. In gas phase, methanol is more acidic than water by 36.0 kJ/mol; however, in aqueous solution, the acidities of methanol and water are almost identical. The acidity of an acid in solution is determined by both the intrinsic gas-phase ionization Gibbs energy and the solvent…

  14. Effects of acid rain and sulfur dioxide on marble dissolution

    USGS Publications Warehouse

    Schuster, Paul F.; Reddy, Michael M.; Sherwood, Susan I.

    1994-01-01

    Acid precipitation and the dry deposition of sulfur dioxide (SO2) accelerate damage to carbonate-stone monuments and building materials. This study identified and quantified environmental damage to a sample of Vermont marble during storms and their preceding dry periods. Results from field experiments indicated the deposition of SO2 gas to the stone surface during dry periods and a twofold increase in marble dissolution during coincident episodes of low rain rate and decreased rainfall pH. The study is widely applicable to the analysis of carbonate-stone damage at locations affected by acid rain and air pollution.

  15. Effects of acid rain and sulfur dioxide on marble dissolution

    SciTech Connect

    Schuster, P.F.; Reddy, M.M. ); Sherwood, S.I. )

    1994-01-01

    Acid precipitation and the dry deposition of sulfur dioxide (SO[sub 2]) accelerate damage to carbonate-stone monuments and building materials. This study identified and quantified environmental damage to a sample of Vermont marble during storms and their preceding dry periods. Results from field experiments indicated the deposition of SO[sub 2] gas to the stone surface during dry periods and a twofold increase in marble dissolution during coincident episodes of low rain rate and decreased rainfall pH. The study is widely applicable to the analysis of carbonate-stone damage at locations affected by acid rain and air pollution.

  16. Coulometric determination of berkelium in sulfuric acid and nitric acid solutions

    SciTech Connect

    Timofeev, G.A.; Chistyakov, V.M.; Erin, E.A.

    1987-03-01

    Results are reported on the study and quantitative determination of berkelium by the coulometric method in 1 M sulfuric acid, in solutions of nitric acid, and in mixtures of these acids. The best results in the determination of berkelium were obtained in solutions of a mixture of nitric and sulfuric acids. In 1 M HNO/sub 3/ + 0.1 M H/sub 2/SO/sub 4/ solutions, berkelium can be determined with an accuracy within approx. +/- 2%, when its content is 10 ..mu..g/ml.

  17. Sulfuric Acid and Soot Particle Formation in Aircraft Exhaust

    NASA Technical Reports Server (NTRS)

    Pueschel, Rudolf F.; Verma, S.; Ferry, G. V.; Howard, S. D.; Vay, S.; Kinne, S. A.; Baumgardner, D.; Dermott, P.; Kreidenweis, S.; Goodman, J.; Gore, Waren J. Y. (Technical Monitor)

    1997-01-01

    A combination of CN counts, Ames wire impactor size analyses and optical particle counter data in aircraft exhaust results in a continuous particle size distribution between 0.01 micrometer and 1 micrometer particle radius sampled in the exhaust of a Boeing 757 research aircraft. The two orders of magnitude size range covered by the measurements correspond to 6-7 orders of magnitude particle concentration. CN counts and small particle wire impactor data determine a nucleation mode, composed of aircraft-emitted sulfuric acid aerosol, that contributes between 62% and 85% to the total aerosol surface area and between 31% and 34% to its volume. Soot aerosol comprises 0.5% of the surface area of the sulfuric acid aerosol. Emission indices are: EIH2SO4 = 0.05 g/kgFUEL and (0.2-0.5) g/kgFUEL (for 75 ppmm and 675 ppmm fuel-S, respectively), 2.5E4sulfur (gas) to H2SO4 (particle) conversion efficiency is between 10% and 25%.

  18. Sulfuric Acid and Soot Particle Formation in Aircraft Exhaust

    NASA Technical Reports Server (NTRS)

    Pueschel, Rudolf F.; Verma, S.; Ferry, G. V.; Howard, S. D.; Vay, S.; Kinne, S. A.; Baumgardner, D.; Dermott, P.; Kreidenweis, S.; Goodman, J.; hide

    1997-01-01

    A combination of CN counts, Ames wire impactor size analyses and optical particle counter data in aircraft exhaust results in a continuous particle size distribution between 0.01 micrometer and 1 micrometer particle radius sampled in the exhaust of a Boeing 757 research aircraft. The two orders of magnitude size range covered by the measurements correspond to 6-7 orders of magnitude particle concentration. CN counts and small particle wire impactor data determine a nucleation mode, composed of aircraft-emitted sulfuric acid aerosol, that contributes between 62% and 85% to the total aerosol surface area and between 31% and 34% to its volume. Soot aerosol comprises 0.5% of the surface area of the sulfuric acid aerosol. Emission indices are: EIH2SO4 = 0.05 g/kgFUEL and (0.2-0.5) g/kgFUEL (for 75 ppmm and 675 ppmm fuel-S, respectively), 2.5E4sulfur (gas) to H2SO4 (particle) conversion efficiency is between 10% and 25%.

  19. A Development of Ceramics Cylinder Type Sulfuric Acid Decomposer for Thermo-Chemical Iodine-Sulfur Process Pilot Plant

    NASA Astrophysics Data System (ADS)

    Minatsuki, Isao; Fukui, Hiroshi; Ishino, Kazuo

    The hydrogen production method applying thermo-chemical Iodine-Sulfur process (IS process) which uses a nuclear high temperature gas cooled reactor is world widely greatly concerned from the view point of a combination as a clean method, free carbon dioxide in essence. In this process, it is essential a using ceramic material, especially SiC because a operation condition of this process is very corrosive due to a sulfuric acid atmosphere with high temperature and high pressure. In the IS process, a sulfuric acid decomposer is the key component which performs evaporating of sulfuric acid from liquid to gas and disassembling to SO2 gas. SiC was selected as ceramic material to apply for the sulfuric acid decomposer and a new type of binding material was also developed for SiC junction. This technology is expected to wide application not only for a sulfuric acid decomposer but also for various type components in this process. Process parameters were provided as design condition for the decomposer. The configuration of the sulfuric acid decomposer was studied, and a cylindrical tubes assembling type was selected. The advantage of this type is applicable for various type of components in the IS process due to manufacturing with using only simple shape part. A sulfuric acid decomposer was divided into two regions of the liquid and the gaseous phase of sulfuric acid. The thermal structural integrity analysis was studied for the liquid phase part. From the result of this analysis, it was investigated that the stress was below the strength of the breakdown probability 1/100,000 at any position, base material or junction part. The prototype model was manufactured, which was a ceramic portion in the liquid phase part, comparatively complicated configuration, of a sulfuric acid decomposer. The size of model was about 1.9m in height, 1.0m in width. Thirty-six cylinders including inlet and outlet nozzles were combined and each part article was joined using the new binder (slurry

  20. A Development of Ceramics Cylinder Type Sulfuric Acid Decomposer for Thermo-Chemical Iodine-Sulfur Process Pilot Plant

    SciTech Connect

    Hiroshi Fukui; Isao Minatsuki; Kazuo Ishino

    2006-07-01

    The hydrogen production method applying thermo-chemical Iodine-Sulfur process (IS process) which uses a nuclear high temperature gas cooled reactor is world widely greatly concerned from the view point of a combination as a clean method, free carbon dioxide in essence. In this process, it is essential a using ceramic material, especially SiC because a operation condition of this process is very corrosive due to a sulfuric acid atmosphere with high temperature and high pressure. In the IS process, a sulfuric acid decomposer is the key component which performs evaporating of sulfuric acid from liquid to gas and disassembling to SO{sub 2} gas. SiC was selected as ceramic material to apply for the sulfuric acid decomposer and a new type of binding material was also developed for SiC junction. This technology is expected to wide application not only for a sulfuric acid decomposer but also for various type components in this process. Process parameters were provided as design condition for the decomposer. The configuration of the sulfuric acid decomposer was studied, and a cylindrical tubes assembling type was selected. The advantage of this type is applicable for various type of components in the IS process due to manufacturing with using only simple shape part. A sulfuric acid decomposer was divided into two regions of the liquid and the gaseous phase of sulfuric acid. The thermal structural integrity analysis was studied for the liquid phase part. From the result of this analysis, it was investigated that the stress was below the strength of the breakdown probability 1/100,000 at any position, base material or junction part. The prototype model was manufactured, which was a ceramic portion in the liquid phase part, comparatively complicated configuration, of a sulfuric acid decomposer. The size of model was about 1.9 m in height, 1.0 m in width. Thirty-six cylinders including inlet and outlet nozzles were combined and each part article was joined using the new binder

  1. Removal characteristics of sulfuric acid aerosols from coal-fired power plants.

    PubMed

    Pan, Danping; Yang, Linjun; Wu, Hao; Huang, Rongting

    2017-03-01

    With increasing attention on sulfuric acid emission, investigations on the removal characteristics of sulfuric acid aerosols by the limestone gypsum wet flue gas desulfurization (WFGD) system and the wet electrostatic precipitator (WESP) were carried out in two coal-fired power plants, and the effects of the WFGD scrubber type and the flue gas characteristics were discussed. The results showed that it was necessary to install the WESP device after desulfurization, as the WFGD system was inefficient to remove sulfuric acid aerosols from the flue gas. The removal efficiency of sulfuric acid aerosols in the WFGD system with double scrubbers ranged from 50% to 65%, which was higher than that with a single scrubber, ranging from 30% to 40%. Furthermore, the removal efficiency of WESP on the sulfuric acid aerosols was from 47.9% to 52.4%. With increased concentrations of SO3 and particles in the flue gas, the removal efficiencies of the WFGD and the WESP on the sulfuric acid aerosols were increased. Investigations on removal of sulfuric acid aerosols by the WFGD and the WESP in the power plants were aimed at the control of sulfuric acid emission. The results showed that the improvement of the WFGD system was beneficial for the reduction of sulfuric acid emission, while the WESP system was essential to control the final sulfuric acid aerosol concentration.

  2. Manganese-catalysed autoxidation of dissolved sulfur dioxide in the atmospheric aqueous phase

    NASA Astrophysics Data System (ADS)

    Berglund, Johan; Elding, Lars I.

    Autoxidation of SO 2(aq) in the presence of manganese(II) is one of the important pathways for sulfuric acid formation in atmospheric clouds and fogs. Recent experimental results indicating that the catalyzed reaction takes place via a complex free-radical mechanism are discussed. Previous literature is reviewed in the light of this mechanism. Under atmospheric conditions of low total concentrations of manganese(II) ( < 2 × 10 -5 M) and sulfur(IV) ( ≤ 10 -5 M) and 2.5 < pH < 5, the rate law for conversion of SO 2(aq) to SO 3(aq) is reduced to d[S(IV)]/d t = k[Mn(II)][S(IV)], where [S(IV)] denotes the total concentration. A value of the overall rate constant k of 1.4 × 10 3 M -1s -1 is recommended for use in atmospheric model calculations.

  3. FURNACE INJECTION OF ALKALINE SORBENTS FOR SULFURIC ACID CONTROL

    SciTech Connect

    Gary M. Blythe

    2003-10-01

    This document summarizes progress on Cooperative Agreement DE-FC26-99FT40718, Furnace Injection of Alkaline Sorbents for Sulfuric Acid Control, during the time period April 1, 2003 through September, 2003. The objective of this project is to demonstrate the use of alkaline reagents injected into the furnace of coal-fired boilers as a means of controlling sulfuric acid emissions. The coincident removal of hydrochloric acid and hydrofluoric acid is also being determined, as is the removal of arsenic, a known poison for NO{sub x} selective catalytic reduction (SCR) catalysts. EPRI, the Tennessee Valley Authority (TVA), FirstEnergy Corporation, American Electric Power (AEP) and the Dravo Lime Company are project co-funders. URS Group is the prime contractor. This is the eighth reporting period for the subject Cooperative Agreement. During previous reporting periods, two long-term sorbent injection tests were conducted, one on Unit 3 at FirstEnergy's Bruce Mansfield Plant (BMP) and one on Unit 1 at AEP's Gavin Plant. Those tests determined the effectiveness of injecting alkaline slurries into the upper furnace of the boiler as a means of controlling sulfuric acid emissions from these units. The alkaline slurries tested included commercially available magnesium hydroxide slurry (Gavin Plant), and a byproduct magnesium hydroxide slurry (both Gavin Plant and BMP). The tests showed that injecting either the commercial or the byproduct magnesium hydroxide slurry could achieve up to 70-75% overall sulfuric acid removal. At BMP, the overall removal was limited by the need to maintain acceptable electrostatic precipitator (ESP) particulate control performance. At Gavin Plant, the overall sulfuric acid removal was limited because the furnace injected sorbent was less effective at removing SO{sub 3} formed across the SCR system installed on the unit for NO{sub x} control than at removing SO{sub 3} formed in the furnace. The SO{sub 3} removal results were presented in the semi

  4. Dilute sulfuric acid pretreatment of sunflower stalks for sugar production.

    PubMed

    Ruiz, Encarnación; Romero, Inmaculada; Moya, Manuel; Cara, Cristóbal; Vidal, Juan D; Castro, Eulogio

    2013-07-01

    In this work the pretreatment of sunflower stalks by dilute sulfuric acid is studied. Pretreatment temperature and the concentration of acid solution were selected as operation variables and modified according to a central rotatable composite experimental design. Based on previous studies pretreatment time was kept constant (5 min) while the variation range for temperature and acid concentration was centered at 175°C and 1.25% (w/v) respectively. Following pretreatment the insoluble solids were separated by filtration and further submitted to enzymatic hydrolysis, while liquid fractions were analyzed for sugars and inhibitors. Response surface methodology was applied to analyze results based on the combined severity of pretreatment experiments. Optimized results show that up to 33 g of glucose and xylose per 100g raw material (65% of the glucose and xylose present in the raw material) may be available for fermentation after pretreatment at 167°C and 1.3% sulfuric acid concentration. Copyright © 2013 Elsevier Ltd. All rights reserved.

  5. Materials study supporting thermochemical hydrogen cycle sulfuric acid decomposer design

    NASA Astrophysics Data System (ADS)

    Peck, Michael S.

    Increasing global climate change has been driven by greenhouse gases emissions originating from the combustion of fossil fuels. Clean burning hydrogen has the potential to replace much of the fossil fuels used today reducing the amount of greenhouse gases released into the atmosphere. The sulfur iodine and hybrid sulfur thermochemical cycles coupled with high temperature heat from advanced nuclear reactors have shown promise for economical large-scale hydrogen fuel stock production. Both of these cycles employ a step to decompose sulfuric acid to sulfur dioxide. This decomposition step occurs at high temperatures in the range of 825°C to 926°C dependent on the catalysis used. Successful commercial implementation of these technologies is dependent upon the development of suitable materials for use in the highly corrosive environments created by the decomposition products. Boron treated diamond film was a potential candidate for use in decomposer process equipment based on earlier studies concluding good oxidation resistance at elevated temperatures. However, little information was available relating the interactions of diamond and diamond films with sulfuric acid at temperatures greater than 350°C. A laboratory scale sulfuric acid decomposer simulator was constructed at the Nuclear Science and Engineering Institute at the University of Missouri-Columbia. The simulator was capable of producing the temperatures and corrosive environments that process equipment would be exposed to for industrialization of the sulfur iodide or hybrid sulfur thermochemical cycles. A series of boron treated synthetic diamonds were tested in the simulator to determine corrosion resistances and suitability for use in thermochemical process equipment. These studies were performed at twenty four hour durations at temperatures between 600°C to 926°C. Other materials, including natural diamond, synthetic diamond treated with titanium, silicon carbide, quartz, aluminum nitride, and Inconel

  6. SULFURIC ACID REMOVAL PROCESS EVALUATION: SHORT-TERM RESULTS

    SciTech Connect

    Gary M. Blythe; Richard McMillan

    2002-03-04

    The objective of this project is to demonstrate the use of alkaline reagents injected into the furnace of coal-fired boilers as a means of controlling sulfuric acid emissions. Sulfuric acid controls are becoming of increasing interest to utilities with coal-fired units for a number of reasons. Sulfuric acid is a Toxic Release Inventory species, a precursor to acid aerosol/condensable emissions, and can cause a variety of plant operation problems such as air heater plugging and fouling, back-end corrosion, and plume opacity. These issues will likely be exacerbated with the retrofit of SCR for NOX control on some coal-fired plants, as SCR catalysts are known to further oxidize a portion of the flue gas SO{sub 2} to SO{sub 3}. The project is testing the effectiveness of furnace injection of four different calcium- and/or magnesium-based alkaline sorbents on full-scale utility boilers. These reagents have been tested during four one- to two-week tests conducted on two FirstEnergy Bruce Mansfield Plant units. One of the sorbents tested was a magnesium hydroxide slurry produced from a wet flue gas desulfurization system waste stream, from a system that employs a Thiosorbic{reg_sign} Lime scrubbing process. The other three sorbents are available commercially and include dolomite, pressure-hydrated dolomitic lime, and commercial magnesium hydroxide. The dolomite reagent was injected as a dry powder through out-of-service burners, while the other three reagents were injected as slurries through air-atomizing nozzles into the front wall of upper furnace, either across from the nose of the furnace or across from the pendant superheater tubes. After completing the four one- to two-week tests, the most promising sorbents were selected for longer-term (approximately 25-day) full-scale tests. The longer-term tests are being conducted to confirm the effectiveness of the sorbents tested over extended operation and to determine balance-of-plant impacts. This reports presents the

  7. SULFURIC ACID REMOVAL PROCESS EVALUATION: SHORT-TERM RESULTS

    SciTech Connect

    Gary M. Blythe; Richard McMillan

    2002-02-04

    The objective of this project is to demonstrate the use of alkaline reagents injected into the furnace of coal-fired boilers as a means of controlling sulfuric acid emissions. Sulfuric acid controls are becoming of increasing interest to utilities with coal-fired units for a number of reasons. Sulfuric acid is a Toxic Release Inventory species, a precursor to acid aerosol/condensable emissions, and can cause a variety of plant operation problems such as air heater plugging and fouling, back-end corrosion, and plume opacity. These issues will likely be exacerbated with the retrofit of SCR for NO{sub x} control on some coal-fired plants, as SCR catalysts are known to further oxidize a portion of the flue gas SO{sub 2} to SO{sub 3}. The project is testing the effectiveness of furnace injection of four different calcium- and/or magnesium-based alkaline sorbents on full-scale utility boilers. These reagents have been tested during four one- to two-week tests conducted on two First Energy Bruce Mansfield Plant units. One of the sorbents tested was a magnesium hydroxide slurry produced from a wet flue gas desulfurization system waste stream, from a system that employs a Thiosorbic{reg_sign} Lime scrubbing process. The other three sorbents are available commercially and include dolomite, pressure-hydrated dolomitic lime, and commercial magnesium hydroxide. The dolomite reagent was injected as a dry powder through out-of-service burners, while the other three reagents were injected as slurries through air-atomizing nozzles into the front wall of upper furnace, either across from the nose of the furnace or across from the pendant superheater tubes. After completing the four one- to two-week tests, the most promising sorbents were selected for longer-term (approximately 25-day) full-scale tests. The longer-term tests are being conducted to confirm the effectiveness of the sorbents tested over extended operation and to determine balance-of-plant impacts. This reports presents

  8. Acid-catalyzed reactions of hexanal on sulfuric acid particles: Identification of reaction products

    NASA Astrophysics Data System (ADS)

    Garland, Rebecca M.; Elrod, Matthew J.; Kincaid, Kristi; Beaver, Melinda R.; Jimenez, Jose L.; Tolbert, Margaret A.

    While it is well established that organics compose a large fraction of the atmospheric aerosol mass, the mechanisms through which organics are incorporated into atmospheric aerosols are not well understood. Acid-catalyzed reactions of compounds with carbonyl groups have recently been suggested as important pathways for transfer of volatile organics into acidic aerosols. In the present study, we use the aerodyne aerosol mass spectrometer (AMS) to probe the uptake of gas-phase hexanal into ammonium sulfate and sulfuric acid aerosols. While both deliquesced and dry non-acidic ammonium sulfate aerosols showed no organic uptake, the acidic aerosols took up substantial amounts of organic material when exposed to hexanal vapor. Further, we used 1H-NMR, Fourier transform infrared (FTIR) spectroscopy and GC-MS to identify the products of the acid-catalyzed reaction of hexanal in acidic aerosols. Both aldol condensation and hemiacetal products were identified, with the dominant reaction products dependent upon the initial acid concentration of the aerosol. The aldol condensation product was formed only at initial concentrations of 75-96 wt% sulfuric acid in water. The hemiacetal was produced at all sulfuric acid concentrations studied, 30-96 wt% sulfuric acid in water. Aerosols up to 88.4 wt% organic/11.1 wt% H 2SO 4/0.5 wt% water were produced via these two dimerization reaction pathways. The UV-VIS spectrum of the isolated aldol condensation product, 2-butyl 2-octenal, extends into the visible region, suggesting these reactions may impact aerosol optical properties as well as aerosol composition. In contrast to previous suggestions, no polymerization of hexanal or its products was observed at any sulfuric acid concentration studied, from 30 to 96 wt% in water.

  9. 40 CFR 721.9220 - Reaction products of secondary alkyl amines with a substituted benzenesulfonic acid and sulfuric...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... amines with a substituted benzenesulfonic acid and sulfuric acid (generic name). 721.9220 Section 721... Reaction products of secondary alkyl amines with a substituted benzenesulfonic acid and sulfuric acid... benzenesulfonic acid and sulfuric acid (PMNs P-89-703, P-89-755, and P-89-756) are subject to reporting under this...

  10. 40 CFR 721.9220 - Reaction products of secondary alkyl amines with a substituted benzenesulfonic acid and sulfuric...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... amines with a substituted benzenesulfonic acid and sulfuric acid (generic name). 721.9220 Section 721... Reaction products of secondary alkyl amines with a substituted benzenesulfonic acid and sulfuric acid... benzenesulfonic acid and sulfuric acid (PMNs P-89-703, P-89-755, and P-89-756) are subject to reporting under this...

  11. 40 CFR 721.9220 - Reaction products of secondary alkyl amines with a substituted benzenesulfonic acid and sulfuric...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... amines with a substituted benzenesulfonic acid and sulfuric acid (generic name). 721.9220 Section 721... Reaction products of secondary alkyl amines with a substituted benzenesulfonic acid and sulfuric acid... benzenesulfonic acid and sulfuric acid (PMNs P-89-703, P-89-755, and P-89-756) are subject to reporting under this...

  12. 40 CFR 721.9220 - Reaction products of secondary alkyl amines with a substituted benzenesulfonic acid and sulfuric...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... amines with a substituted benzenesulfonic acid and sulfuric acid (generic name). 721.9220 Section 721... Reaction products of secondary alkyl amines with a substituted benzenesulfonic acid and sulfuric acid... benzenesulfonic acid and sulfuric acid (PMNs P-89-703, P-89-755, and P-89-756) are subject to reporting under this...

  13. 40 CFR 721.9220 - Reaction products of secondary alkyl amines with a substituted benzenesulfonic acid and sulfuric...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... amines with a substituted benzenesulfonic acid and sulfuric acid (generic name). 721.9220 Section 721... Reaction products of secondary alkyl amines with a substituted benzenesulfonic acid and sulfuric acid... benzenesulfonic acid and sulfuric acid (PMNs P-89-703, P-89-755, and P-89-756) are subject to reporting under this...

  14. SULFURIC ACID REMOVAL PROCESS EVALUATION: LONG-TERM RESULTS

    SciTech Connect

    Gary M. Blythe; Richard McMillan

    2002-07-03

    The objective of this project is to demonstrate the use of alkaline reagents injected into the furnace of coal-fired boilers as a means of controlling sulfuric acid emissions. The project is being co-funded by the U.S. DOE National Energy Technology Laboratory, under Cooperative Agreement DE-FC26-99FT40718, along with EPRI, the American Electric Power Company (AEP), FirstEnergy Corp., the Tennessee Valley Authority, and Dravo Lime, Inc. Sulfuric acid controls are becoming of increasing interest to power generators with coal-fired units for a number of reasons. Sulfuric acid is a Toxic Release Inventory species and can cause a variety of plant operation problems such as air heater plugging and fouling, back-end corrosion, and plume opacity. These issues will likely be exacerbated with the retrofit of selective catalytic reduction (SCR) for NO{sub x} control on many coal-fired plants, as SCR catalysts are known to further oxidize a portion of the flue gas SO{sub 2} to SO{sub 3}. The project previously tested the effectiveness of furnace injection of four different calcium-and/or magnesium-based alkaline sorbents on full-scale utility boilers. These reagents were tested during four one- to two-week tests conducted on two FirstEnergy Bruce Mansfield Plant (BMP) units. One of the sorbents tested was a magnesium hydroxide byproduct slurry produced from a modified Thiosorbic{reg_sign} Lime wet flue gas desulfurization system. The other three sorbents are available commercially and include dolomite, pressure-hydrated dolomitic lime, and commercial magnesium hydroxide. The dolomite reagent was injected as a dry powder through out-of-service burners, while the other three reagents were injected as slurries through air-atomizing nozzles inserted through the front wall of the upper furnace, either across from the nose of the furnace or across from the pendant superheater tubes. After completing the four one- to two-week tests, the most promising sorbents were selected for

  15. Comparison between the single-bubble sonoluminescences in sulfuric acid and in water

    NASA Astrophysics Data System (ADS)

    Huang, Wei; Chen, Weizhong; Gao, Xianxian; Liang, Yue

    2009-02-01

    Single-bubble sonoluminescence (SBSL) is achieved with strong stability in sulfuric acid solutions. Bubble dynamics and the SBSL spectroscopy in the sulfuric acid solutions with different concentrations are studied with phase-locked integral stroboscopic photography method and a spectrograph, respectively. The experimental results are compared with those in water. The SBSL in sulfuric acid is brighter than that in water. One of the most important reasons for that is the larger viscosity of sulfuric acid, which results in the larger ambient radius and thus the more contents of luminous material inside the bubble. However, sonoluminescence bubble’s collapse in sulfuric acid is less violent than that in water, and the corresponding blackbody radiation temperature of the SBSL in sulfuric acid is lower than that in water.

  16. Advances in Acid Concentration Membrane Technology for the Sulfur-Iodine Thermochemical Cycle

    SciTech Connect

    Frederick F. Stewart; Christopher J. Orme

    2006-11-01

    One of the most promising cycles for the thermochemical generation of hydrogen is the Sulfur-Iodine (S-I) process, where aqueous HI is thermochemically decomposed into H2 and I2 at approximately 350 degrees Celsius. Regeneration of HI is accomplished by the Bunsen reaction (reaction of SO2, water, and iodine to generate H2SO4 and HI). Furthermore, SO2 is regenerated from the decomposition of H2SO4 at 850 degrees Celsius yielding the SO2 as well as O2. Thus, the cycle actually consists of two concurrent oxidation-reduction loops. As HI is regenerated, co-produced H2SO4 must be separated so that each may be decomposed. Current flowsheets employ a large amount (~83 mol% of the entire mixture) of elemental I2 to cause the HI and the H2SO4 to separate into two phases. To aid in the isolation of HI, which is directly decomposed into hydrogen, water and iodine must be removed. Separation of iodine is facilitated by removal of water. Sulfuric acid concentration is also required to facilitate feed recycling to the sulfuric acid decomposer. Decomposition of the sulfuric acid is an equilibrium limited process that leaves a substantial portion of the acid requiring recycle. Distillation of water from sulfuric acid involves significant corrosion issues at the liquid-vapor interface. Thus, it is desirable to concentrate the acid without boiling. Recent efforts at the INL have concentrated on applying pervaporation through Nafion-117, Nafion-112, and sulfonated poly(etheretherketone) (S-PEEK) membranes for the removal of water from HI/water and HI/Iodine/water feedstreams. In pervaporation, a feed is circulated at low pressure across the upstream side of the membrane, while a vacuum is applied downstream. Selected permeants sorb into the membrane, transport through it, and are vaporized from the backside. Thus, a concentration gradient is established, which provides the driving force for transport. In this work, membrane separations have been performed at temperatures as high as

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

    PubMed

    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

  18. A rotamer energy level study of sulfuric acid

    NASA Astrophysics Data System (ADS)

    Partanen, Lauri; Pesonen, Janne; Sjöholm, Elina; Halonen, Lauri

    2013-10-01

    It is a common approach in quantum chemical calculations for polyatomic molecules to rigidly constrain some of the degrees of freedom in order to make the calculations computationally feasible. However, the presence of the rigid constraints also affects the kinetic energy operator resulting in the frozen mode correction, originally derived by Pesonen [J. Chem. Phys. 139, 144310 (2013)]. In this study, we compare the effects of this correction to several different approximations to the kinetic energy operator used in the literature, in the specific case of the rotamer energy levels of sulfuric acid. The two stable conformers of sulfuric acid are connected by the rotations of the O-S-O-H dihedral angles and possess C2 and Cs symmetry in the order of increasing energy. Our results show that of the models tested, the largest differences with the frozen mode corrected values were obtained by simply omitting the passive degrees of freedom. For the lowest 17 excited states, this inappropriate treatment introduces an increase of 9.6 cm-1 on average, with an increase of 8.7 cm-1 in the zero-point energies. With our two-dimensional potential energy surface calculated at the CCSD(T)-F12a/VDZ-F12 level, we observe a radical shift in the density of states compared to the harmonic picture, combined with an increase in zero point energy. Thus, we conclude that the quantum mechanical inclusion of the different conformers of sulfuric acid have a significant effect on its vibrational partition function, suggesting that it will also have an impact on the computational values of the thermodynamic properties of any reactions where sulfuric acid plays a role. Finally, we also considered the effect of the anharmonicities for the other vibrational degrees of freedom with a VSCF-calculation at the DF-MP2-F12/VTZ-F12 level of theory but found that the inclusion of the other conformer had the more important effect on the vibrational partition function.

  19. Sulfuric acid cloud interpretation of the infrared spectrum of Venus

    NASA Technical Reports Server (NTRS)

    Martonchik, J. V.

    1974-01-01

    Sulfuric acid single-cloud models are compared with the Venus spectrum in the 8-14 micron region. The results indicate that a cloud composed of a 75 percent H2SO4 solution and with a particle density of 100 per cu cm is in good agreement with observations. In addition to explaining the 11.2 micron absorption, this model also predicts an absorption feature at 16.7 microns which should be detectable if the observation is made from an aircraft.

  20. A rotamer energy level study of sulfuric acid.

    PubMed

    Partanen, Lauri; Pesonen, Janne; Sjöholm, Elina; Halonen, Lauri

    2013-10-14

    It is a common approach in quantum chemical calculations for polyatomic molecules to rigidly constrain some of the degrees of freedom in order to make the calculations computationally feasible. However, the presence of the rigid constraints also affects the kinetic energy operator resulting in the frozen mode correction, originally derived by Pesonen [J. Chem. Phys. 139, 144310 (2013)]. In this study, we compare the effects of this correction to several different approximations to the kinetic energy operator used in the literature, in the specific case of the rotamer energy levels of sulfuric acid. The two stable conformers of sulfuric acid are connected by the rotations of the O-S-O-H dihedral angles and possess C2 and Cs symmetry in the order of increasing energy. Our results show that of the models tested, the largest differences with the frozen mode corrected values were obtained by simply omitting the passive degrees of freedom. For the lowest 17 excited states, this inappropriate treatment introduces an increase of 9.6 cm(-1) on average, with an increase of 8.7 cm(-1) in the zero-point energies. With our two-dimensional potential energy surface calculated at the CCSD(T)-F12a/VDZ-F12 level, we observe a radical shift in the density of states compared to the harmonic picture, combined with an increase in zero point energy. Thus, we conclude that the quantum mechanical inclusion of the different conformers of sulfuric acid have a significant effect on its vibrational partition function, suggesting that it will also have an impact on the computational values of the thermodynamic properties of any reactions where sulfuric acid plays a role. Finally, we also considered the effect of the anharmonicities for the other vibrational degrees of freedom with a VSCF-calculation at the DF-MP2-F12/VTZ-F12 level of theory but found that the inclusion of the other conformer had the more important effect on the vibrational partition function.

  1. FURNACE INJECTION OF ALKALINE SORBENTS FOR SULFURIC ACID CONTROL

    SciTech Connect

    Gary M. Blythe

    2003-06-01

    This document summarizes progress on Cooperative Agreement DE-FC26-99FT40718, Furnace Injection of Alkaline Sorbents for Sulfuric Acid Control, during the time period October 1, 2002 through March 31, 2003. The objective of this project is to demonstrate the use of alkaline reagents injected into the furnace of coal-fired boilers as a means of controlling sulfuric acid emissions. The coincident removal of hydrochloric acid and hydrofluoric acid is also being determined, as is the removal of arsenic, a known poison for NO{sub x} selective catalytic reduction (SCR) catalysts. EPRI, the Tennessee Valley Authority (TVA), FirstEnergy Corporation, American Electric Power (AEP) and the Dravo Lime Company are project co-funders. URS Group is the prime contractor. This is the seventh reporting period for the subject Cooperative Agreement. During previous reporting periods, two long-term sorbent injection tests were conducted, one on Unit 3 at FirstEnergy's Bruce Mansfield Plant (BMP) and one on Unit 1 at AEP's Gavin Plant. Those tests determined the effectiveness of injecting alkaline slurries into the upper furnace of the boiler as a means of controlling sulfuric acid emissions from these units. The alkaline slurries tested included commercially available magnesium hydroxide slurry (Gavin Plant), and a byproduct magnesium hydroxide slurry (both Gavin Plant and BMP). The tests showed that injecting either the commercial or the byproduct magnesium hydroxide slurry could achieve up to 70-75% overall sulfuric acid removal. At BMP, the overall removal was limited by the need to maintain acceptable electrostatic precipitator (ESP) particulate control performance. At Gavin Plant, the overall sulfuric acid removal was limited because the furnace injected sorbent was less effective at removing SO{sub 3} formed across the SCR system installed on the unit for NO{sub x} control than at removing SO{sub 3} formed in the furnace. The SO3 removal results were presented in the semi

  2. 40 CFR 721.7770 - Alkylphenoxypoly(oxyethylene) sulfuric acid ester, substituted amine salt.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... acid ester, substituted amine salt. 721.7770 Section 721.7770 Protection of Environment ENVIRONMENTAL... Significant New Uses for Specific Chemical Substances § 721.7770 Alkylphenoxypoly(oxyethylene) sulfuric acid...) The chemical substance identified as alkyl phenoxypoly(oxyethylene) sulfuric acid ester, substituted...

  3. What Is Required for Highly Oxidized Molecules To Form Clusters with Sulfuric Acid?

    PubMed

    Elm, Jonas; Myllys, Nanna; Kurtén, Theo

    2017-06-15

    We have studied the specific requirements of a given neutral organic molecule to act as a stabilizer in sulfuric acid induced new particle formation. Based on an analysis of the reaction Gibbs free energies between simple functional groups and sulfuric acid, carboxylic acid groups are identified to show the strongest hydrogen bonding interaction with sulfuric acid. The free energy associated with the hydrogen bonding between sulfuric acid and 14 different carboxylic acids of atmospheric relevance reveal that the binding strength is very dependent on the ability of sulfuric acid to form an additional hydrogen bond via its vacant S-OH group to a γ-carbonyl group in the organic molecule. Extending the analysis to monoterpene oxidation products and further to large dimer esters, we identify the following necessary criteria for a given organic oxidation product to efficiently stabilize sulfuric acid clustering: (1) weak or no intramolecular hydrogen bonds in the isolated monomer; (2) more than two carboxylic acid groups. As a proof of concept we show that these requirements correspond to the docking of a sulfuric acid molecule between two non-interacting carboxylic acid groups in the organic molecule. These findings suggests that, for a given organic oxidation product to participate in the initial steps in new particle formation involving sulfuric acid, very distinct molecular features are required.

  4. Acid-base accounting assessment of mine wastes using the chromium reducible sulfur method.

    PubMed

    Schumann, Russell; Stewart, Warwick; Miller, Stuart; Kawashima, Nobuyuki; Li, Jun; Smart, Roger

    2012-05-01

    The acid base account (ABA), commonly used in assessment of mine waste materials, relies in part on calculation of potential acidity from total sulfur measurements. However, potential acidity is overestimated where organic sulfur, sulfate sulfur and some sulfide compounds make up a substantial portion of the sulfur content. The chromium reducible sulfur (CRS) method has been widely applied to assess reduced inorganic sulfur forms in sediments and acid sulfate soils, but not in ABA assessment of mine wastes. This paper reports the application of the CRS method to measuring forms of sulfur commonly found in mine waste materials. A number of individual sulfur containing minerals and real waste materials were analyzed using both CRS and total S and the potential acidity estimates were compared with actual acidity measured from net acid generation tests and column leach tests. The results of the CRS analysis made on individual minerals demonstrate good assessment of sulfur from a range of sulfides. No sulfur was measured using the CRS method in a number of sulfate salts, including jarosite and melanterite typically found in weathered waste rocks, or from dibenzothiophene characteristic of organic sulfur compounds common to coal wastes. Comparison of ABA values for a number of coal waste samples demonstrated much better agreement of acidity predicted from CRS analysis than total S analysis with actual acidity. It also resulted in reclassification of most samples tested from PAF to NAF. Similar comparisons on base metal sulfide wastes generally resulted in overestimation of the acid potential by total S and underestimation of the acid potential by CRS in comparison to acidity measured during NAG tests, but did not generally result in reclassification. In all the cases examined, the best estimate of potential acidity included acidity calculated from both CRS and jarositic S. Copyright © 2012 Elsevier B.V. All rights reserved.

  5. Hydration of pure and base-Containing sulfuric acid clusters studied by computational chemistry methods

    NASA Astrophysics Data System (ADS)

    Henschel, Henning; Ortega, Ismael K.; Kupiainen, Oona; Olenius, Tinja; Kurtén, Theo; Vehkamäki, Hanna

    2013-05-01

    The formation of hydrates of small molecular sulfuric acid clusters and cluster containing both sulfuric acid and base (ammonia or dimethylamine) has been studied by means of computational chemistry. Using a combined ab initio/density functional approach, formation energies of clusters with up to four sulfuric acid molecules, and up to two base molecules, have been calculated. Consequences for the hydration level of the corresponding clusters have been modelled. While the majority of pure sulfuric acid cluster are comparatively strongly hydrated, base containing cluster were found to be less hydrophilic. Dimethylamine is particularly effective in lowering the hydrophilicity of the cluster. Implications of the hydration profiles on atmospheric processes are discussed.

  6. Protonation of Alcohols in Sulfuric Acid Solutions at UT/LS Conditions

    NASA Astrophysics Data System (ADS)

    Michelsen, R. R.; Vernier, K.; Axson, J.; Morley, D.

    2007-12-01

    The protonation of several small alcohols (ethanol, 2-propanol, and 1-butanol) in cold sulfuric acid aqueous solutions was measured using variable temperature 13C nuclear magnetic resonance (NMR) spectroscopy. The acidity of the sulfuric acid + deuterium oxide solutions ranged from 43 to 81 weight percent (wt %) H2SO4. The pKBH+ values, which are a measure of the acidity of each alcohol, range from -2.0 for butanol at room temperature to -2.2 for ethanol at -20°C. The protonation enthalpies of the three alcohols over the temperature range of 22°C to -35°C were found to be small and negative, ranging from -1.8 kJ mol-1 for 2-propanol to -2.3 kJ mol-1 for ethanol. A small, negative protonation enthalpy means that the degree of protonation of the alcohol slightly decreases as temperature decreases. The pKBH+values and protonation enthalpies are used to predict the form of dissolved alcohols in sulfate aerosols. For typical upper troposphere/lower stratosphere (UT/LS) conditions (40-70 wt % H2SO4 and 220 K), all three alcohols increase from approximately 10% protonated in 40 wt % H2SO4 to over 60% protonated in 70 wt % H2SO4. The percent of protonated alcohol depends more strongly on m*, the slope factor of the excess acidity treatment, than on pKBH+ values. This relationship may reflect solvation effects. The treatment of strongly acidic, non-ideal solutions as applied to organic solutes in sulfate aerosol particles will be discussed.

  7. Adsorption of the complex ion Au(CN)2- onto sulfur-impregnated activated carbon in aqueous solutions.

    PubMed

    Ramírez-Muñiz, Kardia; Song, Shaoxian; Berber-Mendoza, Selene; Tong, Shitang

    2010-09-15

    The adsorption of the gold-cyanide complex ion (Au(CN)(2)(-)) on sulfur-impregnated activated carbon in aqueous solution has been studied in order to find a better adsorbent for the gold cyanidation process for extracting gold from ores. This study was performed using sulfur-impregnated activated carbon (SIAC 8.0) made from high-sulfur petroleum coke and an artificial aqueous solution of Au(CN)(2)(-). The experimental results have shown that Au(CN)(2)(-) strongly adsorbed onto the SIAC 8.0, leading the gold adsorption capacity of the SIAC 8.0 to be 2.25x that on conventional activated carbon. It has been also found that the adsorption fit the Langmuir isotherm well, and the adsorption density of Au(CN)(2)(-) on the SIAC 8.0 in aqueous solution increased with increasing temperature, suggesting chemical adsorption. The chemical adsorption might be attributed to the formation of S-Au-CN on SIAC 8.0 surfaces through the covalent bond between the gold atom of the ion and the sulfur in the molecular structure of the SIAC 8.0. In addition, the desorption test has demonstrated that the majority of the adsorption was irreversible, which depended on the density of the adsorption sites on the SIAC.

  8. Heterogeneous Chemistry of HONO on Liquid Sulfuric Acid: A New Mechanism of Chlorine Activation on Stratospheric Sulfate Aerosols

    NASA Technical Reports Server (NTRS)

    Zhang, Renyi; Leu, Ming-Taun; Keyser, Leon F.

    1996-01-01

    Heterogeneous chemistry of nitrous acid (HONO) on liquid sulfuric acid (H2SO4) Was investigated at conditions that prevail in the stratosphere. The measured uptake coefficient (gamma) of HONO on H2SO4 increased with increasing acid content, ranging from 0.03 for 65 wt % to about 0.1 for 74 wt %. In the aqueous phase, HONO underwent irreversible reaction with H2SO4 to form nitrosylsulfuric acid (NO(+)HSO4(-). At temperatures below 230 K, NO(+)HSO4(-) was observed to be stable and accumulated in concentrated solutions (less than 70 wt % H2SO4) but was unstable and quickly regenerated HONO in dilute solutions (less than 70 wt %). HCl reacted with HONO dissolved in sulfuric acid, releasing gaseous nitrosyl chloride (ClNO). The reaction probability between HCl and HONO varied from 0.01 to 0.02 for 60-72 wt % H2SO4. In the stratosphere, ClNO photodissociates rapidly to yield atomic chlorine, which catalytically destroys ozone. Analysis of the laboratory data reveals that the reaction of HCl with HONO on sulfate aerosols can affect stratospheric ozone balance during elevated sulfuric acid loadings after volcanic eruptions or due to emissions from the projected high-speed civil transport (HSCT). The present results may have important implications on the assessment of environmental acceptability of HSCT.

  9. Heterogeneous Chemistry of HONO on Liquid Sulfuric Acid: A New Mechanism of Chlorine Activation on Stratospheric Sulfate Aerosols

    NASA Technical Reports Server (NTRS)

    Zhang, Renyi; Leu, Ming-Taun; Keyser, Leon F.

    1996-01-01

    Heterogeneous chemistry of nitrous acid (HONO) on liquid sulfuric acid (H2SO4) Was investigated at conditions that prevail in the stratosphere. The measured uptake coefficient (gamma) of HONO on H2SO4 increased with increasing acid content, ranging from 0.03 for 65 wt % to about 0.1 for 74 wt %. In the aqueous phase, HONO underwent irreversible reaction with H2SO4 to form nitrosylsulfuric acid (NO(+)HSO4(-). At temperatures below 230 K, NO(+)HSO4(-) was observed to be stable and accumulated in concentrated solutions (less than 70 wt % H2SO4) but was unstable and quickly regenerated HONO in dilute solutions (less than 70 wt %). HCl reacted with HONO dissolved in sulfuric acid, releasing gaseous nitrosyl chloride (ClNO). The reaction probability between HCl and HONO varied from 0.01 to 0.02 for 60-72 wt % H2SO4. In the stratosphere, ClNO photodissociates rapidly to yield atomic chlorine, which catalytically destroys ozone. Analysis of the laboratory data reveals that the reaction of HCl with HONO on sulfate aerosols can affect stratospheric ozone balance during elevated sulfuric acid loadings after volcanic eruptions or due to emissions from the projected high-speed civil transport (HSCT). The present results may have important implications on the assessment of environmental acceptability of HSCT.

  10. Copper-Sulfate Pentahydrate as a Product of the Waste Sulfuric Acid Solution Treatment

    NASA Astrophysics Data System (ADS)

    Marković, Radmila; Stevanović, Jasmina; Avramović, Ljiljana; Nedeljković, Dragutin; Jugović, Branimir; Stajić-Trošić, Jasna; Gvozdenović, Milica

    2012-12-01

    The aim of this study is synthesis of copper-sulfate pentahydrate from the waste sulfuric acid solution-mother liquor generated during the regeneration process of copper bleed solution. Copper is removed from the mother liquor solution in the process of the electrolytic treatment using the insoluble lead anodes alloyed with 6 mass pct of antimony on the industrial-scale equipment. As the result of the decopperization process, copper is removed in the form of the cathode sludge and is precipitated at the bottom of the electrolytic cell. By this procedure, the content of copper could be reduced to the 20 mass pct of the initial value. Chemical characterization of the sludge has shown that it contains about 90 mass pct of copper. During the decopperization process, the very strong poison, arsine, can be formed, and the process is in that case terminated. The copper leaching degree of 82 mass pct is obtained using H2SO4 aqueous solution with the oxygen addition during the cathode sludge chemical treatment at 80 °C ± 5 °C. Obtained copper salt satisfies the requirements of the Serbian Standard for Pesticide, SRPS H.P1. 058. Therefore, the treatment of waste sulfuric acid solutions is of great economic and environmental interest.

  11. Laboratory measurements of heterogeneous reactions on sulfuric acid surfaces

    NASA Technical Reports Server (NTRS)

    Williams, Leah R.; Manion, Jeffrey A.; Golden, David M.; Tolbert, Margaret A.

    1994-01-01

    Increasing evidence from field, modeling, and laboratory studies suggests that heterogeneous reactions on stratospheric sulfate aerosol particles may contribute to global ozone depletion. Using a Knudsen cell reactor technique, the authors have studied the uptake, reactivity, and solubility of several trace atmospheric species on cold sulfuric acid surfaces representative of stratospheric aerosol particles. The results suggest that the heterogeneous conversion of N2O5 to HNO3 is fast enough to significantly affect the partitioning of nitrogen species in the global stratosphere and thus contribute to global ozone depletion. The hydrolysis of ClONO2 is slower and unlikely to be important under normal conditions at midlatitudes. The solubilities of HCl and HNO3 in sulfuric acid down to 200 K were found to be quite low. For HCl, this means that little HCl is available for reaction on the surfaces of stratospheric sulfate aerosol particles. The low solubility of HNO3 means that this product of heterogeneous reactions will enter the gas phase, and the denitrification observed in polar regions is unlikely to occur in the global stratosphere.

  12. Heterogeneous atmospheric reactions - Sulfuric acid aerosols as tropospheric sinks

    NASA Technical Reports Server (NTRS)

    Baldwin, A. C.; Golden, D. M.

    1979-01-01

    The reaction probabilities of various atmospheric species incident on a bulk sulfuric acid surface are measured in order to determine the role of sulfuric acid aerosols as pollutant sinks. Reaction products and unreacted starting materials leaving a Knudsen cell flow reactor after collision at 300 K with a H2SO4 surface or a soot surface were detected by mass spectrometry. Significant collision reaction probabilities are observed on a H2SO4 surface for H2O2, HNO3, HO2NO2, ClONO2, N2O5, H2O and NH3, and on soot for NH3. Estimates of the contribution of heterogeneous reactions to pollutant removal under atmospheric conditions indicate that while aerosol removal in the stratosphere is insignificant (loss rate constants approximately 10 to the -10th/sec), heterogeneous reactions may be the dominant loss process for several tropospheric species (loss rate constant approximately 10 to the -5th/sec, comparable to photolysis rate constants).

  13. Laboratory measurements of heterogeneous reactions on sulfuric acid surfaces

    NASA Technical Reports Server (NTRS)

    Williams, Leah R.; Manion, Jeffrey A.; Golden, David M.; Tolbert, Margaret A.

    1994-01-01

    Increasing evidence from field, modeling, and laboratory studies suggests that heterogeneous reactions on stratospheric sulfate aerosol particles may contribute to global ozone depletion. Using a Knudsen cell reactor technique, the authors have studied the uptake, reactivity, and solubility of several trace atmospheric species on cold sulfuric acid surfaces representative of stratospheric aerosol particles. The results suggest that the heterogeneous conversion of N2O5 to HNO3 is fast enough to significantly affect the partitioning of nitrogen species in the global stratosphere and thus contribute to global ozone depletion. The hydrolysis of ClONO2 is slower and unlikely to be important under normal conditions at midlatitudes. The solubilities of HCl and HNO3 in sulfuric acid down to 200 K were found to be quite low. For HCl, this means that little HCl is available for reaction on the surfaces of stratospheric sulfate aerosol particles. The low solubility of HNO3 means that this product of heterogeneous reactions will enter the gas phase, and the denitrification observed in polar regions is unlikely to occur in the global stratosphere.

  14. Solubility of HBr in sulfuric acid at stratospheric temperatures

    SciTech Connect

    Williams, L.R.; Golden, D.M.; Huestis, D.L.

    1995-04-20

    The solubility of HBr in 54 to 72 wt % sulfuric acid at low temperatures (200 to 240 K) was measured using two different experimental techniques. In the first, the time dependence of the uptake coefficient of HBr was measured in a Knudsen cell reactor and analyzed to give the effective Henry`s law coefficient. In the second, equilibrium vapor pressures of HBr (gas) over solutions containing known concentrations of HBr (dissolved) were measured. The two techniques were in good agreement. Typical values of the effective Henry`s law coefficient at 220 K were 1.5 x 10{sup 7} M/atm for 54 wt %, 2.2 x 10{sup 6} M/atm for 60 wt %, 1.5 x 10{sup 5} M/atm for 66 wt %, and 8.5 x 10{sup 3} M/atm for 72 wt % sulfuric acid. The measured solubilities combined with the stratospheric gas phase concentration of HBr indicate that very little HBr will be dissolved in stratospheric sulfate aerosol particles. 28 refs., 4 figs., 2 tabs.

  15. Involvement of Intermediate Sulfur Species in Biological Reduction of Elemental Sulfur under Acidic, Hydrothermal Conditions

    PubMed Central

    Druschel, Gregory K.

    2013-01-01

    The thermoacidophile and obligate elemental sulfur (S80)-reducing anaerobe Acidilobus sulfurireducens 18D70 does not associate with bulk solid-phase sulfur during S80-dependent batch culture growth. Cyclic voltammetry indicated the production of hydrogen sulfide (H2S) as well as polysulfides after 1 day of batch growth of the organism at pH 3.0 and 81°C. The production of polysulfide is likely due to the abiotic reaction between S80 and the biologically produced H2S, as evinced by a rapid cessation of polysulfide formation when the growth temperature was decreased, inhibiting the biological production of sulfide. After an additional 5 days of growth, nanoparticulate S80 was detected in the cultivation medium, a result of the hydrolysis of polysulfides in acidic medium. To examine whether soluble polysulfides and/or nanoparticulate S80 can serve as terminal electron acceptors (TEA) supporting the growth of A. sulfurireducens, total sulfide concentration and cell density were monitored in batch cultures with S80 provided as a solid phase in the medium or with S80 sequestered in dialysis tubing. The rates of sulfide production in 7-day-old cultures with S80 sequestered in dialysis tubing with pore sizes of 12 to 14 kDa and 6 to 8 kDa were 55% and 22%, respectively, of that of cultures with S80 provided as a solid phase in the medium. These results indicate that the TEA existed in a range of particle sizes that affected its ability to diffuse through dialysis tubing of different pore sizes. Dynamic light scattering revealed that S80 particles generated through polysulfide rapidly grew in size, a rate which was influenced by the pH of the medium and the presence of organic carbon. Thus, S80 particles formed through abiological hydrolysis of polysulfide under acidic conditions appeared to serve as a growth-promoting TEA for A. sulfurireducens. PMID:23335768

  16. FURNACE INJECTION OF ALKALINE SORBENTS FOR SULFURIC ACID REMOVAL

    SciTech Connect

    Gary M. Blythe

    2004-01-01

    The objective of this project has been to demonstrate the use of alkaline reagents injected into the furnace of coal-fired boilers as a means of controlling sulfuric acid emissions. The project was co-funded by the U.S. DOE National Energy Technology Laboratory under Cooperative Agreement DE-FC26-99FT40718, along with EPRI, the American Electric Power Company (AEP), FirstEnergy Corporation, the Tennessee Valley Authority, and Carmeuse North America. Sulfuric acid controls are becoming of increased interest for coal-fired power generating units for a number of reasons. In particular, sulfuric acid can cause plant operation problems such as air heater plugging and fouling, back-end corrosion, and plume opacity. These issues will likely be exacerbated with the retrofit of selective catalytic reduction (SCR) for NOX control, as SCR catalysts are known to further oxidize a portion of the flue gas SO{sub 2} to SO{sub 3}. The project tested the effectiveness of furnace injection of four different magnesium-based or dolomitic alkaline sorbents on full-scale utility boilers. These reagents were tested during one- to two-week tests conducted on two FirstEnergy Bruce Mansfield Plant (BMP) units. One of the sorbents tested was a magnesium hydroxide slurry byproduct from a modified Thiosorbic{reg_sign} Lime wet flue gas desulfurization process. The other three sorbents are available commercially and include dolomite, pressure-hydrated dolomitic lime, and commercially available magnesium hydroxide. The dolomite reagent was injected as a dry powder through out-of-service burners. The other three reagents were injected as slurries through air-atomizing nozzles inserted through the front wall of the upper furnace. After completing the four one- to two-week tests, the most promising sorbents were selected for longer-term (approximately 25-day) full-scale tests on two different units. The longer-term tests were conducted to confirm sorbent effectiveness over extended operation on two

  17. Interaction of Ethyl Alcohol Vapor with Sulfuric Acid Solutions

    NASA Technical Reports Server (NTRS)

    Leu, Ming-Taun

    2006-01-01

    We investigated the uptake of ethyl alcohol (ethanol) vapor by sulfuric acid solutions over the range approx.40 to approx.80 wt % H2SO4 and temperatures of 193-273 K. Laboratory studies used a fast flow-tube reactor coupled to an electron-impact ionization mass spectrometer for detection of ethanol and reaction products. The uptake coefficients ((gamma)) were measured and found to vary from 0.019 to 0.072, depending upon the acid composition and temperature. At concentrations greater than approx.70 wt % and in dilute solutions colder than 220 K, the values approached approx.0.07. We also determined the effective solubility constant of ethanol in approx.40 wt % H2SO4 in the temperature range 203-223 K. The potential implications to the budget of ethanol in the global troposphere are briefly discussed.

  18. Interaction of Ethyl Alcohol Vapor with Sulfuric Acid Solutions

    NASA Technical Reports Server (NTRS)

    Leu, Ming-Taun

    2006-01-01

    We investigated the uptake of ethyl alcohol (ethanol) vapor by sulfuric acid solutions over the range approx.40 to approx.80 wt % H2SO4 and temperatures of 193-273 K. Laboratory studies used a fast flow-tube reactor coupled to an electron-impact ionization mass spectrometer for detection of ethanol and reaction products. The uptake coefficients ((gamma)) were measured and found to vary from 0.019 to 0.072, depending upon the acid composition and temperature. At concentrations greater than approx.70 wt % and in dilute solutions colder than 220 K, the values approached approx.0.07. We also determined the effective solubility constant of ethanol in approx.40 wt % H2SO4 in the temperature range 203-223 K. The potential implications to the budget of ethanol in the global troposphere are briefly discussed.

  19. Sulfuric Acid Monohydrate: Formation and Heterogeneous Chemistry in the Stratosphere

    NASA Technical Reports Server (NTRS)

    Zhang, Renyi; Leu, Ming-Taun; Keyser, Leon F.

    1995-01-01

    We have investigated some thermodynamic properties (i.e., freezing/melting points) and heterogeneous chemistry of sulfuric acid monohydrate (SAM, H2SO4.H2O), using a fast flow reactor coupled to a quadrupole mass spectrometer. The freezing point observations of thin liquid sulfuric acid films show that for acid contents between 75 and 85 wt % the monohydrate crystallizes readily at temperatures between 220 and 240 K on a glass substrate. Once formed, SAM can be thermodynamically stable in the H2O partial pressure range of (1-4) x 10(exp -4) torr and in the temperature range of 220-240 K. For a constant H2O partial pressure, lowering the temperature causes SAM to melt when the temperature and water partial pressure conditions are out of its stability regime. The reaction probability measurements indicate that the hydrolysis of N2O5 is significantly suppressed owing to the formation of crystalline SAM: The reaction probability on water-rich SAM (with higher relative humidity, or RH) is of the order of 10(exp -3) at 210 K and decreases by more than an order of magnitude for the acid-rich form (with lower RH). The hydrolysis rate of ClONO2 on water-rich SAM is even smaller, of the order of 10(exp -4) at 195 K. These reported values on crystalline SAM are much smaller than those on liquid solutions. No enhancement of these reactions is observed in the presence of HCl vapor at the stratospheric concentrations. In addition, Brunauer, Emmett, and Teller analysis of gas adsorption isotherms and photomicrography have been performed to characterize the surface roughness and porosities of the SAM substrate. The results suggest the possible formation of SAM in some regions of the middle- or low-latitude stratosphere and, consequently, much slower heterogeneous reactions on the frozen aerosols.

  20. Sulfuric acid monohydrate: Formation and heterogeneous chemistry in the stratosphere

    NASA Astrophysics Data System (ADS)

    Zhang, Renyi; Leu, Ming-Taun; Keyser, Leon F.

    1995-09-01

    We have investigated some thermodynamic properties (i.e., freezing/melting points) and heterogeneous chemistry of sulfuric acid monohydrate (SAM, H2SO4 · H2O), using a fast flow reactor coupled to a quadrupole mass spectrometer. The freezing point observations of thin liquid sulfuric acid films show that for acid contents between 75 and 85 wt % the monohydrate crystallizes readily at temperatures between 220 and 240 K on a glass substrate. Once formed, SAM can be thermodynamically stable in the H2O partial pressure range of (1-4)×10-4 torr and in the temperature range of 220-240 K. For a constant H2O partial pressure, lowering the temperature causes SAM to melt when the temperature and water partial pressure conditions are out of its stability regime. The reaction probability measurements indicate that the hydrolysis of N2O5 is significantly suppressed owing to the formation of crystalline SAM: The reaction probability on water-rich SAM (with higher relative humidity, or RH) is of the order of 10-3 at 210 K and decreases by more than an order of magnitude for the acid-rich form (with lower RH). The hydrolysis rate of ClONO2 on water-rich SAM is even smaller, of the order of 10-4 at 195 K. These reported values on crystalline SAM are much smaller than those on liquid solutions. No enhancement of these reactions is observed in the presence of HCl vapor at the stratospheric concentrations. In addition, Brunauer, Emmett, and Teller analysis of gas adsorption isotherms and photomicrography have been performed to characterize the surface roughness and porosities of the SAM substrate. The results suggest the possible formation of SAM in some regions of the middle- or low-latitude stratosphere and, consequently, much slower heterogeneous reactions on the frozen aerosols.

  1. Sulfuric Acid Monohydrate: Formation and Heterogeneous Chemistry in the Stratosphere

    NASA Technical Reports Server (NTRS)

    Zhang, Renyi; Leu, Ming-Taun; Keyser, Leon F.

    1995-01-01

    We have investigated some thermodynamic properties (i.e., freezing/melting points) and heterogeneous chemistry of sulfuric acid monohydrate (SAM, H2SO4.H2O), using a fast flow reactor coupled to a quadrupole mass spectrometer. The freezing point observations of thin liquid sulfuric acid films show that for acid contents between 75 and 85 wt % the monohydrate crystallizes readily at temperatures between 220 and 240 K on a glass substrate. Once formed, SAM can be thermodynamically stable in the H2O partial pressure range of (1-4) x 10(exp -4) torr and in the temperature range of 220-240 K. For a constant H2O partial pressure, lowering the temperature causes SAM to melt when the temperature and water partial pressure conditions are out of its stability regime. The reaction probability measurements indicate that the hydrolysis of N2O5 is significantly suppressed owing to the formation of crystalline SAM: The reaction probability on water-rich SAM (with higher relative humidity, or RH) is of the order of 10(exp -3) at 210 K and decreases by more than an order of magnitude for the acid-rich form (with lower RH). The hydrolysis rate of ClONO2 on water-rich SAM is even smaller, of the order of 10(exp -4) at 195 K. These reported values on crystalline SAM are much smaller than those on liquid solutions. No enhancement of these reactions is observed in the presence of HCl vapor at the stratospheric concentrations. In addition, Brunauer, Emmett, and Teller analysis of gas adsorption isotherms and photomicrography have been performed to characterize the surface roughness and porosities of the SAM substrate. The results suggest the possible formation of SAM in some regions of the middle- or low-latitude stratosphere and, consequently, much slower heterogeneous reactions on the frozen aerosols.

  2. Aqueous-phase source of formic acid in clouds

    NASA Technical Reports Server (NTRS)

    Chameides, W. L.; Davis, D. D.

    1983-01-01

    The coupled gas- and aqueous-phase cloud chemistry of HCOOH were examined for controlling factors in the acidity of cloud and rainwater. Attention was given to the aqueous OH/HO2 system that yields an OH species that is highly reactive with other species, notably SO2 and the formaldehyde/formic acid complex. A numerical model was developed to simulate the cloud chemistry in the remote troposphere, with considerations given to CH4-CO-NO(x)-O3-H(x)O(y) system. It was determined that aqueous phase OH radicals can produce and destroy formic acid droplets in daylight conditions, as well as control formic acid levels in rainwater. It is sugested that the same types of reactions may be involved in the control of acetic acid and other organic acids.

  3. Theoretical estimation of equilibrium sulfur isotope fractionations among aqueous sulfite species: Implications for isotope models of microbial sulfate reduction

    NASA Astrophysics Data System (ADS)

    Eldridge, D. L.; Farquhar, J.; Guo, W.

    2015-12-01

    Sulfite (sensu lato), an intermediate in a variety sulfur redox processes, plays a particularly important role in microbial sulfate reduction. It exists intracellularly as multiple species between sets of enzymatic reactions that transform sulfate to sulfide, with the exact speciation depending on pH, T, and ionic strength. However, the complex speciation of sulfite is ignored in current isotope partitioning models of microbial sulfate reduction and simplified solely to the pyramidal SO32- (sulfite sensu stricto), due to a lack of appropriate constraints. We theoretically estimated the equilibrium sulfur isotope fractionations (33S/32S, 34S/32S, 36S/32S) among all documented sulfite species in aqueous solution, including sulfite (SO32-), bisulfite isomers and dimers ((HS)O3-, (HO)SO2-, S2O52-), and SO2(aq), through first principles quantum mechanical calculations. The calculations were performed at B3LYP/6-31+G(d,p) level using cluster models with 30-40 water molecules surrounding the solute. Our calculated equilibrium fractionation factors compare well to the available experimental constraints and suggest that the minor and often-ignored tetrahedral (HS)O3- isomer of bisulfite strongly influences isotope partitioning behavior in the sulfite system under most environmentally relevant conditions, particularly fractionation magnitudes and unusual temperature dependence. For example, we predict that sulfur isotope fractionation between sulfite and bulk bisulfite in solution should have an apparent inverse temperature dependence due to the influence of (HS)O3- and its increased stability at higher temperatures. Our findings highlight the need to appropriately account for speciation/isomerization of sulfur species in sulfur isotope studies. We will also present similar calculation results of other aqueous sulfur compounds (e.g., H2S/HS-, SO42-, S2O32-, S3O62-, and poorly documented SO22- species), and discuss the implication of our results for microbial sulfate

  4. Evaluating the Effects of Sediment Reworking on the Sulfur Isotopic Composition of Aqueous and Mineral Sulfides

    NASA Astrophysics Data System (ADS)

    Johnson, D.; Rose, C.; Fike, D. A.

    2014-12-01

    The sulfur isotopic compositions of sulfide minerals preserved in the rock record are widely used in reconstructions of past ocean and atmospheric chemistry, but little is known about how syn- and post-depositional processes may affect these compositions. Furthermore, recent discoveries of pyrite more enriched in 34S than coeval sulfate in the rock record (e.g., Ries et al., 2009) and in modern deltaic sediments (e.g., Aller et al., 2010) have indicated a need to develop a better understanding of the controls on isotopic fractionation during sulfur cycling in natural environments. Here, we report the results of a controlled laboratory experiment designed to simulate the repeated oxidative reworking of sediments using a series of sediment columns constructed with bulk carbonate mud from Florida Bay, Florida. A rapid decline in [H2S] was observed in reworked sediments during the first 12 weeks of the experiment. Decreases in the δ34S of sulfide phases and increases in Δ34SSO4-H2S (i.e., the difference between the δ34S of sulfate, δ34SSO4, and that of hydrogen sulfide, δ34SH2S, at a given depth) were also documented across all columns. These results indicate a decline in labile organic matter concentrations within the sediments and a corresponding decrease in MSR rates with time. Complete reoxidation did not generate superheavy pyrite in this study, but did stimulate biological activity through the generation of sharp redox boundaries. Partial oxidation of aqueous sulfide and an associated increase in residual δ34SH2S must thus be key if oxidation itself is important to superheavy pyrite formation. These findings further suggest that organic matter lability may have played a more fundamental role than [SO42-] in regulating MSR fractionation throughout Earth history and provide motivation for future research.

  5. Friction and wear of nickel in sulfuric acid

    NASA Technical Reports Server (NTRS)

    Rengstorff, G. W. P.; Miyoshi, K.; Buckley, D. H.

    1984-01-01

    Experiments were conducted with elemental nickel sliding on aluminum oxide in aerated sulfuric acid in concentrations ranging from very dilute (10 -4 N, i.e., 5 ppm) to very concentrated (96 percent) acid. Load and reciprocating sliding speeds were kept constant. With the most dilute concentration (10 -4 N) no observable corrosion occurred in or outside the wear area. This was used as the base condition to determine the high contribution of corrosion to total wear loss at acid concentrations between 0.5 percent (0.1 N) and 75 percent. Corrosion reached a maximum rate of 100 millimeters per year at 30 percent acid. At the same time, general corrosion outside the wear area was very low, in agreement with published information. It is clear that friction and wear greatly accelerated corrosion in the wear area. At dilute concentrations of 0.001 and 0.01 N, corrosion in the wear area was low, and general corrosion outside was also low, but local outside regions in the direction of the wear motion experienced some enhanced corrosion, apparently due to fluid motion of the acid.

  6. Synergy effect of naphthenic acid corrosion and sulfur corrosion in crude oil distillation unit

    NASA Astrophysics Data System (ADS)

    Huang, B. S.; Yin, W. F.; Sang, D. H.; Jiang, Z. Y.

    2012-10-01

    The synergy effect of naphthenic acid corrosion and sulfur corrosion at high temperature in crude oil distillation unit was studied using Q235 carbon-manganese steel and 316 stainless steel. The corrosion of Q235 and 316 in corrosion media containing sulfur and/or naphthenic acid at 280 °C was investigated by weight loss, scanning electron microscope (SEM), EDS and X-ray diffractometer (XRD) analysis. The results showed that in corrosion media containing only sulfur, the corrosion rate of Q235 and 316 first increased and then decreased with the increase of sulfur content. In corrosion media containing naphthenic acid and sulfur, with the variations of acid value or sulfur content, the synergy effect of naphthenic acid corrosion and sulfur corrosion has a great influence on the corrosion rate of Q235 and 316. It was indicated that the sulfur accelerated naphthenic acid corrosion below a certain sulfur content but prevented naphthenic acid corrosion above that. The corrosion products on two steels after exposure to corrosion media were investigated. The stable Cr5S8 phases detected in the corrosion products film of 316 were considered as the reason why 316 has greater corrosion resistance to that of Q235.

  7. Relative Order of Sulfuric Acid, Bisulfate, Hydronium, and Cations at the Air-Water Interface.

    PubMed

    Hua, Wei; Verreault, Dominique; Allen, Heather C

    2015-11-04

    Sulfuric acid (H2SO4), bisulfate (HSO4(-)), and sulfate (SO4(2-)) are among the most abundant species in tropospheric and stratospheric aerosols due to high levels of atmospheric SO2 emitted from biomass burning and volcanic eruptions. The air/aqueous interfaces of sulfuric acid and bisulfate solutions play key roles in heterogeneous reactions, acid rain, radiative balance, and polar stratospheric cloud nucleation. Molecular-level knowledge about the interfacial distribution of these inorganic species and their perturbation of water organization facilitates a better understanding of the reactivity and growth of atmospheric aerosols and of the aerosol surface charge, thus shedding light on topics of air pollution, climate change, and thundercloud electrification. Here, the air/aqueous interface of NaHSO4, NH4HSO4, and Mg(HSO4)2 salt solutions as well as H2SO4 and HCl acid solutions are investigated by means of vibrational sum frequency generation (VSFG) and heterodyne-detected (HD) VSFG spectroscopy. VSFG spectra of all acid solutions show higher SFG response in the OH-bonded region relative to neat water, with 1.1 M H2SO4 being more enhanced than 1.1 M HCl. In addition, VSFG spectra of bisulfate salt solutions highly resemble that of the dilute H2SO4 solution (0.26 M) at a comparable pH. HD-VSFG (Im χ((2))) spectra of acid and bisulfate salt solutions further reveal that hydrogen-bonded water molecules are oriented preferentially toward the bulk liquid phase. General agreement between Im χ((2)) spectra of 1.1 M H2SO4 and 1.1 M HCl acid solutions indicate that HSO4(-) ions have a similar surface preference as that of chloride (Cl(-)) ions. By comparing the direction and magnitude of the electric fields arising from the interfacial ion distributions and the concentration of each species, the most reasonable relative surface preference that can be deduced from a simplified model follows the order H3O(+) > HSO4(-) > Na(+), NH4(+), Mg(2+) > SO4(2-). Interestingly

  8. Sulfur redox reactions: Hydrocarbons, native sulfur, Mississippi Valley-type deposits, and sulfuric acid karst in the Delaware Basin, New Mexico and Texas

    SciTech Connect

    Hill, C.A.

    1995-02-01

    Hydrocarbons, native sulfur, Mississippi Valley-type (MVT) deposits, and sulfuric acid karst in the Delaware Basin, southeastern New Mexico, and west Texas, USA, are all genetically related through a series of sulfur redox reactions. The relationship began with hydrocarbons in the basin that reacted with sulfate ions from evaporite rock to produce isotopically light ({delta}{sup 34}S = -22 to -12) H{sub 2}S and bioepigenetic limestone (castiles). This light H{sub 2}S was then oxidized at the redox interface to produce economic native sulfur deposits ({delta}{sup 34}S = -15 to +9) in the castiles, paleokarst, and along graben-boundary faults. This isotopically light H{sub 2}S also migrated from the basin into its margins to accumulate in structural (anticlinal) and stratigraphic (Yates siltstone) traps, where it formed MVT deposits within the zone of reduction ({delta}{sup 34}S = -15 to +7). Later in time, in the zone of oxidation, this H{sub 2}S reacted with oxygenated water to produce sulfuric acid, which dissolved the caves (e.g., Carlsbad Cavern and Lechuguilla Cave, Guadalupe Mountains). Massive gypsum blocks on the floors of the caves ({delta}{sup 34}S = -25 to +4) were formed as a result of this reaction. The H{sub 2}S also produced isotopically light cave sulfur ({delta}{sup 34}S = -24 to -15), which is now slowly oxidizing to gypsum in the presence of vadose drip water. 16 refs., 10 figs.

  9. Effect of Bisulfate, Ammonia, and Ammonium on the Clustering of Organic Acids and Sulfuric Acid.

    PubMed

    Myllys, Nanna; Olenius, Tinja; Kurtén, Theo; Vehkamäki, Hanna; Riipinen, Ilona; Elm, Jonas

    2017-06-29

    We investigate the effect of the bisulfate anion HSO4(-), ammonium cation NH4(+), and ammonia NH3 on the clustering of sulfuric acid and pinic acid or 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA). The systems were chosen based on their expected relevance in atmospheric new particle formation. Using quantum chemical methods together with kinetic calculations, we study the ability of these compounds to enhance cluster formation and growth. The cluster structures are obtained and frequencies are calculated using three different DFT functionals (M06-2X, PW91, and ωB97X-D) with the 6-31++G(d,p) basis set. The electronic energies are corrected using an accurate DLPNO-CCSD(T)/def2-QZVPP level of theory. The evaporation rates are evaluated based on the calculated Gibbs free energies. The interaction between the ions and sulfuric acid or carboxylic acid group is strong, and thereby small two-component ionic clusters are found to be very stable against evaporation. The presence of bisulfate stimulates the cluster formation through addition of the sulfuric acid, whereas the presence of ammonium favors the addition of organic acids. Bisulfate and ammonium enhance the first steps of cluster formation; however, at atmospheric conditions further cluster growth is limited due to the weak interaction and fast evaporation of the larger three-component clusters. On the basis of our results it is therefore unlikely that the studied organic acids and sulfuric acid, even together with bisulfate, ammonia, or ammonium can drive new-particle formation via clustering mechanisms. Other mechanisms such as chemical reactions are needed to explain observed new-particle formation events in the presence of oxidized organic compounds resembling the acids studied here.

  10. A new test procedure for biogenic sulfuric acid corrosion of concrete

    PubMed

    Vincke; Verstichel; Monteny; Verstraete

    1999-01-01

    A new test method is described for biogenic sulfuric acid corrosion of concrete, more specifically in sewer conditions. The aim of the new test method is the development of an accelerated and reproducible procedure for monitoring the resistance of different types of concrete with regard to biogenic sulfuric acid corrosion. This experimental procedure reflects worst case conditions by providing besides H2S, also an enrichment of thiobacilli and biologically produced sulfur. By simulating the cyclic processes occurring in sewer pipes, significant differences between concrete mixtures could be detected after 51 days. Concrete modified by a styrene-acrylic ester polymer demonstrated a higher resistance against biogenic sulfuric acid attack.

  11. Coupled diffusion in aqueous weak acid + alkanolamine absorbents

    SciTech Connect

    Leaist, D.G.; Li, Y.; Poissant, R.

    1998-11-01

    Taylor dispersion and differential refractometry are used to measure ternary interdiffusion coefficients (D{sub ik}) for aqueous solutions of acetic acid + triethanolamine (TEA) and aqueous solutions of oxalic acid + TEA at 25 C. The D{sub ik} coefficients give the coupled fluxes of acid and TEA driven by the gradient in the concentration of each solute. Ternary Fick equations with variable D{sub ik} coefficients are integrated numerically to calculate accurate concentration profiles and the moving reaction front produced by the interdiffusion of TEA and acetic or oxalic acid. Ternary diffusion coefficients are also used to predict the rate of dissolution of oxalic acid in 1.00 mol/dm{sup 3} aqueous TEA, a process analogous to the absorption of a diprotic acid gas by an alkanolamine absorbent. The diffusion of oxalic acid drives a significant counterflow of TEA. The resulting buildup of TEA at the surface of the dissolving acid increases the interfacial concentration of TEA from 1.00 to 1.20 mol/dm{sup 3}, which in turn increases the solubility of the acid by 0.20 mol/dm{sup 3}. Nernst-Planck equations are used to predict D{sub ik} coefficients for aqueous weak acid + alkanolamine solutions. The fluxes of these solutes are shown to be strongly coupled by the electric field that is generated by the diffusing ions.

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

    PubMed

    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.

  13. Cyclic process for the removal of sulfur dioxide and the recovery of sulfur from gases

    SciTech Connect

    Lo, C.L.

    1991-11-19

    This patent describes a process for the removal of sulfur dioxide from a gas containing sulfur dioxide. It comprises contacting a gas containing sulfur dioxide with an aqueous solution comprising water, ferric chloride and a salt selected from the group consisting of barium chloride and calcium chloride to form ferrous chloride, hydrochloric acid and a precipitate selected from the group consisting of barium sulfate and calcium sulfate; and treating the aqueous solution with an oxidizing agent to convert ferrous chloride to ferric chloride.

  14. Thin-film sulfuric acid anodizing as a replacement for chromic acid anodizing

    NASA Technical Reports Server (NTRS)

    Kallenborn, K. J.; Emmons, J. R.

    1995-01-01

    Chromic acid has long been used to produce a thin, corrosion resistant (Type I) coating on aluminum. Following anodizing, the hardware was sealed using a sodium dichromate solution. Sealing closes up pores inherent in the anodized coating, thus improving corrosion resistance. The thinness of the brittle coating is desirable from a fatigue standpoint, and chromium was absorbed by the coating during the sealing process, further improving corrosion resistance. Unfortunately, both chromic acid and sodium dichromate contain carcinogenic hexavalent chromium. Sulfuric acid is being considered as a replacement for chromic acid. Sulfuric acid of 10-20 percent concentration has traditionally been used to produce relatively thick (Types II and III) or abrasion resistant (Type III) coatings. A more dilute, that is five weight percent, sulfuric acid anodizing process, which produces a thinner coating than Type II or III, with nickel acetate as the sealant has been developed. The process was evaluated in regard to corrosion resistance, throwing power, fatigue life, and processing variable sensitivity, and shows promise as a replacement for the chromic acid process.

  15. Unexpectedly acidic nanoparticles formed in dimethylamine-ammonia-sulfuric-acid nucleation experiments at CLOUD

    NASA Astrophysics Data System (ADS)

    Lawler, Michael J.; Winkler, Paul M.; Kim, Jaeseok; Ahlm, Lars; Tröstl, Jasmin; Praplan, Arnaud P.; Schobesberger, Siegfried; Kürten, Andreas; Kirkby, Jasper; Bianchi, Federico; Duplissy, Jonathan; Hansel, Armin; Jokinen, Tuija; Keskinen, Helmi; Lehtipalo, Katrianne; Leiminger, Markus; Petäjä, Tuukka; Rissanen, Matti; Rondo, Linda; Simon, Mario; Sipilä, Mikko; Williamson, Christina; Wimmer, Daniela; Riipinen, Ilona; Virtanen, Annele; Smith, James N.

    2016-11-01

    New particle formation driven by acid-base chemistry was initiated in the CLOUD chamber at CERN by introducing atmospherically relevant levels of gas-phase sulfuric acid and dimethylamine (DMA). Ammonia was also present in the chamber as a gas-phase contaminant from earlier experiments. The composition of particles with volume median diameters (VMDs) as small as 10 nm was measured by the Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS). Particulate ammonium-to-dimethylaminium ratios were higher than the gas-phase ammonia-to-DMA ratios, suggesting preferential uptake of ammonia over DMA for the collected 10-30 nm VMD particles. This behavior is not consistent with present nanoparticle physicochemical models, which predict a higher dimethylaminium fraction when NH3 and DMA are present at similar gas-phase concentrations. Despite the presence in the gas phase of at least 100 times higher base concentrations than sulfuric acid, the recently formed particles always had measured base : acid ratios lower than 1 : 1. The lowest base fractions were found in particles below 15 nm VMD, with a strong size-dependent composition gradient. The reasons for the very acidic composition remain uncertain, but a plausible explanation is that the particles did not reach thermodynamic equilibrium with respect to the bases due to rapid heterogeneous conversion of SO2 to sulfate. These results indicate that sulfuric acid does not require stabilization by ammonium or dimethylaminium as acid-base pairs in particles as small as 10 nm.

  16. Uptake of Ethyl Alcohol Vapor in Sulfuric Acid Solutions

    NASA Astrophysics Data System (ADS)

    Leu, M.

    2002-12-01

    The uptake of ethyl alcohol vapor in liquid sulfuric acid has been investigated over the composition range of 40 - 80 wt % H2SO4 and between the temperatures of 193-273 K. Laboratory studies were performed using a flow-tube reactor coupled to an electron-impact ionization mass spectrometer for detection of ethanol and possible reaction products, ethyl hydrogen sulfate and diethyl sulfate. The uptake coefficients (gamma) have been measured and found to vary from 0.018 to 0.065, depending upon the acid composition and temperature. For example, at concentrated acids greater than 70 wt % and dilute solutions (<70 wt %) colder than 210 K, the gamma values are approaching ~ 0.06. Under other conditions, the gamma values are smaller. The adsorption and thermal desorption measurements have been used to distinguish the possible uptake mechanisms, either solubility or reactive uptake. The results suggest that reactive uptakes are greater than 50 % under all conditions. For dilute acids, we also determine the effective Henry's law constants (H*). We will compare the results with the uptake of gaseous methyl alcohol and acetone in H2SO4 determined previously in our laboratory. The potential implications to the budget of ethyl alcohol in the global troposphere will also be discussed.

  17. Dilute sulfuric acid pretreatment of transgenic switchgrass for sugar production.

    PubMed

    Zhou, Xu; Xu, Jiele; Wang, Ziyu; Cheng, Jay J; Li, Ruyu; Qu, Rongda

    2012-01-01

    Conventional Alamo switchgrass and its transgenic counterparts with reduced/modified lignin were subjected to dilute sulfuric acid pretreatment for improved sugar production. At 150 °C, the effects of acid concentration (0.75%, 1%, 1.25%) and residence time (5, 10, 20, 30 min) on sugar productions in pretreatment and enzymatic hydrolysis were investigated, with the optimal pretreatment conditions determined for each switchgrass genotype based on total sugar yield and the amounts of sugar degradation products generated during the pretreatment. The results show that genetic engineering, although did not cause an appreciable lignin reduction, resulted in a substantial increase in the ratio of acid soluble lignin:acid insoluble lignin, which led to considerably increased sugar productions in both pretreatment and enzymatic hydrolysis. At an elevated threshold concentration of combined 5-hydroxyfuranmethal and furfural (2.0 g/L), the overall carbohydrate conversions of conventional switchgrass and its transgenic counterparts, 10/9-40 and 11/5-47, reached 75.9%, 82.6%, and 82.2%, respectively.

  18. Biological sulfuric acid transformation: Reactor design and process optimization

    SciTech Connect

    Stucki, G.; Huerzeler, R.A. ); Hanselmann, K.W. )

    1993-02-05

    As an alternative to the current disposal technologies for waste sulfuric acid, a new combination of recycling processes was developed. The strong acid (H[sub 2]SO[sub 4]) is biologically converted with the weak acid (CH[sub 3]COOH) into two volatile weak acids (H[sub 2]S, H[sub 2]CO[sub 3]) by sulfate-reducing bacteria. The transformation is possible without prior neutralization of the sulfuric acid. The microbially mediated transformation can be followed by physiocochemical processes for the further conversion of the H[sub 2]S. The reduction of sulfate to H[sub 2]S is carried out under carbon-limited conditions at pH 7.5 to 8.5. A fixed-bed biofilm column reactor is used in conjunction with a separate gas-stripping column which was installed in the recycle stream. Sulfate, total sulfide, and the carbon substrate (in most cases acetate) were determined quantitatively. H[sub 2]S and CO[sub 2] are continually removed by stripping with N[sub 2]. Optimal removal is achieved under pH conditions which are adjusted to values below the pK[sup a]-values of the acids. The H[sub 2]S concentrations in the stripped gas was 2% to 8% (v/v) if H[sub 2]SO[sub 4] and CH[sub 3]COOH are fed to the recycle stream just before the stripping column. Microbial conversion rates of 65 g of sulfate reduced per liter of bioreactor volume per day are achieved and bacterial conversion efficiencies for sulfate of more than 95% can be maintained if the concentration of undissociated dH[sub 2]S is kept below 40 to 50 mg/L. Porous glass spheres, lava beads, and polyurethane pellets are useful matrices for the attachment of the bacterial biomass. Theoretical aspects and the dependence of the overall conversion performance on selected process parameters are illustrated in the Appendix.

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

    PubMed

    Balci, Nurgul; Brunner, Benjamin; Turchyn, Alexandra V

    2017-01-01

    Sulfur compounds in intermediate valence states, for example elemental sulfur, thiosulfate, and tetrathionate, are important players in the biogeochemical sulfur cycle. However, key understanding about the pathways of oxidation involving mixed-valance state sulfur species is still missing. Here we report the sulfur and oxygen isotope fractionation effects during the oxidation of tetrathionate (S4O6(2-)) and elemental sulfur (S°) to sulfate in bacterial cultures in acidic conditions. Oxidation of tetrathionate by Acidithiobacillus thiooxidans produced thiosulfate, elemental sulfur and sulfate. Up to 34% of the tetrathionate consumed by the bacteria could not be accounted for in sulfate or other intermediate-valence state sulfur species over the experiments. The oxidation of tetrathionate yielded sulfate that was initially enriched in (34)S (ε(34)SSO4-S4O6) by +7.9‰, followed by a decrease to +1.4‰ over the experiment duration, with an average ε(34)SSO4-S4O6 of +3.5 ± 0.2‰ after a month of incubation. We attribute this significant sulfur isotope fractionation to enzymatic disproportionation reactions occurring during tetrathionate decomposition, and to the incomplete transformation of tetrathionate into sulfate. The oxygen isotope composition of sulfate (δ(18)OSO4) from the tetrathionate oxidation experiments indicate that 62% of the oxygen in the formed sulfate was derived from water. The remaining 38% of the oxygen was either inherited from the supplied tetrathionate, or supplied from dissolved atmospheric oxygen (O2). During the oxidation of elemental sulfur, the product sulfate became depleted in (34)S between -1.8 and 0‰ relative to the elemental sulfur with an average for ε(34)SSO4-S0 of -0.9 ± 0.2‰ and all the oxygen atoms in the sulfate derived from water with an average normal oxygen isotope fractionation (ε(18)OSO4-H2O) of -4.4‰. The differences observed in δ(18)OSO4 and the sulfur isotope composition of sulfate (δ(34)SSO4), acid

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

    PubMed Central

    Balci, Nurgul; Brunner, Benjamin; Turchyn, Alexandra V.

    2017-01-01

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

  1. What Is the Boiling Point and Heat of Vaporization of Sulfuric Acid?

    ERIC Educational Resources Information Center

    Myers, R. Thomas

    1983-01-01

    Discusses the values presented in various handbooks for the boiling point and heat of vaporization of sulfuric acid, noting discrepencies. Analyzes various approaches to data presentation, discussing the data on sulfuric acid in light of the Trouton constant. Points out the need for a more critical use of tables. (JM)

  2. What Is the Boiling Point and Heat of Vaporization of Sulfuric Acid?

    ERIC Educational Resources Information Center

    Myers, R. Thomas

    1983-01-01

    Discusses the values presented in various handbooks for the boiling point and heat of vaporization of sulfuric acid, noting discrepencies. Analyzes various approaches to data presentation, discussing the data on sulfuric acid in light of the Trouton constant. Points out the need for a more critical use of tables. (JM)

  3. [Gene mining of sulfur-containing amino acid metabolic enzymes in soybean].

    PubMed

    Qiu, Hongmei; Hao, Wenyuan; Gao, Shuqin; Ma, Xiaoping; Zheng, Yuhong; Meng, Fanfan; Fan, Xuhong; Wang, Yang; Wang, Yueqiang; Wang, Shuming

    2014-09-01

    The genes of sulfur-containing amino acid synthetases in soybean are essential for the synthesis of sulfur-containing amino acids. Gene mining of these enzymes is the basis for the molecular assistant breeding of high sulfur-containing amino acids in soybean. In this study, using software BioMercator2.1, 113 genes of sulfur-containing amino acid enzymes and 33 QTLs controlling the sulfur-containing amino acids content were mapped onto Consensus Map 4.0, which was integrated by genetic and physical maps of soybean. Sixteen candidate genes associated to the synthesis of sulfur-containing amino acids were screened based on the synteny between gene loci and QTLs, and the effect values of QTLs. Through a bioinformatic analysis of the copy number, SNP information, and expression profile of candidate genes, 12 related enzyme genes were identified and mapped on 8 linkage groups, such as D1a, M, A2, K, and G. The genes corresponding to QTL regions can explain 6%?38.5% genetic variation of sulfur-containing amino acids, and among them, the indirect effect values of 9 genes were more than 10%. These 12 genes were involved in sulfur-containing amino acid metabolism and were highly expressed in the cotyledons and flowers, showing an abundance of SNPs. These genes can be used as candidate genes for the development of functional markers, and it will lay a foundation for molecular design breeding in soybean.

  4. Correlation of Sulfuric Acid Hydrate Abundance with Charged Particle Flux at the Surface of Europa

    NASA Astrophysics Data System (ADS)

    Dalton, James B.; Paranicas, C. P.; Cassidy, T. A.; Shirley, J. H.

    2010-10-01

    The trailing hemisphere of Jupiter's moon Europa is bombarded by charged particles trapped within Jupiter's magnetosphere. Sulfur ion implantation and impacting energetic electrons strongly affect the surface chemistry of Europa. Understanding these processes is important for disentangling the extrinsic and intrinsic components of Europa's surface chemistry. In the sulfur cycle model of Carlson et al. (Science 286, 97, 1999), hydrated sulfuric acid represents the dominant reaction product of radiolytic surface modification processes on Europa. In recent compositional investigations employing linear mixture modeling, Dalton et al. (LPSC XV, #2511, 2009) and Shirley et al. (Icarus, in press, 2010) document a well-defined gradient of hydrated sulfuric acid abundance for a study area spanning the leading side - trailing side boundary in Argadnel Regio. Sulfuric acid hydrate abundance in this region increases toward the trailing side apex. Here we compare the derived sulfuric acid hydrate abundances at 41 locations on Europa's surface with independent model results describing 1) the sulfur ion flux (Hendrix et al., 2010, in preparation), and 2) the energetic electron flux, at the same locations. We improve upon the prior calculation of electron energy into the surface of Paranicas et al. (2009, in Europa, U. Arizona, p529; Pappalardo, McKinnon, & Khurana eds.) by incorporating a realistic pitch angle dependence of the distribution. While the sulfur ion implantation and electron energy deposition model distributions differ in important details, both show trailing side gradients similar to that found for the sulfuric acid hydrate. Correlation coefficients exceed 0.9 in comparisons of each of these models with the sulfuric acid hydrate distribution. Our results support models in which the electron energy flux drives reactions that utilize implanted sulfur to produce sulfuric acid hydrate. This work was performed at the California Institute of Technology-Jet Propulsion

  5. Sulfur-Doped Graphene Oxide Quantum Dots as Photocatalysts for Hydrogen Generation in the Aqueous Phase.

    PubMed

    Gliniak, Jacek; Lin, Jia-Hoa; Chen, Yi-Ting; Li, Chuen-Ru; Jokar, Efat; Chang, Chin-Hao; Peng, Chun-Sheng; Lin, Jui-Nien; Lien, Wan-Hsiang; Tsai, Hui-Min; Wu, Tung-Kung

    2017-08-24

    Sulfur-doped graphene oxide quantum dots (S-GOQDs) were synthesized and investigated for efficient photocatalytic hydrogen generation application. The UV/Vis, FTIR, and photoluminescence spectra of the synthesized S-GOQDs exhibit three absorption bands at 333, 395, and 524 nm, characteristic of C=S and C-S stretching vibration signals at 1075 and 690 cm(-1) , and two excitation-wavelength-independent emission signals with maxima at 451 and 520 nm, respectively, confirming the successful doping of S atom into the GOQDs. Electronic structural analysis suggested that the S-GOQDs exhibit conduction band minimum (CBM) and valence band maximum (VBM) levels suitable for water splitting. Under direct sunlight irradiation, an initial rate of 18 166 μmol h(-1)  g(-1) in pure water and 30 519 μmol h(-1)  g(-1) in 80 % ethanol aqueous solution were obtained. Therefore, metal-free and inexpensive S-GOQDs hold great potential in the development of sustainable and environmentally friendly photocatalysts for efficient hydrogen generation from water splitting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. FTIR studies of low temperature sulfuric acid aerosols

    NASA Technical Reports Server (NTRS)

    Anthony, S. E.; Tisdale, R. T.; Disselkamp, R. S.; Tolbert, M. A.; Wilson, J. C.

    1995-01-01

    Sub-micrometer sized sulfuric acid H2SO4 particles were generated using a constant output atomizer source. The particles were then exposed to water vapor before being injected into a low temperature cell. Multipass transmission Fourier Transformation Infrared (FTIR) spectroscopy was used to determine the phase and composition of the aerosols as a function of time for periods of up to five hours. Binary H2SO4H2O aerosols with compositions from 35 to 95 wt % H2SO4 remained liquid for over 3 hours at room temperatures ranging from 189-240 K. These results suggest that it is very difficut to freeze SSAs via homogeneous nucleation. Attempts to form aerosols more dilute than 35 wt % H2SO4 resulted in ice formation.

  7. Sulfuric acid leaching kinetics of South African chromite

    NASA Astrophysics Data System (ADS)

    Zhao, Qing; Liu, Cheng-jun; Shi, Pei-yang; Zhang, Bo; Jiang, Mao-fa; Zhang, Qing-song; Zevenhoven, Ron; Saxén, Henrik

    2015-03-01

    The sulfuric acid leaching kinetics of South African chromite was investigated. The negative influence of a solid product layer constituted of a silicon-rich phase and chromium-rich sulfate was eliminated by crushing the chromite and by selecting proper leaching conditions. The dimensionless change in specific surface area and the conversion rate of the chromite were observed to exhibit a proportional relationship. A modified shrinking particle model was developed to account for the change in reactive surface area, and the model was fitted to experimental data. The resulting model was observed to describe experimental findings very well. Kinetics analysis revealed that the leaching process is controlled by a chemical reaction under the employed experimental conditions and the activation energy of the reaction is 48 kJ·mol-1.

  8. Aldol Condensation Products and Polyacetals in Organic Films Formed from Reactions of Propanal in Sulfuric Acid at Upper Troposphere/Lower Stratosphere (UT/LS) Aerosol Acidities

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    Aerosols in the upper troposphere and lower stratosphere (UT/LS) consist mostly of concentrated sulfuric acid (40-80 wt. %) which is highly reflective towards UV and visible radiation. However, airborne measurements have shown that these particles may also contain a significant amount of organic material. Experiments combining organics (propanal, glyoxal and/or methylglyoxal) with sulfuric acid at concentrations typical of UT/LS aerosols produced highly colored surface films (and solutions) that have the potential to impact chemical, optical and/or cloud-forming properties of aerosols. In order to assess the potential for such films to impact aerosol chemistry or climate properties, experiments were performed to identify the chemical processes responsible for film formation. Surface films were analyzed via Attenuated Total Reflectance-FTIR and Nuclear Magnetic Resonance spectroscopies and are shown to consist primarily of aldol condensation products and cyclic and linear polyacetals, the latter of which are likely responsible for separation from the aqueous phase.

  9. Health effects of air pollutants: Sulfuric acid, the old and the new

    SciTech Connect

    Amdur, M.O. )

    1989-05-01

    Data from exposure of experimental animals and human subjects to sulfuric acid presents a consistent picture of its toxicology. Effects on airway resistance in asthmatic subjects were well predicted by data obtained on guinea pigs. Sulfuric acid increases the irritant response to ozone in both rats and man. In donkeys, rabbits, and human subjects, sulfuric acid alters clearance of particles from the lung in a similar manner. These changes resemble those produced by cigarette smoke and could well lead to chronic bronchitis. Data obtained on guinea pigs indicate that very small amounts of sulfuric acid on the surface of ultrafine metal oxide aerosols produce functional, morphological, and biochemical pulmonary effects. Such particles are typical of those emitted from coal combustion and smelting operations. Sulfate is an unsatisfactory surrogate in existing epidemiology studies. Sulfuric acid measurement is a critical need in such studies. 31 references.

  10. A Demonstration of Acid Rain and Lake Acidification: Wet Deposition of Sulfur Dioxide.

    ERIC Educational Resources Information Center

    Goss, Lisa M.

    2003-01-01

    Introduces a science demonstration on the dissolution of sulfuric oxide emphasizing the concept of acid rain which is an environmental problem. Demonstrates the acidification from acid rain on two lake environments, limestone and granite. Includes safety information. (YDS)

  11. A Demonstration of Acid Rain and Lake Acidification: Wet Deposition of Sulfur Dioxide.

    ERIC Educational Resources Information Center

    Goss, Lisa M.

    2003-01-01

    Introduces a science demonstration on the dissolution of sulfuric oxide emphasizing the concept of acid rain which is an environmental problem. Demonstrates the acidification from acid rain on two lake environments, limestone and granite. Includes safety information. (YDS)

  12. Infrared studies of sulfuric acid and its impact on polar and global ozone

    NASA Astrophysics Data System (ADS)

    Iraci, Laura Tracy

    Sulfuric acid aerosols are present throughout the lower stratosphere and play an important role in both polar and global ozone depletion. In the polar regions, stratospheric sulfate aerosols (SSAs) act as nuclei for the growth of polar stratospheric clouds (PSCs). Heterogeneous reactions can occur on these PSCs, leading to chlorine activation and catalytic ozone destruction. This thesis addresses the issue of polar ozone depletion through laboratory studies which examine the nucleation of PSCs on sulfuric acid. In addition, chemistry which occurs directly on sulfate aerosols may impact ozone at midlatitudes, and studies describing one such reaction are presented as well. To study the growth of type I PSCs on sulfuric acid, thin H2SO4 films were exposed to water and nitric acid vapors at stratospheric temperatures. Fourier transform infrared spectroscopy was used to probe the phase of the sulfuric acid and to identify the HNO3/H2O films which condensed. Supercooled liquid sulfuric acid films showed uptake of HNO3 to form ternary solutions, followed by crystallization of nitric acid trihydrate (NAT). When crystalline sulfuric acid tetrahydrate (SAT) films were exposed to nitric acid and water, condensation of a supercooled HNO3/H2O layer was often observed. As predicted by theory, some of the SAT crystal then dissolved, creating a ternary H2SO4/HNO3/H2O solution. From this solution, NAT nearly always crystallized, halting the phase change of sulfuric acid. If a supercooled nitric acid layer did not condense on frozen sulfuric acid, crystalline NAT was not deposited from the gas phase when SNAT/leq41. At significantly higher supersaturations, NAT could be forced to condense on sulfuric acid, regardless of its phase. Calculations of the contact parameter from experimental data indicate that m<0.79 for NAT on SAT, predicting a significant barrier to nucleation of NAT from the gas phase. While PSCs can form only in the cold polar regions of the stratosphere, sulfuric

  13. Involvement of intermediate sulfur species in biological reduction of elemental sulfur under acidic, hydrothermal conditions.

    PubMed

    Boyd, Eric S; Druschel, Gregory K

    2013-03-01

    The thermoacidophile and obligate elemental sulfur (S(8)(0))-reducing anaerobe Acidilobus sulfurireducens 18D70 does not associate with bulk solid-phase sulfur during S(8)(0)-dependent batch culture growth. Cyclic voltammetry indicated the production of hydrogen sulfide (H(2)S) as well as polysulfides after 1 day of batch growth of the organism at pH 3.0 and 81°C. The production of polysulfide is likely due to the abiotic reaction between S(8)(0) and the biologically produced H(2)S, as evinced by a rapid cessation of polysulfide formation when the growth temperature was decreased, inhibiting the biological production of sulfide. After an additional 5 days of growth, nanoparticulate S(8)(0) was detected in the cultivation medium, a result of the hydrolysis of polysulfides in acidic medium. To examine whether soluble polysulfides and/or nanoparticulate S(8)(0) can serve as terminal electron acceptors (TEA) supporting the growth of A. sulfurireducens, total sulfide concentration and cell density were monitored in batch cultures with S(8)(0) provided as a solid phase in the medium or with S(8)(0) sequestered in dialysis tubing. The rates of sulfide production in 7-day-old cultures with S(8)(0) sequestered in dialysis tubing with pore sizes of 12 to 14 kDa and 6 to 8 kDa were 55% and 22%, respectively, of that of cultures with S(8)(0) provided as a solid phase in the medium. These results indicate that the TEA existed in a range of particle sizes that affected its ability to diffuse through dialysis tubing of different pore sizes. Dynamic light scattering revealed that S(8)(0) particles generated through polysulfide rapidly grew in size, a rate which was influenced by the pH of the medium and the presence of organic carbon. Thus, S(8)(0) particles formed through abiological hydrolysis of polysulfide under acidic conditions appeared to serve as a growth-promoting TEA for A. sulfurireducens.

  14. Radiolysis of aqueous solutions of 2-aminoethanethiosulfuric acid. [Gamma radiation

    SciTech Connect

    Grachev, S.A.; Koroleva, I.K.; Kropachev, E.V.; Litvyakova, G.I.

    1982-07-10

    In the radiolysis products of aerated and deaerated solutions of the 2-aminoethanethiosulfuric acid the authors have identified cystamine monoxide, cystamine, taurine, mercamine, the sulfate ion, the sulfite ion, and the dithionate ion. The yields of these products under different conditions have been determined. Results indicated that the sulfate ion is formed both from the divalent and the hexavalent sulfur atom of the 2-aminoethanethiosulfuric acid moelcule. A possible radiolysis mechanism is discussed.

  15. Theoretical estimates of equilibrium sulfur isotope effects in aqueous sulfur systems: Highlighting the role of isomers in the sulfite and sulfoxylate systems

    NASA Astrophysics Data System (ADS)

    Eldridge, D. L.; Guo, W.; Farquhar, J.

    2016-12-01

    We present theoretical calculations for all three isotope ratios of sulfur (33S/32S, 34S/32S, 36S/32S) at the B3LYP/6-31+G(d,p) level of theory for aqueous sulfur compounds modeled in 30-40H2O clusters spanning the range of sulfur oxidation state (Sn, n = -2 to +6) for estimating equilibrium fractionation factors in aqueous systems. Computed 34β values based on major isotope (34S/32S) reduced partition function ratios (RPFRs) scale to a first order with sulfur oxidation state and coordination, where 34β generally increase with higher oxidation state and increasing coordination of the sulfur atom. Exponents defining mass dependent relationships based on β values (x/34κ = ln(xβ)/ln(34β), x = 33 or 36) conform to tight ranges over a wide range of temperature for all aqueous compounds (33/34κ ≈ 0.5148-0.5159, 36/34κ ≈ 1.89-1.90 from T ⩾ 0 °C). The exponents converge near a singular value for all compounds at the high temperature limit (33/34κT→∞ = 0.51587 ± 0.00003 and 36/34κT→∞ = 1.8905 ± 0.0002; 1 s.d. of all computed compounds), and typically follow trends based on oxidation state and coordination similar to those seen in 34β values at lower temperatures. Theoretical equilibrium fractionation factors computed from these β-values are compared to experimental constraints for HSO3-T(aq)/SO2(g, aq), SO2(aq)/SO2(g), H2S(aq)/H2S(g), H2S(aq)/HS-(aq), SO42-(aq)/H2ST(aq), S2O32-(aq) (intramolecular), and S2O32-(aq)/H2ST(aq), and generally agree within a reasonable estimation of uncertainties. We make predictions of fractionation factors where other constraints are unavailable. Isotope partitioning of the isomers of protonated compounds in the sulfite and sulfoxylate systems depend strongly on whether protons are bound to either sulfur or oxygen atoms. The magnitude of the HSO3-T/SO32- major isotope (34S/32S) fractionation factor is predicted to increase with temperature from 0 to 70 °C due to the combined effects of the large magnitude (HS)O3

  16. Aqueous infrared carboxylate absorbances: Aliphatic di-acids

    USGS Publications Warehouse

    Cabaniss, S.E.; Leenheer, J.A.; McVey, I.F.

    1998-01-01

    Aqueous attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectra of 18 aliphatic di-carboxylic acids are reported as a function of pH. The spectra show isosbestic points and intensity changes which indicate that Beer's law is obeyed, and peak frequencies lie within previously reported ranges for aqueous carboxylates and pure carboxylic acids. Intensity sharing from the symmetric carboxylate stretch is evident in many cases, so that bands which are nominally due to alkyl groups show increased intensity at higher pH. The asymmetric stretch of the HA- species is linearly related to the microscopic acidity constant of the H2A species, with ??pK 2 intervening atoms). The results suggest that aqueous ATR-FTIR may be able to estimate 'intrinsic' pKa values of carboxylic acids, in addition to providing quantitative estimates of ionization. ?? 1998 Elsevier Science B.V. All rights reserved.

  17. Tungstate sulfuric acid (TSA)/KMnO4 as a novel heterogeneous system for rapid deoximation.

    PubMed

    Karami, Bahador; Montazerozohori, Morteza

    2006-09-28

    Neat chlorosulfonic acid reacts with anhydrous sodium tungstate to give tungstate sulfuric acid (TSA), a new dibasic inorganic solid acid in which two sulfuric acid molecules connect to a tungstate moiety via a covalent bond. A variety of oximes were oxidized to their parent carbonyl compounds under mild conditions with excellent yields in short times by a heterogeneous wet TSA/KMnO4 in dichloromethane system.

  18. Properties of nanocellulose isolated from corncob residue using sulfuric acid, formic acid, oxidative and mechanical methods.

    PubMed

    Liu, Chao; Li, Bin; Du, Haishun; Lv, Dong; Zhang, Yuedong; Yu, Guang; Mu, Xindong; Peng, Hui

    2016-10-20

    In this work, nanocellulose was extracted from bleached corncob residue (CCR), an underutilized lignocellulose waste from furfural industry, using four different methods (i.e. sulfuric acid hydrolysis, formic acid (FA) hydrolysis, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation, and pulp refining, respectively). The self-assembled structure, morphology, dimension, crystallinity, chemical structure and thermal stability of prepared nanocellulose were investigated. FA hydrolysis produced longer cellulose nanocrystals (CNCs) than the one obtained by sulfuric acid hydrolysis, and resulted in high crystallinity and thermal stability due to its preferential degradation of amorphous cellulose and lignin. The cellulose nanofibrils (CNFs) with fine and individualized structure could be isolated by TEMPO-mediated oxidation. In comparison with other nanocellulose products, the intensive pulp refining led to the CNFs with the longest length and the thickest diameter. This comparative study can help to provide an insight into the utilization of CCR as a potential source for nanocellulose production.

  19. Suicidal carbon monoxide poisoning by combining formic acid and sulfuric acid within a confined space.

    PubMed

    Lin, Peter T; Dunn, William A

    2014-01-01

    Suicide by inhalation of carbon monoxide produced by mixing formic acid and sulfuric acid within a confined space is a rare method of suicide. This method is similar to the so-called "detergent suicide" method where an acid-based detergent is mixed with a sulfur source to produce hydrogen sulfide. Both methods produce a toxic gas that poses significant hazards for death investigators, first responders and bystanders. Carbon monoxide is an odorless gas, while hydrogen sulfide has a characteristic rotten eggs odor, so the risks associated with carbon monoxide are potentially greater due to lack of an important warning signal. While detergent suicides have become increasingly common in the USA, suicide with formic acid and sulfuric acid is rare with only three prior cases being reported. Greater awareness of this method among death investigators is warranted because of the special risks of accidental intoxication by toxic gas and the possibility that this method of suicide will become more common in the future. © 2013 American Academy of Forensic Sciences.

  20. Ambient temperature effect on single-bubble sonoluminescence in different concentrations of sulfuric acid solutions

    NASA Astrophysics Data System (ADS)

    Imani, Kh.; Bemani, F.; Silatani, M.; Sadighi-Bonabi, R.

    2012-01-01

    The effect of ambient temperature on the parameters of the single-bubble sonoluminescence in sulfuric acid (SA) diluted in water is studied. Using a hydrochemical model, three dominant instabilities of shape, Bjerknes, and diffusion are considered. The phase diagrams of the bubble in the (R0 - Pa) space are presented, and the parametric dependence of the light intensity is discussed. In contrast to water, the calculated thermal-bremsstrahlung mechanism of light emission at the fixed degassing condition of high SA concentrations shows that, with increasing the temperature of aqueous SA solutions, the light intensity increases. However, at diluted SA solutions similar to water, the light intensity decreases with increasing the ambient temperature. For 50 wt % SA, it was observed that the emitted light was almost temperature independent. Furthermore, it is found that, at the fixed temperatures of 20 °C, 10 °C, and 0 °C, the aqueous solutions of 65 wt %, 50 wt %, and 45 wt % SA, respectively, have the maximum light emission.

  1. Sediment biogeochemistry of iron and sulfur in an acidic lake

    NASA Astrophysics Data System (ADS)

    White, Jeffrey R.; Gubala, Chad P.; Fry, Brian; Owen, Jeffrey; Mitchell, Myron J.

    1989-10-01

    The biogeochemical cycling of Fe and S in the sediments of acidic Big Moose Lake, Adirondack Park, NY, U.S.A., was investigated. Sediment cores and porewater samples were collected along a depth transect from the hypolimnion (24 m water depth), metalimnion (17 m), and epilimion (8, 12 m). Four vertically distinguishable zones in the sediment environment were observed at each site: 1) NO3- disappearance near the sediment/water interface; 2) accumulation of solid-phase Fe in the top 5 cm; 3) coincident accumulation of chromium reducible sulfur (CRS), disappearance of SO4- and minima in C:S and δ34S at or slightly below maxima in oxide-bound Fe; and 4) homogenous background concentrations in S and Fe below 30 and 10 cm, respectively. Iron and sulfur accumulations in the upper 10 cm occurred at the same depths in cores of different ages, indicating that diagenetic rather than depositional processes played a dominant role in determining near-surface Fe and S profiles. Although sediment accumulation rates varied along the transect, the four zones were located at similar depths in the sediment column at all sites. Diagenetic processes play a major role in the development of these features in Big Moose Lake. The extent of Fe enrichment was considerably greater in the metalimnetic and epilimnetic sediments. In contrast, concentrations of Fe were lower in hypolimnetic sediments, which appeared to be losing Fe to the water column. At all sites, increases in total S from a background concentration of 60-80 μmol g-1 of dry mass occurred in sediments dated approximately 1850. More recent increases to 560 μmol Sg-1 occurred asynchronously in the cores, indicating an important role of sulfate reduction in adding S to sediments. However, organic sulfur accumulation accounted for 22-56% of the recent increase in sediment S. Concentrations of iron and organic carbon were high in lake sediments and probably do not limit S storage in this lake.

  2. Sulfur amino acids in diet-induced fatty liver: a new perspective based on recent findings.

    PubMed

    Toohey, John I

    2014-06-19

    The relationship of sulfur amino acids to diet-induced fatty liver was established 80 years ago, with cystine promoting the condition and methionine preventing it. This relationship has renewed importance today because diet-induced fatty liver is relevant to the current epidemics of obesity, non-alcoholic fatty liver disease, metabolic syndrome, and type 2 diabetes. Two recent papers provide the first evidence linking sulfane sulfur to diet-induced fatty liver opening a new perspective on the problem. This review summarizes the early data on sulfur amino acids in fatty liver and correlates that data with current knowledge of sulfur metabolism. Evidence is reviewed showing that the lipotropic effect of methionine may be mediated by sulfane sulfur and that the hepatosteatogenic effect of cystine may be related to the removal of sulfane sulfur by cysteine catabolites. Possible preventive and therapeutic strategies are discussed.

  3. Decomposition Studies of Triphenylboron, Diphenylborinic Acid and Phenylboric Acid in Aqueous Alkaline Solutions Containing Copper

    SciTech Connect

    Crawford, C.L.; Peterson, R. A.

    1997-02-11

    This report documents the copper-catalyzed chemical kinetics of triphenylboron, diphenylborinic acid and phenylboric acid (3PB, 2PB and PBA) in aqueous alkaline solution contained in carbon-steel vessels between 40 and 70 degrees C.

  4. Benefits of the stirred, autorefrigerated reactor in sulfuric acid alkylation

    SciTech Connect

    Ackerman, S.; Lerner, H.; Zaczepinski, S.

    1996-12-01

    Alkylation is a process which combines propylenes, butylenes, and pentylenes with isobutane in the presence of an acid catalyst (H{sub 2}SO{sub 4} or HF) to produce a premium quality gasoline blendstock. The alkylation process was developed in the late 1930`s and processing capacity grew tremendously during World War II in response to demand for aviation gasoline. Since that time, alkylation capacity has steadily grown to supply an important motor gasoline component. Now, more than 50 years later, alkylation is in the spotlight again for reformulated gasoline. Alkylate is a high octane, low sensitivity, low RVP, totally paraffinic material which represents the ideal blendstock for modern gasoline manufacture. Two types of modern reactor systems are currently offered for license to the refining industry for sulfuric acid alkylation. These are the stirred, autorefrigerated system offered by Exxon Research and Engineering (ERE) and the indirect, or effluent refrigerated system offered by others. By means of a case study example, this paper discusses the autorefrigerated reaction system and its benefits.

  5. [Determination of thoracic and inhalable fraction of sulfuric acid(VI) in workplace air].

    PubMed

    Szewczyńska, Małgorzata; Pośniak, Małgorzata; Pągowska, Emilia

    The article presents the results of the determination of the inhalable and thoracic fraction of sulfuric acid(VI) in 3 workplaces producing or processing this chemical. To collect thoracic fractions of sulfuric acid(VI) Parallel Particle Impactor (PPI) was used. To isolate inhalable fraction of sulfuric acid(VI) from the air we used a sampler developed at the Institute of Occupational Medicine (IOM), United Kingdom. Parallel Particle Impactor and IOM samplers worked with pumps at a flow of 2 l/min. For the chromatographic determination of the inhalable and thoracic fraction of sulfuric acid(VI) in workplace the ion chromatography with conductometric detection was used. Depending on the sampling place the concentration of thoracic fraction of sulfuric acid(VI) was: 0.0015-0.01 mg/m3 in workplace A, 0.0019-0.25 mg/m3 in workplace B, and 0.002-0.01 mg/m3 in workplace C. Of 22 tested workstations in workplace B only 7 exceeded the threshold limit value (TLV) for the concentration of thoracic fraction of sulfuric acid(VI). The results confirmed the utility of PPI for sampling the thoracic fraction of sulfuric acid(VI). The studies show that at 22 workstations in the establishments producing or processing sulfuric acid(VI) thoracic fraction of acid is emitted to the work environment. The collected data showed that the thoracic fraction of sulfuric acid(VI) represents on average 64% of the inhalable fraction. Med Pr 2016;67(4):509-515. This work is available in Open Access model and licensed under a CC BY-NC 3.0 PL license.

  6. Strong Hydrogen Bonded Molecular Interactions between Atmospheric Diamines and Sulfuric Acid.

    PubMed

    Elm, Jonas; Jen, Coty N; Kurtén, Theo; Vehkamäki, Hanna

    2016-05-26

    We investigate the molecular interaction between methyl-substituted N,N,N',N'-ethylenediamines, propane-1,3-diamine, butane-1,4-diamine, and sulfuric acid using computational methods. Molecular structure of the diamines and their dimer clusters with sulfuric acid is studied using three density functional theory methods (PW91, M06-2X, and ωB97X-D) with the 6-31++G(d,p) basis set. A high level explicitly correlated CCSD(T)-F12a/VDZ-F12 method is used to obtain accurate binding energies. The reaction Gibbs free energies are evaluated and compared with values for reactions involving ammonia and atmospherically relevant monoamines (methylamine, dimethylamine, and trimethylamine). We find that the complex formation between sulfuric acid and the studied diamines provides similar or more favorable reaction free energies than dimethylamine. Diamines that contain one or more secondary amino groups are found to stabilize sulfuric acid complexes more efficiently. Elongating the carbon backbone from ethylenediamine to propane-1,3-diamine or butane-1,4-diamine further stabilizes the complex formation with sulfuric acid by up to 4.3 kcal/mol. Dimethyl-substituted butane-1,4-diamine yields a staggering formation free energy of -19.1 kcal/mol for the clustering with sulfuric acid, indicating that such diamines could potentially be a key species in the initial step in the formation of new particles. For studying larger clusters consisting of a diamine molecule with up to four sulfuric acid molecules, we benchmark and utilize a domain local pair natural orbital coupled cluster (DLPNO-CCSD(T)) method. We find that a single diamine is capable of efficiently stabilizing sulfuric acid clusters with up to four acid molecules, whereas monoamines such as dimethylamine are capable of stabilizing at most 2-3 sulfuric acid molecules.

  7. Pt/TiO2 (Rutile) Catalysts for Sulfuric Acid Decomposition in Sulfur-Based Thermochemical Water-Splitting Cycles

    SciTech Connect

    L. M. Petkovic; D. M. Ginosar; H. W. Rollins; K. C. Burch; P. J. Pinhero; H. H. Farrell

    2008-04-01

    Thermochemical cycles consist of a series of chemical reactions to produce hydrogen from water at lower temperatures than by direct thermal decomposition. All the sulfur-based cycles for water splitting employ the sulfuric acid decomposition reaction. This work reports the studies performed on platinum supported on titania (rutile) catalysts to investigate the causes of catalyst deactivation under sulfuric acid decomposition reaction conditions. Samples of 1 wt% Pt/TiO2 (rutile) catalysts were submitted to flowing concentrated sulfuric acid at 1123 K and atmospheric pressure for different times on stream (TOS) between 0 and 548 h. Post-operation analyses of the spent catalyst samples showed that Pt oxidation and sintering occurred under reaction conditions and some Pt was lost by volatilization. Pt loss rate was higher at initial times but total loss appeared to be independent of the gaseous environment. Catalyst activity showed an initial decrease that lasted for about 66 h, followed by a slight recovery of activity between 66 and 102 h TOS, and a period of slower deactivation after 102 h TOS. Catalyst sulfation did not seem to be detrimental to catalyst activity and the activity profile suggested that a complex dynamical situation involving platinum sintering, volatilization, and oxidation, along with TiO2 morphological changes affected catalyst activity in a non-monotonic way.

  8. Acid-activated spent bleaching earth as a sorbent for chromium (VI) in aqueous solution.

    PubMed

    Low, K S; Lee, C K; Lee, T S

    2003-02-01

    Spent bleaching earth, an industrial waste produced after the bleaching of crude palm oil, was investigated for its potential in removing Cr(VI) from aqueous solution. The earth was treated with different amounts of sulfuric acid and under different activation temperatures. Results show that the optimum treatment process involved 10% sulfuric acid at 350 degrees C. The effects of contact time, pH, initial concentration, sorbent dosage, temperature, sorption isotherms and the presence of other anions on its sorption capacity were studied. Isotherm data could be fitted into a modified Langmuir isotherm model implying monolayer coverage of Cr(VI) on acid activated spent bleaching earth. The maximum sorption capacity derived from the Langmuir isotherm was 21.2 mg g(-1). This value was compared with those of some other low cost sorbents. Studies of anion effect on the uptake of Cr(VI) on acid activated spent bleaching earth provided the following order of suppression: EDTA >PO4(3-)>SO4(2-)>NO3(-)>Cl(-).

  9. Sulfuric acid karst and its relationship to hydrocarbon reservoir porosity, native sulfur deposits, and the origin of Mississippi Valley-type ore deposits

    SciTech Connect

    Hill, C.A. , Albuquerque, NM )

    1993-03-01

    The Delaware Basin of southeastern New Mexico and West Texas contains hydrocarbons and native sulfur in the basin and sulfuric acid-formed caves and Mississippi Valley-type (MVT) ore deposits around the margins of the basin. Hydrocarbons reacting with sulfate evaporite rock produced hydrogen sulfide gas, which gas oxidized to native sulfur in the basin and which gas also migrated from basin to reef and accumulated there in structural and stratigraphic traps. In the reduced zone of the carbonate reef margin the H[sub 2]S combined with metal-chloride complexes to form MVTs, and in the oxidized zone later in time the H[sub 2]S formed sulfuric acid which dissolved out the famous caves of the region (e.g., Carlsbad Cavern, Lechuguilla Cave). Sulfuric acid karst can be recognized by the discontinuity, large size, and spongework nature of its cave passages, and by the presence of native sulfur, endellite, and large gypsum deposits within these caves. Sulfuric acid oilfield karst refers to cavernous porosity filled with hydrocarbons and can be produced by the mixing of waters of different H[sub 2]S content or by the oxidation of H[sub 2]S to sulfuric acid. Sulfur and carbon-oxygen isotopes have been used to establish and trace the sequence of related hydrocarbon, sulfur, MVT, and karst events in the Delaware Basin.

  10. Polymerization of beta-amino acids in aqueous solution

    NASA Technical Reports Server (NTRS)

    Liu, R.; Orgel, L. E.; Bada, J. L. (Principal Investigator)

    1998-01-01

    We have compared carbonyl diimidazole (CDI) and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDAC) as activating agents for the oligomerization of negatively-charged alpha- and beta-amino acids in homogeneous aqueous solution. alpha-Amino acids can be oligomerized efficiently using CDI, but not by EDAC. beta-Amino acids can be oligomerized efficiently using EDAC, but not by CDI. Aspartic acid, an alpha- and beta-dicarboxylic acid is oligomerized efficiently by both reagents. These results are explained in terms of the mechanisms of the reactions, and their relevance to prebiotic chemistry is discussed.

  11. Polymerization of beta-amino acids in aqueous solution

    NASA Technical Reports Server (NTRS)

    Liu, R.; Orgel, L. E.; Bada, J. L. (Principal Investigator)

    1998-01-01

    We have compared carbonyl diimidazole (CDI) and 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDAC) as activating agents for the oligomerization of negatively-charged alpha- and beta-amino acids in homogeneous aqueous solution. alpha-Amino acids can be oligomerized efficiently using CDI, but not by EDAC. beta-Amino acids can be oligomerized efficiently using EDAC, but not by CDI. Aspartic acid, an alpha- and beta-dicarboxylic acid is oligomerized efficiently by both reagents. These results are explained in terms of the mechanisms of the reactions, and their relevance to prebiotic chemistry is discussed.

  12. Uptake kinetics of three epoxides into sulfuric acid solution

    NASA Astrophysics Data System (ADS)

    Wang, Tianhe; Liu, Ze; Wang, Weigang; Ge, Maofa

    2012-09-01

    This work presents a study of the uptake of isoprene epoxide, butadiene epoxide (BMO) and butadiene diepoxide (BDO) into sulfuric acid solutions which helps to understand the reactivity of epoxides existing in the atmosphere toward acidic aerosols. The uptake of these three compounds into 0-30 wt % H2SO4 solutions were measured using a rotated wetted-wall reactor (RWW) coupled to a single-photon ionization time of flight mass spectrometer (SPI-TOFMS). The epoxides were found to be very easily taken up by H2SO4 solutions even in dilute concentrations of pH levels. Isoprene epoxide was found to partition reversibly into solution at pH = 4, whereas irreversible uptake was observed when pH ≤ 3. We reported the reactive uptake coefficients from 1.87 × 10-5 to 2.67 × 10-3 for pH = 3-20 wt % H2SO4 solutions. A chemical reaction for isoprene epoxide was responsible for the reactive uptake. By means of mass spectrometry, gas chromatography and FTIR spectroscopy, a gas product was identified to be 2-methyl-3-butenal. The uptake behavior of butadiene epoxide was similar with that of isoprene epoxide, while butadiene diepoxide partitioned irreversibly over the whole acidity range of 0-30 wt %, and the reactive uptake coefficients increased slightly (0.849 × 10-4-1.36 × 10-4) from pure water to pH = 1. The reactivity that displayed close dependence on the hydrolysis rates of the three epoxides was analyzed and compared according to their molecular structural differences. The atmospheric lifetimes were calculated and atmospheric implication was discussed based on the corresponding reactive uptake coefficients.

  13. Amine Reactivity with Nanoclusters of Sulfuric Acid and Ammonia

    NASA Astrophysics Data System (ADS)

    Johnston, M. V.; Bzdek, B. R.; DePalma, J.

    2011-12-01

    Alkyl amines have emerged as key species in new particle formation and growth. This interest is reinforced by ambient measurements of amines (e.g. Smith et al., 2010) and enhanced levels of nitrogen (e.g. Bzdek et al., 2011) during growth of newly formed particles. An important mechanism of amine uptake is aminium salt formation, either by substituting for ammonium ions that already exist in the particle or by opening new channels for salt formation that are not favorable with ammonia. This presentation will focus on recent experimental and computational work in our group to study amine uptake into charged nanoclusters of sulfuric acid and ammonia. In the experimental work, clusters are produced by electrospray of an ammonium sulfate solution and then drawn into a Fourier transform ion cyclotron resonance mass spectrometer where a specific cluster is isolated and exposed to amine vapor. We find that amine reactivity is dependent on the size, composition and charge of the isolated cluster. For small clusters of either polarity, all ammonium ions reside on the surface and amine substitution occurs with near unit reaction probability. As the cluster size increases, an ammonium ion can be encapsulated in the center of the cluster, which provides a steric hindrance to amine substitution. Negatively charged clusters are more likely to be acidic than positively charged clusters. For acidic clusters, incoming amine molecules first substitute for preexisting ammonium ions and then add to the cluster until a "neutralized" aminium bisulfate composition is reached. Computational studies of these clusters provide fundamental insight into the thermodynamics and kinetics of amine uptake.

  14. Reaction kinetics of waste sulfuric acid using H2O2 catalytic oxidation.

    PubMed

    Wang, Jiade; Hong, Binxun; Tong, Xinyang; Qiu, Shufeng

    2016-12-01

    The process of recovering waste sulfuric acids using H2O2 catalytic oxidation is studied in this paper. Activated carbon was used as catalyst. Main operating parameters, such as temperature, feed rate of H2O2, and catalyst dosage, have effects on the removal of impurities from waste sulfuric acids. The reaction kinetics of H2O2 catalytic oxidation on impurities are discussed. At a temperature of 90°C, H2O2 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 H2O2 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. H2O2 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 H2O2, 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.

  15. Mechanisms of volatile production from non-sulfur amino acids by irradiation

    NASA Astrophysics Data System (ADS)

    Ahn, Dong Uk; Lee, Eun Joo; Feng, Xi; Zhang, Wangang; Lee, Ji Hwan; Jo, Cheorun; Nam, Kichang

    2016-02-01

    Non-sulfur amino acid monomers were used to study the mechanisms of volatile production in meat by irradiation. Irradiation not only produced many volatiles but also increased the amounts of volatiles from non-sulfur amino acid monomers. The major reaction mechanisms involved in volatile production from each group of the amino acids by irradiation differ significantly. However, we speculate that the radiolysis of amino acid side chains were the major mechanism. In addition, Strecker degradation, especially the production of aldehydes from aliphatic group amino acids, and deamination, isomerization, decarboxylation, cyclic reaction and dehydrogenation of the initial radiolytic products were also contributed to the production of volatile compounds. Each amino acid monomers produced different odor characteristics, but the intensities of odor from all non-sulfur amino acid groups were very weak. This indicated that the contribution of volatiles produced from non-sulfur amino acids was minor. If the volatile compounds from non-sulfur amino acids, especially aldehydes, interact with other volatiles compounds such as sulfur compounds, however, they can contribute to the off-odor of irradiated meat significantly.

  16. Effects of ozone and sulfuric acid aerosol on gas trapping in the guinea pig lung

    SciTech Connect

    Silbaugh, S.A.; Mauderly, J.L.

    1986-01-01

    Four groups of 20 guinea pigs were sequentially exposed by inhalation to either air followed by sulfuric acid aerosol, ozone followed by sulfuric acid aerosol, ozone followed by air, or air followed by air to determine whether ozone preexposure sensitizes guinea pigs to the airway constrictive effects of sulfuric acid aerosol. All first exposures to ozone or air were 2 h in duration; all second exposures to sulfuric acid or air were for 1 h. All ozone and sulfuric acid exposures were 0.8 ppm and 12 mg/m3, respectively. Animals were observed for respiratory distress during exposure, and excised lungs were quantitated for trapped gas and wet/dry ratios. None of the guinea pigs developed dyspnea, and wet/dry ratios were not altered. Ozone significantly (p less than 0.05) increased trapped gas volumes, which were 44% (ozone-acid) to 68% (ozone-air) greater than in the air-air group. Trapped gas volume was 23% greater in the ozone-acid group than in the air-acid group, but the difference was not statistically significant (p less than 0.20). Thus, ozone increased gas trapping but did not significantly sensitize guinea pigs to the bronchoconstrictive action of sulfuric acid.

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

    PubMed

    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.

  18. Ion Irradiation of Sulfuric Acid: Implications for its Stability on Europa

    NASA Technical Reports Server (NTRS)

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

    2010-01-01

    The Galileo near-infrared mapping spectrometer (NIMS) detected regions on Europa's surface containing distorted H2O bands. This distortion likely indicates that there are other molecules mixed with the water ice. Based on spectral comparison, some of the leading possibilities are sulfuric acid, salts. or possibly H3O(+). Previous laboratory studies have shown that sulfuric acid can be created by irradiation of H2OSO2 mixtures, and both molecules are present on Europa. In this project, we were interested in investigating the radiation stability of sulfuric acid (H2SO4) and determining its lifetime on the surface of Europa.

  19. Sulfuric acid-methanol electrolytes as an alternative to sulfuric-hydrofluoric acid mixtures for electropolishing of niobium

    SciTech Connect

    Zhao, Xin; Corcoran, Sean G.; Kelley, Michael J.

    2011-06-01

    Attainment of the greatest possible interior surface smoothness is critical to meeting the performance demands placed upon niobium superconducting radiofrequency (SRF) accelerator cavities by next generation projects. Electropolishing with HF-H{sub 2}SO{sub 4} electrolytes yields cavities that meet SRF performance goals, but a less-hazardous, more environmentally-friendly process is desirable. Reported studies of EP on chemically-similar tantalum describe the use of sulfuric acid-methanol electrolytes as an HF-free alternative. Reported here are the results of experiments on niobium samples with this electrolyte. Voltammetry experiments indicate a current plateau whose voltage range expands with increasing acid concentration and decreasing temperature. Impedance spectroscopy indicates that a compact salt film is responsible for the current plateau. Equivalent findings in electropolishing chemically-similar tantalum with this electrolyte were interpreted due to as mass transfer limitation by diffusion of Ta ions away from the anode surface. We infer that a similar mechanism is at work here. Conditions were found that yield leveling and brightening comparable to that obtained with HF-H{sub 2}SO{sub 4} mixtures.

  20. Persistent ion pairing in aqueous hydrochloric acid.

    PubMed

    Baer, Marcel D; Fulton, John L; Balasubramanian, Mahalingam; Schenter, Gregory K; Mundy, Christopher J

    2014-07-03

    For strong acids, like hydrochloric acid, the complete dissociation into an excess proton and conjugated base as well as the formation of independent solvated charged fragments is assumed. The existence of chloride-hydronium (Cl(-)···H3O(+)) contact ion pairs even in moderate concentration hydrochloric acid (2.5 m) demonstrates that the counterions do not behave merely as spectators. Through comparison of recent extended X-ray absorption fine structure (EXAFS) measurements to state-of-the-art density functional theory (DFT) simulations, we are able to obtain a unique view into the molecular structure of medium-to-high concentrated electrolytes. Here we report that the Cl(-)···H3O(+) contact ion pair structure persists throughout the entire concentration range studied and that these structures differ significantly from moieties studied in microsolvated hydrochloric acid gas phase clusters. Characterizing distinct populations of these ion pairs gives rise to a novel molecular level description of how to view the reaction network for acid dissociation and how it relates to our picture of acid-base equilibria.

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

    PubMed

    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.

  2. Unusual refinery boiler tube failures due to corrosion by sulfuric acid induced by steam leaks

    SciTech Connect

    Lopez-Lopez, D.; Wong-Moreno, A.

    1998-12-31

    Corrosion by sulfuric acid in boilers is a low probability event because gas temperature and metal temperature of boiler tubes are high enough to avoid the condensation of sulfuric acid from flue gases. This degradation mechanism is frequently considered as an important cause of air preheaters materials degradation, where flue gases are cooled by heat transfer to the combustion air. Corrosion is associated to the presence of sulfuric acid, which condensates if metal temperature (or gas temperature) is below of the acid dew point. In economizer tubes, sulfuric acid corrosion is an unlikely event because flue gas and tube temperatures are normally over the acid dewpoint. In this paper, the failure analysis of generator tubes (similar to the economizer of bigger boilers) of two small oil-fired subcritical boilers is reported. It is concluded that sulfuric acid corrosion was the cause of the failure. The sulfuric acid condensation was due to the contact of flue gases containing SO{sub 3} with water-steam spray coming from leaks at the interface of rolled tube to the drum. Considering the information gathered from these two cases studied, an analysis of this failure mechanism is presented including a description of the thermodynamics condition of water leaking from the drum, and an analysis of the factors favoring it.

  3. Mechanochemical leaching of chalcopyrite concentrate by sulfuric acid

    NASA Astrophysics Data System (ADS)

    Mohammadabad, Farhad Khorramshahi; Hejazi, Sina; khaki, Jalil Vahdati; Babakhani, Abolfazl

    2016-04-01

    This study aimed to introduce a new cost-effective methodology for increasing the leaching efficiency of chalcopyrite concentrates at ambient temperature and pressure. Mechanical activation was employed during the leaching (mechanochemical leaching) of chalcopyrite concentrates in a sulfuric acid medium at room temperature and atmospheric pressure. High energy ball milling process was used during the leaching to provide the mechanochemical leaching condition, and atomic absorption spectroscopy and cyclic voltammetry were used to determine the leaching behavior of chalcopyrite. Moreover, X-ray diffraction and scanning electron microscopy were used to characterize the chalcopyrite powder before and after leaching. The results demonstrated that mechanochemical leaching was effective; the extraction of copper increased significantly and continuously. Although the leaching efficiency of chalcopyrite was very low at ambient temperature, the percentages of copper dissolved in the presence of hydrogen peroxide (H2O2) and ferric sulfate (Fe2(SO4)3) after 20 h of mechanochemical leaching reached 28% and 33%, respectively. Given the efficiency of the developed method and the facts that it does not require the use of an autoclave and can be conducted at room temperature and atmospheric pressure, it represents an economical and easy-to-use method for the leaching industry.

  4. Sulfur amino acid metabolism in Zucker diabetic fatty rats.

    PubMed

    Kwak, Hui Chan; Kim, Young-Mi; Oh, Soo Jin; Kim, Sang Kyum

    2015-08-01

    The present study was aimed to investigate the metabolomics of sulfur amino acids in Zucker diabetic fatty (ZDF) rats, an obese type 2 diabetic animal model. Plasma levels of total cysteine, homocysteine and methionine, but not glutathione (GSH) were markedly decreased in ZDF rats. Hepatic methionine, homocysteine, cysteine, betaine, taurine, spermidine and spermine were also decreased. There are no significant difference in hepatic S-adenosylmethionine, S-adenosylhomocysteine, GSH, GSH disulfide, hypotaurine and putrescine between control and ZDF rats. Hepatic SAH hydrolase, betaine-homocysteine methyltransferase and methylene tetrahydrofolate reductase were up-regulated while activities of gamma-glutamylcysteine ligase and methionine synthase were decreased. The area under the curve (AUC) of methionine and methionine-d4 was not significantly different in control and ZDF rats treated with a mixture of methionine (60mg/kg) and methionine-d4 (20mg/kg). Moreover, the AUC of the increase in plasma total homocysteine was comparable between two groups, although the homocysteine concentration curve was shifted leftward in ZDF rats, suggesting that the plasma total homocysteine after the methionine loading was rapidly increased and normalized in ZDF rats. These results show that the AUC of plasma homocysteine is not responsive to the up-regulation of hepatic BHMT in ZDF rats. The present study suggests that the decrease in hepatic methionine may be responsible for the decreases in its metabolites, such as homocysteine, cysteine, and taurine in liver and consequently decreased plasma homocysteine levels.

  5. Theoretical study of ultraviolet induced photodissociation dynamics of sulfuric acid

    NASA Astrophysics Data System (ADS)

    Murakami, Tatsuhiro; Ohta, Ayumi; Suzuki, Tomoya; Ikeda, Kumiko; Danielache, Sebastian O.; Nanbu, Shinkoh

    2015-05-01

    Photodissociation dynamics of sulfuric acid after excitation to the first and second excited states (S1 and S2) were studied by an on-the-fly ab initio molecular dynamics simulations based on the Zhu-Nakamura version of the trajectory surface hopping (ZN-TSH). Forces acting on the nuclear motion were computed on-the-fly by CASSCF method with Dunning's augmented cc-pVDZ basis set. It was newly found that the parent molecule dissociated into two reaction-channels (i) HSO4(12A″) + H(2S) by S1-excitation, and (ii) HSO4(22A″) + H(2S) by S2-excitation. The direct dissociation dynamics yield products different from the SO2 + 2OH fragments often presented in the literature. Both channels result in the same product and differs only in the electronic state of the HSO4 fragment. The trajectories running on S2 do not hop with S0 and a nonadiabatic transition happens at the S2-S1 conical intersection located at a longer OH bond-length than the S1-S0 intersection producing an electronic excited state (22A″) of HSO4 product.

  6. Temperature and intensity of sonoluminescence radiation in sulfuric acid.

    PubMed

    Moshaii, A; Hoseini, M A; Gharibzadeh, S; Tavakoli-Anaraki, A

    2012-07-01

    The spectral radiation of sonoluminescence (SL) from sulfuric acid doped with various Xe concentrations has been studied in a hydrochemical simulation, including radiation effects of both continuum and line emissions. The simulation considers the same temperature for both continuum and line parts of the SL spectrum and gives results in agreement with the experiment. Also, it can properly show period-doubling dynamics for a 50 torr bubble. For most of the allowable driving pressures, it is shown that both the temperature and the intensity of SL for a 4 torr bubble are greater than those of a 50 torr bubble. However, for the range of pressures near the maximum driving conditions of the 50 torr bubble, the SL intensity of this bubble can be up to three orders of magnitude greater than the 4 torr bubble. This case, which is in agreement with the experiment, is obtained when the light-emitting region of the 50 torr bubble is about three orders of magnitude greater than the 4 torr bubble.

  7. Interaction of Atmospheric-Pressure Air Microplasmas with Amino Acids as Fundamental Processes in Aqueous Solution

    PubMed Central

    Zhou, Renwu; Zhou, Rusen; Zhuang, Jinxing; Zong, Zichao; Zhang, Xianhui; Liu, Dongping; Bazaka, Kateryna; Ostrikov, Kostya

    2016-01-01

    Plasma medicine is a relatively new field that investigates potential applications of cold atmospheric-pressure plasmas in bioengineering, such as for bacterial inactivation and degradation of organic molecules in water. In order to enunciate mechanisms of bacterial inactivation at molecular or atomic levels, we investigated the interaction of atmospheric-pressure air microplasmas with amino acids in aqueous solution by using high-resolution mass spectrometry (HRMS). Results show that the oxidation effect of plasma-induced species on the side chains of the amino acids can be categorized into four types, namely hydroxylation, nitration, dehydrogenation and dimerization. In addition, relative activities of amino acids resulting from plasma treatment come in descending order as follows: sulfur-containing carbon-chain amino acids > aromatic amino acids > five-membered ring amino acids > basic carbon-chain amino acids. Since amino acids are building blocks of proteins vital to the growth and reproduction of bacteria, these results provide an insight into the mechanism of bacterial inactivation by plasma. PMID:27183129

  8. Interaction of Atmospheric-Pressure Air Microplasmas with Amino Acids as Fundamental Processes in Aqueous Solution.

    PubMed

    Zhou, Renwu; Zhou, Rusen; Zhuang, Jinxing; Zong, Zichao; Zhang, Xianhui; Liu, Dongping; Bazaka, Kateryna; Ostrikov, Kostya

    2016-01-01

    Plasma medicine is a relatively new field that investigates potential applications of cold atmospheric-pressure plasmas in bioengineering, such as for bacterial inactivation and degradation of organic molecules in water. In order to enunciate mechanisms of bacterial inactivation at molecular or atomic levels, we investigated the interaction of atmospheric-pressure air microplasmas with amino acids in aqueous solution by using high-resolution mass spectrometry (HRMS). Results show that the oxidation effect of plasma-induced species on the side chains of the amino acids can be categorized into four types, namely hydroxylation, nitration, dehydrogenation and dimerization. In addition, relative activities of amino acids resulting from plasma treatment come in descending order as follows: sulfur-containing carbon-chain amino acids > aromatic amino acids > five-membered ring amino acids > basic carbon-chain amino acids. Since amino acids are building blocks of proteins vital to the growth and reproduction of bacteria, these results provide an insight into the mechanism of bacterial inactivation by plasma.

  9. Size-resolved sulfuric acid mist concentrations at phosphate fertilizer manufacturing facilities in Florida.

    PubMed

    Hsu, Yu-Mei; Wu, Chang-Yu; Lundgren, Dale A; Birky, Brian K

    2007-01-01

    Strong inorganic acid mists containing sulfuric acid were identified as a 'known human carcinogen' in a National Toxicology Program (NTP) report where phosphate fertilizer manufacture was listed as one of many occupational exposures to strong acids. To properly assess the occupational exposure to sulfuric acid mists in modern facilities, approved National Institute for Occupational Safety and Health (NIOSH) Method 7903 and a cascade impactor were used for measuring the total sulfuric acid mist concentration and size-resolved sulfuric acid mist concentration, respectively. Sampling was conducted at eight phosphate fertilizer plants and two background sites in Florida and there were 24 sampling sites in these plants. Samples were analyzed by ion chromatography (IC) to quantify the water-soluble ion species. The highest sulfuric acid concentrations by the cascade impactor were obtained at the sulfuric acid pump tank area. When high aerosol mass concentrations (100 micro g m(-3)) were observed at this area, the sulfuric acid mists were in the coarse mode. The geometric mean sulfuric acid concentrations (+/-geometric standard deviation) of PM(23) (aerodynamic cut size smaller than 23 micro m), PM(10) and PM(2.5) from the cascade impactor were 41.7 (+/-5.5), 37.9 (+/-5.8) and 22.1 (+/-4.5) micro g m(-3), respectively. The geometric mean (+/-geometric standard deviation) for total sulfuric acid concentration from the NIOSH method samples was 143 (+/-5.08) micro g m(-3). Sulfuric acid mist concentrations varied significantly among the plants and even at the same location. The measurements by the NIOSH method were 1.5-229 times higher than those by the cascade impactor. Moreover, using the NIOSH method, the sulfuric acid concentrations measured at the lower flow rate (0.30 Lpm) were higher than those at the higher flow rate (0.45 Lpm). One possible reason for the significant differences between the results from the cascade impactor and the NIOSH method is the potential

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

    PubMed

    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).

  11. On the stability and dynamics of (sulfuric acid) (ammonia) and (sulfuric acid) (dimethylamine) clusters: A first-principles molecular dynamics investigation

    NASA Astrophysics Data System (ADS)

    Loukonen, V.; Kuo, I.-F. W.; McGrath, M. J.; Vehkamäki, H.

    2014-01-01

    The main pathway of new-particle formation in the atmosphere is likely to begin from small sulfuric acid clusters stabilized by other compounds, such as ammonia or amines. Here, we present the results of first-principles molecular dynamics simulations probing the stability and dynamics of (sulfuric acid) (ammonia/dimethylamine) clusters with two, three and four sulfuric acid molecules and a varying number of the bases. In each of the eight simulated clusters, an energetic equilibrium was reached and 35 ps of equilibrium data was collected in the NVT(T=300 K) ensemble. The clusters exhibited pronounced thermal motion including rotations of the molecules within the clusters. Regardless of the continuous movement, the clusters stayed bound together. The calculated electric dipole moments were found to be sensitive to the thermal motion and consequently, large fluctuations were observed. In addition, the vibrational spectra for all the clusters were determined, indicating that the thermal motion differs from purely harmonic motion.

  12. Sulfur dioxide effects on plants exhibiting Crassulacean Acid Metabolism.

    PubMed

    Olszyk, D M; Bytnerowicz, A; Fox, C A

    1987-01-01

    The effects of SO(2) on species exhibiting Crassulacean Acid Metabolism (CAM) were determined with short term-high concentration 'acute' greenhouse exposures (0.6 to 3.0 microl liter(-1) (ppm) SO(2) for 2 and 8 h), and long term-low concentration 'chronic' field exposures (0.35 to 0.90 microl liter(-1) SO(2) for 32 to 79 h periodically over 7 to 13 days). In the acute greenhouse exposures, visible injury was observed on Opuntia basilaris Engelm. & Bigel., exposed to 2.0 microl liter(-1) SO(2), but no injury was observed on Ananas comosus (L.) Merr., Bryophyllum blossfeldiana Poelln., Bryophyllum pinnata (Lam.) Pers., or Bryophyllum tubiflora (Harv.) Hamet, exposed to up to 2.8 microl liter(-1) SO(2) for 8 h. Stomatal conductance during the exposures averaged 0.067+/-0.021mol(-2)s(-1) for Opuntia basilaris, 0.029+/-0.008mol(-2)s(-1) for Ananas comosus, and 0.029+/-0.008mol m(-2)s(-1) for Bryophyllum pinnata. Opuntia basilaris was injured early during the day, but not at night; with the injury appearing as a white necrotic banding across just fully expanded pads. Moderately injured pads would regreen beginning 1 to 2 weeks after exposure. In chronic field exposures, no visible injury from SO(2) was observed on Opuntia basilaris, Dudleya arizonica Rose or Agave deserti Engelm. plants, grown either with supplemental irrigation or natural rainfall. In addition, in the field SO(2) had no effect on CO(2) uptake, total sulfur content, transpiration, or tissue acidity in either the light or the dark, or in irrigated vs natural rainfall plots.

  13. Persistent Ion Pairing in Aqueous Hydrochloric Acid

    SciTech Connect

    Baer, Marcel D.; Fulton, John L.; Balasubramanian, Mahalingam; Schenter, Gregory K.; Mundy, Christopher J.

    2014-07-03

    For strong acids, like hydrochloric acid, the complete dissociation into an excess proton and conjugated base as well as the formation of independent solvated charged fragments is assumed. The existence of a chloride-Hyronium (Cl-H3O+) contact ion pairs even in moderate concentration hydrochloric acid (2.5 m) demonstrates that the counter ions do not behave merely as spectators. Through the use of modern extended X-ray absorption fine structure (EXAFS) measurements in conjunction with state-of-the-art density functional theory (DFT) simulations, we are able to obtain an unprecedented view into the molecular structure of medium to high concentrated electrolytes. Here we report that the Cl-H3O+ contact ion pair structure persists throughout the entire concentration range studied and that these structures differ significantly from moieties studied in micro-solvated hydrochloric acid clusters. Characterizing distinct populations of these ion pairs gives rise to a novel molecular level description of how to think about the activity of the proton that impacts our picture of the pH scale. Funding for CJM, GKS, and JLF was provided by DOE Office of Science, Office of Basic Energy Science, Division of Chemical Sciences, Geosciences, and Biosciences. Funding for MDB was provided throught the Laboratory Directed Research and Development program at Pacific Northwest National Laboratory. MB was funded through Argonne National Laboratory.

  14. 40 CFR 721.3130 - Sulfuric acid, mono-C9-11-alkyl esters, sodium salts.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Sulfuric acid, mono-C9-11-alkyl esters... Specific Chemical Substances § 721.3130 Sulfuric acid, mono-C9-11-alkyl esters, sodium salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as sulfuric...

  15. 40 CFR 721.3130 - Sulfuric acid, mono-C9-11-alkyl esters, sodium salts.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Sulfuric acid, mono-C9-11-alkyl esters... Specific Chemical Substances § 721.3130 Sulfuric acid, mono-C9-11-alkyl esters, sodium salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as sulfuric...

  16. 40 CFR 721.3130 - Sulfuric acid, mono-C9-11-alkyl esters, sodium salts.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Sulfuric acid, mono-C9-11-alkyl esters... Specific Chemical Substances § 721.3130 Sulfuric acid, mono-C9-11-alkyl esters, sodium salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as sulfuric...

  17. 40 CFR 721.3130 - Sulfuric acid, mono-C9-11-alkyl esters, sodium salts.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Sulfuric acid, mono-C9-11-alkyl esters... Specific Chemical Substances § 721.3130 Sulfuric acid, mono-C9-11-alkyl esters, sodium salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as sulfuric...

  18. 40 CFR 721.3130 - Sulfuric acid, mono-C9-11-alkyl esters, sodium salts.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Sulfuric acid, mono-C9-11-alkyl esters... Specific Chemical Substances § 721.3130 Sulfuric acid, mono-C9-11-alkyl esters, sodium salts. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as sulfuric...

  19. Reaction of isoprene on thin sulfuric acid films: kinetics, uptake, and product analysis.

    PubMed

    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.

  20. Cytotoxicity of sulfurous acid on cell membrane and bioactivity of Nitrosomonas europaea.

    PubMed

    Jiang, Ruiyu; Wang, Mingqing; Xue, Jianliang; Xu, Ning; Hou, Guihua; Zhang, Wubing

    2015-01-01

    Nitrosomonas europaea, an ammonia oxidizing bacterium, was chosen as a research model to study the alteration of cell membrane in the presence of sulfurous acid and biodegradation of acetochlor. Significant changes of the outer cell membrane were observed in the presence of sulfurous acid using scanning electron microscopy (SEM) and Atomic Force Microscopy (AFM). The fluorescence polarization has shown a significant decrease in membrane fluidity and the increase of permeability of cell membrane. Lysozyme experiment show the cell becomes easily influenced by substance in medium. Inductively Coupled Plasma-Mass Spectrometry (ICP-MS) measurements show considerable amount of Ca(2+) and Mg(2+) in the supernatant from the sulfurous acid exposed cells. Sulfurous acid treatment enhanced the ability of N. europaea to degrade acetochlor. On this basis, it can be concluded that the increased cell permeability is favor for the absorbability of nutrition. As a result, N. europaea grows faster and the biodegradation efficiency was improved.

  1. First-principles molecular dynamics simulations of (sulfuric acid)1(dimethylamine)1 cluster formation

    NASA Astrophysics Data System (ADS)

    Loukonen, Ville; Bork, Nicolai; Vehkamäki, Hanna

    2013-05-01

    The clustering process (sulfuric acid) + (base)→(sulfuric acid)1(base)1 is of fundamental importance in the atmospheric new-particle formation. Especially interesting are the collisions where a proton transfer reaction can happen, as the reaction often leads to relatively strongly bound clusters. Here, we studied the clustering process of (sulfuric acid) + (dimethylamine) → (sulfuric acid)1(dimethylamine)1 using first-principles molecular dynamics simulations. The collision of the two molecules was simulated starting with various spatial orientations and the evolution of the cluster was followed in the NVE ensemble. The simulations suggest that the proton transfer reaction takes place regardless of the intial collision orientation. However, due to the energy released in the process, the newly-formed cluster is not able to reach the minimun energy configuration, which might affect the following growth processes.

  2. Measurement of neutral sulfuric acid-dimethylamine clusters using CI-APi-TOF-MS

    NASA Astrophysics Data System (ADS)

    Simon, Mario; Kürten, Andreas; Jokinen, Tuija; Sarnela, Nina; Sipilä, Mikko; Rondo, Linda; Ehrhart, Sebastian; Junninen, Heikki; Hutterli, Manuel; Kirkby, Jasper; Worsnop, Douglas R.; Curtius, Joachim; Cloud Collaboration

    2013-05-01

    Recent studies suggest that dimethylamine could be a key ternary species in the formation and early growth of atmospheric aerosol particles. We report on nucleation studies for the ternary system of sulfuric acid, water and dimethylamine which have been performed at the CERN CLOUD chamber. These studies were conducted at atmospherically relevant concentrations of sulfuric acid and dimethylamine at 278 K and 38% RH. Two newly developed Chemical Ionization-Atmospheric Pressure interface-Time of Flight-Mass Spectrometers (CIAPi-TOF-MS) were used to measure the time-resolved concentration of neutral clusters containing sulfuric acid and dimethylamine. Results from other instrumental techniques are included in the analysis as well to obtain a deeper insight into the occurring mechanisms. It is the first time that the neutral nucleation pathway has been studied in such detail from the early generation of sulfuric acid monomers up to particle sizes reaching several nanometers.

  3. Freezing behavior of single sulfuric acid aerosols suspended in a quadrupole trap

    NASA Astrophysics Data System (ADS)

    Carleton, K. L.; Sonnenfroh, D. M.; Rawlins, W. T.; Wyslouzil, B. E.; Arnold, S.

    1997-03-01

    The freezing properties of sulfuric acid droplets were studied by suspending single 20- to 30-μm-diameter particles in a quadrupole trap and cooling them to stratospheric temperatures (≥191.5 K). Each particle's dc balance voltage was measured to determine the particle composition as a function of temperature and map out the particle's trajectory relative to the sulfuric acid phase diagram. Angularly resolved optical scattering patterns were monitored to detect freezing events. Particles cooled through the sulfuric acid tetrahydrate region (35-70 wt % H2SO4) did not freeze and remained spherical liquid droplets for several hours. Only particles cooled through the ice-liquid equilibrium region (<35 wt% H2SO4) showed evidence of freezing. This supports previous experimental and field observations that stratospheric sulfuric acid aerosols are likely to remain liquid to within a few degrees of the ice frost point.

  4. Effect of amino acid intake on brush-border membrane uptake of sulfur amino acids.

    PubMed

    Chesney, R W; Gusowski, N; Padilla, M; Lippincott, S

    1986-07-01

    Alterations in the intake of sulfur amino acids (SAA) changes the rat renal brush-border membrane uptake of the beta-amino acid, taurine. A low-SAA diet enhances and a high-taurine diet reduces uptake (Chesney et al., Kidney Int. 24: 588-594, 1983). Neither the low-SAA diet nor the high-taurine diet alters the time course or concentration-dependent accumulation of the sulfur amino acids methionine and cystine or of inorganic sulfate. By contrast the uptake of beta-alanine, another beta-amino acid that competes with taurine, is greater in animals on the low-SAA diet. The high-taurine diet does not change beta-alanine uptake. The plasma levels of taurine are altered by dietary change, but not the values for methionine and cystine. This study indicates that renal adaptation is expressed for beta-alanine, a nonsulfur-containing beta-amino acid. By contrast, methionine, cystine, and sulfate, which participate in a variety of synthetic and conjugative processes, are not conserved by the renal brush-border surface following ingestion of either a low-methionine and -cystine diet or high-taurine diet.

  5. Dental erosion and sulfuric ion exposure levels in individuals working with sulfuric acid in lead storage battery manufacturing plant measured with mouth-rinse index.

    PubMed

    Suyama, Yuji; Takaku, Satoru; Okawa, Yoshikazu; Matsukubo, Takashi

    2010-01-01

    To investigate dental erosion in employees working with sulfuric acid at a lead storage battery manufacturing plant and level of personal exposure to sulfuric ions, we measured sulfuric ion concentrations in the mouth rinse of those employees. We also measured exposure levels from air samples obtained from 2 employees from the same plant who did not work with sulfuric acid using a portable air sampler. At the same time, we collected and compared their mouth rinses with those from other employees. More specifically, we measured and compared sulfuric ion, calcium, and magnesium concentrations, along with pH levels from the mouth rinse of these two groups. Positive correlations were found between sulfuric ion and calcium concentrations (r=0.61, p<0.005), calcium and magnesium concentrations (r=0.61, p<0.005), Ca/Mg and calcium concentrations (r=0.64, p<0.005), and sulfuric ion and magnesium concentrations (r=0.55, p<0.005). Negative correlations were found between sulfuric ion concentrations and pH levels (r=-0.31, p<0.01), and magnesium concentrations and pH levels (r=-0.32, p<0.01). This suggests that mouth rinse from employees working with sulfuric acid could function as an indicator of sulfuric ion concentration in the work environment. Furthermore, this could lead to the development of a more accurate indicator of individual exposure.

  6. Unexpectedly acidic nanoparticles formed in dimethylamine-ammonia-sulfuric-acid nucleation experiments at CLOUD

    DOE PAGES

    Lawler, Michael J.; Winkler, Paul M.; Kim, Jaeseok; ...

    2016-11-03

    New particle formation driven by acid–base chemistry was initiated in the CLOUD chamber at CERN by introducing atmospherically relevant levels of gas-phase sulfuric acid and dimethylamine (DMA). Ammonia was also present in the chamber as a gas-phase contaminant from earlier experiments. The composition of particles with volume median diameters (VMDs) as small as 10 nm was measured by the Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS). Particulate ammonium-to-dimethylaminium ratios were higher than the gas-phase ammonia-to-DMA ratios, suggesting preferential uptake of ammonia over DMA for the collected 10–30 nm VMD particles. This behavior is not consistent with present nanoparticle physicochemical models,more » which predict a higher dimethylaminium fraction when NH3 and DMA are present at similar gas-phase concentrations. Despite the presence in the gas phase of at least 100 times higher base concentrations than sulfuric acid, the recently formed particles always had measured base : acid ratios lower than 1 : 1. The lowest base fractions were found in particles below 15 nm VMD, with a strong size-dependent composition gradient. The reasons for the very acidic composition remain uncertain, but a plausible explanation is that the particles did not reach thermodynamic equilibrium with respect to the bases due to rapid heterogeneous conversion of SO2 to sulfate. Furthermore, these results indicate that sulfuric acid does not require stabilization by ammonium or dimethylaminium as acid–base pairs in particles as small as 10 nm.« less

  7. Unexpectedly acidic nanoparticles formed in dimethylamine-ammonia-sulfuric-acid nucleation experiments at CLOUD

    SciTech Connect

    Lawler, Michael J.; Winkler, Paul M.; Kim, Jaeseok; Ahlm, Lars; Trostl, Jasmin; Praplan, Arnaud P.; Schobesberger, Siegfried; Kurten, Andreas; Kirkby, Jasper; Bianchi, Federico; Duplissy, Jonathan; Hansel, Armin; Jokinen, Tuija; Keskinen, Helmi; Lehtipalo, Katrianne; Leiminger, Markus; Petaja, Tuukka; Rissanen, Matti; Rondo, Linda; Simon, Mario; Sipila, Mikko; Williamson, Christina; Wimmer, Daniela; Riipinen, Ilona; Virtanen, Annele; Smith, James N.

    2016-11-03

    New particle formation driven by acid–base chemistry was initiated in the CLOUD chamber at CERN by introducing atmospherically relevant levels of gas-phase sulfuric acid and dimethylamine (DMA). Ammonia was also present in the chamber as a gas-phase contaminant from earlier experiments. The composition of particles with volume median diameters (VMDs) as small as 10 nm was measured by the Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS). Particulate ammonium-to-dimethylaminium ratios were higher than the gas-phase ammonia-to-DMA ratios, suggesting preferential uptake of ammonia over DMA for the collected 10–30 nm VMD particles. This behavior is not consistent with present nanoparticle physicochemical models, which predict a higher dimethylaminium fraction when NH3 and DMA are present at similar gas-phase concentrations. Despite the presence in the gas phase of at least 100 times higher base concentrations than sulfuric acid, the recently formed particles always had measured base : acid ratios lower than 1 : 1. The lowest base fractions were found in particles below 15 nm VMD, with a strong size-dependent composition gradient. The reasons for the very acidic composition remain uncertain, but a plausible explanation is that the particles did not reach thermodynamic equilibrium with respect to the bases due to rapid heterogeneous conversion of SO2 to sulfate. Furthermore, these results indicate that sulfuric acid does not require stabilization by ammonium or dimethylaminium as acid–base pairs in particles as small as 10 nm.

  8. Changes in the levels of major sulfur metabolites and free amino acids in pea cotyledons recovering from sulfur deficiency

    SciTech Connect

    Macnicol, P.K.; Randall, P.J.

    1987-02-01

    Changes in levels of sulfur metabolites and free amino acids were followed in cotyledons of sulfur-deficient, developing pea seeds (Pisum sativum L.) for 24 hours after resupply of sulfate, during which time the legumin mRNA levels returned almost to normal. Two recovery situations were studied: cultured seeds, with sulfate added to the medium, and seeds attached to the intact plant, with sulfate added to the roots. In both situations the levels of cysteine, glutathione, and methionine rose rapidly, glutathione exhibiting an initial lag. In attached but not cultured seeds methionine markedly overshot the level normally found in sulfur-sufficient seeds. In the cultured seed S-adenosylmethionine (AdoMet), but not S-methylmethionine, showed a sustained rise; in the attached seed the changes were slight. The composition of the free amino acid pool did not change substantially in either recovery situation. In the cultured seed the large rise in AdoMet level occurred equally in nonrecovering seeds. It was accompanied by 6-fold and 10-fold increases in ..gamma..-aminobutyrate and alanine, respectively. These effects are attributed to wounding resulting from excision of the seed. /sup 35/S-labeling experiments showed that there was no significant accumulation of label in unidentified sulfur-containing amino compounds in either recovery situation. It was concluded from these results and those of other workers that, at the present level of knowledge, the most probable candidate for a signal compound, eliciting recovery of legumin mRNA level in response to sulfur-feeding, is cysteine.

  9. Sulfuric Acid droplet formation and growth in the stratosphere after the 1982 eruption of el chichon.

    PubMed

    Hofmann, D J; Rosen, J M

    1983-10-21

    The eruption of El Chichón Volcano in March and April 1982 resulted in the nucleation of large numbers of new sulfuric acid droplets and an increase by nearly an order of magnitude in the size of the preexisting particles in the stratosphere. Nearly 10(7) metric tons of sulfuric acid remained in the stratosphere by the end of 1982, about 40 times as much as was deposited by Mount St. Helens in 1980.

  10. Optical constants of sulfuric acid - Application to the clouds of Venus

    NASA Technical Reports Server (NTRS)

    Palmer, K. F.; Williams, D.

    1975-01-01

    Young (1973) and Sill (1972) have independently suggested that the clouds of Venus may well consist of particles composed of sulfuric acid molecules with attached water molecules. For a further study of this hypothesis an investigation has been conducted with the objective to supply the needed laboratory data for a wide range of sulfuric acid concentrations. Optical constants have been determined for the visible, near infrared, and intermediate infrared wavelength regions.

  11. Therapeutic paracetamol treatment in older persons induces dietary and metabolic modifications related to sulfur amino acids.

    PubMed

    Pujos-Guillot, Estelle; Pickering, Gisèle; Lyan, Bernard; Ducheix, Gilles; Brandolini-Bunlon, Marion; Glomot, Françoise; Dardevet, Dominique; Dubray, Claude; Papet, Isabelle

    2012-02-01

    Sulfur amino acids are determinant for the detoxification of paracetamol (N-acetyl-p-aminophenol) through sulfate and glutathione conjugations. Long-term paracetamol treatment is common in the elderly, despite a potential cysteine/glutathione deficiency. Detoxification could occur at the expense of anti-oxidative defenses and whole body protein stores in elderly. We tested how older persons satisfy the extra demand in sulfur amino acids induced by long-term paracetamol treatment, focusing on metabolic and nutritional aspects. Effects of 3 g/day paracetamol for 14 days on fasting blood glutathione, plasma amino acids and sulfate, urinary paracetamol metabolites, and urinary metabolomic were studied in independently living older persons (five women, five men, mean (±SEM) age 74 ± 1 years). Dietary intakes were recorded before and at the end of the treatment and ingested sulfur amino acids were evaluated. Fasting blood glutathione, plasma amino acids, and sulfate were unchanged. Urinary nitrogen excretion supported a preservation of whole body proteins, but large-scale urinary metabolomic analysis revealed an oxidation of some sulfur-containing compounds. Dietary protein intake was 13% higher at the end than before paracetamol treatment. Final sulfur amino acid intake reached 37 mg/kg/day. The increase in sulfur amino acid intake corresponded to half of the sulfur excreted in urinary paracetamol conjugates. In conclusion, older persons accommodated to long-term paracetamol treatment by increasing dietary protein intake without any mobilization of body proteins, but with decreased anti-oxidative defenses. The extra demand in sulfur amino acids led to a consumption far above the corresponding population-safe recommendation.

  12. [Studies on carbonization of saccharides by using aqueous solution of various acids].

    PubMed

    Zhang, Xin; He, An-Qi; Kang, Ting-Guo; Xia, Jin-Ming; Weng, Shi-Fu; Xu, Yi-Zhuang; Wu, Jin-Guang

    2014-09-01

    The authors tried to establish an approach to use acids to convert biomass into a fuel with higher carbon content and lower oxygen content in a zero-energy-consumption fashion. Considering that biomass is composed of monosaccharide, we used aqueous solutions of variation acids including hydrochloric acid, sulfuric acid and perchloric acid to treat 2-deoxy-ribose and fructose at ambient temperature and pressure. Black substances were produced after a period of time when 2-deoxy-ribose and fructose were mixed with aqueous solutions containing 8 mol · L(-1) acids. The black substance was collected and characterized by using elemental analysis, Fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). Elemental analysis results indicate that the contents of carbon increases significantly in the black substances in comparison with 2-deoxy-ribose and fructose. Moreover, XPS results indicate that the content of oxygen in the black substance undergoes a significant decrease compared with pure 2-deoxy-ribose and fructose. In the XPS spectra, the is peaks of 2-deoxy-ribose, strong sub peak at 286. 05 eV, which is assigned to carbon linked to oxygen directly, dominate in the C is peak envelop. After treatment by HClO4, the peak decreased dramatically. This result also supports the conclusion that the content of oxygen in mono-saccharide is significantly reduced after treatment by acids. In the FTIR spectra of the black substances, strong peaks can be observed around 1 600 cm(-1), indicating that C==C bond is formed in the product. The above results suggest that treatments with acids may be developed as a new zero-energy-consumption approach to convert biomass in a new fuel with improved energy output efficiency.

  13. Photon and Water Mediated Sulfur Oxide and Acid Chemistry in the Atmosphere of Venus

    NASA Astrophysics Data System (ADS)

    Kroll, Jay A.; Vaida, Veronica

    2014-06-01

    Sulfur compounds have been observed in the atmospheres of a number of planetary bodies in our solar system including Venus, Earth, Mars, Io, Europa, and Callisto. The global cloud cover on Venus located at an altitude between 50 and 80 kilometers is composed primarily of sulfuric acid (H_2SO_4) and water. Planetary photochemical models have attempted to explain observations of sulfuric acid and sulfur oxides with significant discrepancies remaining between models and observation. In particular, high SO_2 mixing ratios are observed above 90 km which exceed model predictions by orders of magnitude. Work recently done in the Vaida lab has shown red light can drive photochemistry through overtone pumping for acids like H_2SO_4 and has been successful in explaining much of the sulfur chemistry in Earth's atmosphere. Water can have a number of interesting effects such as catalysis, suppression, and anti-catalysis of thermal and photochemical processes. We investigate the role of water complexes in the hydration of sulfur oxides and dehydration of sulfur acids and present spectroscopic studies to document such effects. We investigate these reactions using FTIR and UV/Vis spectroscopy and will report on our findings.

  14. Nucleation modeling of the Antarctic stratospheric CN layer and derivation of sulfuric acid profiles

    NASA Astrophysics Data System (ADS)

    Münch, Steffen; Curtius, Joachim

    2017-06-01

    Recent analysis of long-term balloon-borne measurements of Antarctic stratospheric condensation nuclei (CN) between July and October showed the formation of a volatile CN layer at 21-27 km altitude in a background of existing particles. We use the nucleation model SAWNUC to simulate these CN in subsiding air parcels and study their nucleation and coagulation characteristics. Our simulations confirm recent analysis that the development of the CN layer can be explained with neutral sulfuric acid-water nucleation and we show that outside the CN layer the measured CN concentrations are well reproduced just considering coagulation and the subsidence of the air parcels. While ion-induced nucleation is expected as the dominating formation process at higher temperatures, it does not play a significant role during the CN layer formation as the charged clusters recombine too fast. Further, we derive sulfuric acid concentrations for the CN layer formation. Our concentrations are about 1 order of magnitude higher than previously presented concentrations as our simulations consider that nucleated clusters have to grow to CN size and can coagulate with preexisting particles. Finally, we calculate threshold sulfuric acid profiles that show which concentration of sulfuric acid is necessary for nucleation and growth to observable size. These threshold profiles should represent upper limits of the actual sulfuric acid outside the CN layer. According to our profiles, sulfuric acid concentrations seem to be below midlatitude average during Antarctic winter but above midlatitude average for the CN layer formation.

  15. Amino-acid contamination of aqueous hydrochloric acid.

    NASA Technical Reports Server (NTRS)

    Wolman, Y.; Miller, S. L.

    1971-01-01

    Considerable amino-acid contamination in commercially available analytical grade hydrochloric acid (37% HCl) was found. One bottle contained 8,300 nmol of amino-acids per liter. A bottle from another supplier contained 6,700 nmol per liter. The contaminants were mostly protein amino-acids and several unknowns. Data on the volatility of the amino-acids during HCl distillation were also obtained.

  16. Amino-acid contamination of aqueous hydrochloric acid.

    NASA Technical Reports Server (NTRS)

    Wolman, Y.; Miller, S. L.

    1971-01-01

    Considerable amino-acid contamination in commercially available analytical grade hydrochloric acid (37% HCl) was found. One bottle contained 8,300 nmol of amino-acids per liter. A bottle from another supplier contained 6,700 nmol per liter. The contaminants were mostly protein amino-acids and several unknowns. Data on the volatility of the amino-acids during HCl distillation were also obtained.

  17. Backscatter laser depolarization studies of simulated stratospheric aerosols - Crystallized sulfuric acid droplets

    NASA Technical Reports Server (NTRS)

    Sassen, Kenneth; Zhao, Hongjie; Yu, Bing-Kun

    1989-01-01

    The optical depolarizing properties of simulated stratospheric aerosols were studied in laboratory laser (0.633 micrometer) backscattering experiments for application to polarization lidar observations. Clouds composed of sulfuric acid solution droplets, some treated with ammonia gas, were observed during evaporation. The results indicate that the formation of minute ammonium sulfate particles from the evaporation of acid droplets produces linear depolarization ratios of beta equivalent to 0.02, but beta equivalent to 0.10 to 0.15 are generated from aged acid cloud aerosols and acid droplet crystalization effects following the introduction of ammonia gas into the chamber. It is concluded that partially crystallized sulfuric acid droplets are a likely candidate for explaining the lidar beta equivalent to 0.10 values that have been observed in the lower stratosphere in the absence of the relatively strong backscattering from homogeneous sulfuric acid droplet (beta equivalent to 0) or ice crystal (beta equivalent to 0.5) clouds.

  18. Backscatter laser depolarization studies of simulated stratospheric aerosols: Crystallized sulfuric acid droplets

    NASA Technical Reports Server (NTRS)

    Sassen, Kenneth; Zhao, Hongjie; Yu, Bing-Kun

    1988-01-01

    The optical depolarizing properties of simulated stratospheric aerosols were studied in laboratory laser (0.633 micrometer) backscattering experiments for application to polarization lidar observations. Clouds composed of sulfuric acid solution droplets, some treated with ammonia gas, were observed during evaporation. The results indicate that the formation of minute ammonium sulfate particles from the evaporation of acid droplets produces linear depolarization ratios of beta equivalent to 0.02, but beta equivalent to 0.10 to 0.15 are generated from aged acid cloud aerosols and acid droplet crystallization effects following the introduction of ammonia gas into the chamber. It is concluded that partially crystallized sulfuric acid droplets are a likely candidate for explaining the lidar beta equivalent to 0.10 values that have been observed in the lower stratosphere in the absence of the relatively strong backscattering from homogeneous sulfuric acid droplet (beta equivalent to 0) or ice crystal (beta equivalent to 0.5) clouds.

  19. Freezing of sulfuric and nitric acid solutions: Implications for polar stratospheric cloud formation

    NASA Astrophysics Data System (ADS)

    Salcedo Gonzalez, Dara

    2000-12-01

    Polar Stratospheric Clouds (PSCs) play an important role in ozone chemistry during the polar winter. The magnitude of their effect depends on their phase, composition and formation mechanism, which are not fully understood yet. In order to understand how liquid PSCs freeze, two apparatus were designed to study the freezing behavior of small drops using a Fourier transform infrared (FTIR) spectrometer and an optical microscope. Sulfuric acid aqueous drops with composition of 10 to 50 wt % were studied with the FTIR apparatus. The surface on which the drops stand caused heterogeneous nucleation of ice, but not of the sulfuric acid hydrates. The more concentrated solutions (>40 wt %) supercooled to 130 K without freezing. Below 150 K these solutions formed an amorphous solid, which liquefied upon warming. Drops with composition of 40 to 64 wt % HNO3 were prepared and their phase transitions were detected with the optical microscope apparatus. Freezing temperatures of the drops were determined and homogeneous nucleation rates of nitric acid dihydrate (JNAD) and nitric acid trihydrate (JNAT) between 170 and 190 K were calculated. JNAT and JNAD depend predominantly on the saturation of the solid in the liquid solution: higher saturation ratios correspond to higher nucleation rates. Classical nucleation theory was used to parameterize this relation. Since the saturation ratios of NAD and NAT vary with temperature and composition in different ways, NAT or NAD can form preferentially under different conditions. Evidence was found that NAD catalyzes the nucleation of NAT below ~183 K. Mullite, cristobalite and alumina were tested as possible heterogeneous nuclei of volcanic origin for PSCs. They catalyze freezing of NAD and NAT at temperatures below 179 K, which are too low to be stratospherically important. The results suggest that the largest drops in a PSC will freeze homogeneously if the stratospheric temperature remains below the NAT condensation temperature for more

  20. ENERGY EFFICIENCY LIMITS FOR A RECUPERATIVE BAYONET SULFURIC ACID DECOMPOSITION REACTOR FOR SULFUR CYCLE THERMOCHEMICAL HYDROGEN PRODUCTION

    SciTech Connect

    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.

  1. γ-Irradiation of malic acid in aqueous solutions

    NASA Astrophysics Data System (ADS)

    Negron-Mendoza, Alicia; Graff, Rebecca L.; Ponnamperuma, Cyril

    1980-12-01

    The γ-irradiation of malic acid in aqueous solutions was studied under initially oxygenated and oxygen-free conditions in an attempt to determine the possible interconversion of malic acid into other carboxylic acids, specifically those associated with Krebs cycle. The effect of dose on product formation of the system was investigated. Gas-liquid chromatography combined with mass spectrometry was used as the principal means of identification of the non-volatile products. Thin layer chromotography and direct probe mass spectroscopy were also employed. The findings show that a variety of carboxylic acids are formed, with malonic and succinic acids in greatest abundance. These products have all been identified as being formed in the γ-irradiation of acetic acid, suggesting a common intermediary. Since these molecules fit into a metabolic cycle, it is strongly suggestive that prebiotic pathways provided the basis for biological systems.

  2. Irradiation stability of folic Acid in powder and aqueous solution.

    PubMed

    Araújo, Michel M; Marchioni, Eric; Bergaentzle, Martine; Zhao, Minjie; Kuntz, Florent; Hahn, Emeline; Villavicencio, Anna Lucia C H

    2011-02-23

    This study attempts to examine the folic acid stability after irradiation treatment, under different physical states, pH values, and atmosphere conditions. Aqueous folic acid samples, folic acid in powder, and wheat flour fortified with folic acid were irradiated by an electron beam (E-beam) between 0 (control) and 10.0 kGy. It was realized that the physical state of folic acid plays an important role on its stability toward E-beam processing, being largely unstable in solution, no matter the pH and atmosphere conditions assayed. Otherwise, folic acid in powder showed huge irradiation stability, even when mixed in a dry food matrix, such as fortified wheat flour samples.

  3. Reduction in environmental impact of sulfuric acid hydrolysis of bamboo for production of fuel ethanol.

    PubMed

    Sun, Zhao-Yong; Tang, Yue-Qin; Morimura, Shigeru; Kida, Kenji

    2013-01-01

    Fuel ethanol can be produced from bamboo by concentrated sulfuric acid hydrolysis followed by continuous ethanol fermentation. To reduce the environmental impact of this process, treatment of the stillage, reuse of the sulfuric acid and reduction of the process water used were studied. The total organic carbon (TOC) concentration of stillage decreased from 29,688 to 269 mg/l by thermophilic methane fermentation followed by aerobic treatment. Washing the solid residue from acid hydrolysis with effluent from the biological treatment increased the sugar recovery from 69.3% to 79.3%. Sulfuric acid recovered during the acid-sugar separation process was condensed and reused for hydrolysis, resulting in a sugar recovery efficiency of 76.8%, compared to 80.1% when fresh sulfuric acid was used. After acetate removal, the condensate could be reused as elution water in the acid-sugar separation process. As much as 86.3% of the process water and 77.6% of the sulfuric acid could be recycled. Copyright © 2012 Elsevier Ltd. All rights reserved.

  4. Mutual antagonism of sulfur dioxide and abscisic acid in their effect on stomatal aperture in broad bean (Vicia faba L. ) epidermal strips

    SciTech Connect

    Taylor, J.S.; Reid, D.M.; Pharis, R.P.

    1981-12-01

    Abscisic acid (ABA) was found to counteract the stomatal opening in Vicia faba L. caused by SO/sub 2/. The antagonism between SO/sub 2/ and ABA was mutual, and their combined effect depended upon which compound was in the greatest concentration. Stomatal apertures were monitored in detached epidermal strips floated in the light on aqueous solutions of SO/sub 2/ (sulfurous acid) and/or ABA in 0.01 molar sodium citrate buffer (pH 5.8). Low concentrations of sulfurous acid (10/sup -10/ to 10/sup -7/ molar) increased stomatal aperture, but concentrations greater than 10/sup -5/ molar decreased it. A progressive decrease in aperture size occurred as ABA was increased from 10/sup -10/ to 10/sup -5/ molar. No evidence was found for a direct chemical reaction between the buffered sulfurous acid and ABA (exogenous or endogenous). Extractable, endogenous ABA in the strips remained relatively constant after exposure to several different concentrations of sulfurous acid. A technique for quantitating ABA from methanolic extracts of small samples of epidermis (20 milligrams dry weight) using reverse phase high performance liquid chromatography is described.

  5. Comparison of sulfuric and oxalic acid anodizing for preparation of thermal control coatings for spacecraft

    NASA Technical Reports Server (NTRS)

    Le, Huong G.; Watcher, John M.; Smith, Charles A.

    1988-01-01

    The development of thermal control surfaces, which maintain stable solar absorptivity and infrared emissivity over long periods, is challenging due to severe conditions in low-Earth orbit (LEO). Some candidate coatings are second-surface silver-coated Teflon; second-surface, silvered optical solar reflectors made of glass or quartz; and anodized aluminum. Sulfuric acid anodized and oxalic acid anodized aluminum was evaluated under simulated LEO conditions. Oxalic acid anodizing shows promise of greater stability in LEO over long missions, such as the 30 years planned for the Space Station. However, sulfuric acid anodizing shows lower solar absorptivity.

  6. Is there an energy barrier in the growth of sulfuric acid clusters?

    NASA Astrophysics Data System (ADS)

    Olenius, Tinja; Kupiainen, Oona; Ortega, Ismael K.; Vehkamäki, Hanna

    2013-05-01

    We have used a kinetic model and quantum chemical formation free energy data to study the growth of molecular clusters consisting of sulfuric acid and ammonia or sulfuric acid and dimethylamine in atmospherically relevant conditions. All simulations were performed both with and without charged clusters. We show that the cluster growth in the acid-ammonia system involves energy barriers in both electrically neutral and ionic systems, while in the acid-DMA system the growth along the major pathways is barrierless and occurs via electrically neutral clusters also when ions are present.

  7. Investigation of acyl migration in mono- and dicaffeoylquinic acids under aqueous basic, aqueous acidic, and dry roasting conditions.

    PubMed

    Deshpande, Sagar; Jaiswal, Rakesh; Matei, Marius Febi; Kuhnert, Nikolai

    2014-09-17

    Acyl migration in chlorogenic acids describes the process of migration of cinnamoyl moieties from one quinic acid alcohol group to another, thus interconverting chlorogenic acid regioisomers. It therefore constitutes a special case of transesterification reaction. Acyl migration constitutes an important reaction pathway in both coffee roasting and brewing, altering the structure of chlorogenic acid initially present in the green coffee bean. In this contribution we describe detailed and comprehensive mechanistic studies comparing inter- and intramolecular acyl migration involving the seven most common chlorogenic acids in coffee. We employe aqueous acidic and basic conditions mimicking the brewing of coffee along with dry roasting conditions. We show that under aqueous basic conditions intramolecular acyl migration is fully reversible with basic hydrolysis competing with acyl migration. 3-Caffeoylquinic acid was shown to be most labile to basic hydrolysis. We additionally show that the acyl migration process is strongly pH dependent with increased transesterification taking place at basic pH. Under dry roasting conditions acyl migration competes with dehydration to form lactones. We argue that acyl migration precedes lactonization, with 3-caffeoylquinic acid lactone being the predominant product.

  8. Pervaporation of Water from Aqueous Hydriodic Acid and Iodine Mixtures Using Nafion (R) Membranes

    SciTech Connect

    Christopher J. Orme; Frederick F. Stewart

    2007-11-01

    The sulfur-iodine (S-I) process for generation of hydrogen has been proposed as a thermochemical cycle for study due to its predicted high efficiencies. Improvements in the cycle that will yield the greatest gain in both operating and capital costs involve chemical separations. To date, membrane processes have been largely unexplored. In this work, a materials compatibility study into the application of Nafion-117® and Nafion-112® as membranes for the pervaporation of water from aqueous mixtures of hydriodic acid (HI) and HI/iodine at 134 ºC was conducted. Significant fluxes of water were measured with respect to feed water concentration and high separation factors were calculated. Most surprisingly, HI and HI/iodine feeds acted very differently in that HI-iodine complexes formed result in higher fluxes and separation factors than what was observed for HI alone.

  9. Dissolution of sulfuric acid tetrahydrate at low temperatures and subsequent growth of nitric acid trihydrate

    NASA Astrophysics Data System (ADS)

    Iraci, Laura T.; Fortin, Tara J.; Tolbert, Margaret A.

    1998-04-01

    Crystalline sulfuric acid tetrahydrate (SAT) has been observed to change phase at temperatures below its melting point, in agreement with recent theoretical predictions of deliquescence. Dissolution of SAT was observed in 63% of experiments expected to show a phase change, leading to formation of a ternary HNO3/H2SO4/H2O solution. This solution, which still contained a portion of the original solid SAT, crystallized to form nitric acid trihydrate (NAT). NAT then continued to grow by condensation of additional nitric acid and water at temperatures several degrees above the ice frost point. This process of SAT dissolution followed by NAT crystallization and growth may offer a mechanism for the formation of type Ia polar stratospheric clouds on frozen sulfate aerosols when SNAT>15.

  10. First direct sulfuric acid detection in the exhaust plume of a jet aircraft in flight

    NASA Astrophysics Data System (ADS)

    Curtius, J.; Sierau, B.; Arnold, F.; Baumann, R.; Busen, R.; Schulte, P.; Schumann, U.

    Sulfuric acid (SA) was for the first time directly detected in the exhaust plume of a jet aircraft in flight. The measurements were made by a novel aircraft-based VACA (Volatile Aerosol Component Analyzer) instrument of MPI-K Heidelberg while the research aircraft Falcon was chasing another research aircraft ATTAS. The VACA measures the total SA in the gas and in volatile submicron aerosol particles. During the chase the engines of the ATTAS alternatively burned sulfur-poor and sulfur-rich fuel. In the sulfur-rich plume very marked enhancements of total SA were observed of up to 1300 pptv which were closely correlated with ΔCO2 and ΔT and were far above the local ambient atmospheric background-level of typically 15-50 pptv. Our observations indicate a lower limit for the efficiency ɛ for fuel-sulfur conversion to SA of 0.34 %.

  11. Aqueous synthesis of Cu-doped ZnCdS/ZnS core/shell nanocrystals with a new and highly reactive sulfur source

    NASA Astrophysics Data System (ADS)

    Zeng, Ruosheng; Shen, Rongan; Zhao, Yunqiang; Li, Xingsheng; Sun, Zhiguo; Shen, Yayun

    2014-04-01

    A new sulfur precursor with a highly reactive chemical nature was prepared with S powder and NaBH4 at the high temperature of 180 °C in a closed autoclave and made it possible to carry out the synthesis of high quality metal sulfide nanocrystals (NCs) with diverse composition and structure. Using this new sulfur source, we demonstrated aqueous synthesis of colloidal Cu-doped ZnCdS NCs (d-dots) with pure, color-tunable photoluminescence (PL) in a wide spectral range (from 517 to 650 nm) based on the ‘co-nucleation doping’ strategy. The influences of the various experimental variables, including Cd/Zn ratio, Cu-doping concentration, pH value and amount of mercaptopropionic acid (MPA), on the optical properties of Cu-doped ZnCdS NCs were systematically investigated. Furthermore, highly efficient and stable dopant emission from Cu:ZnCdS/ZnS core/shell d-dots with PL quantum yield as high as 40% was achieved by the deposition of a ZnS shell around the bare Cu:ZnCdS cores; this is the highest reported to date for aqueous doped NCs. The optical properties and structure of the d-dots were characterized by UV-vis absorption spectra, PL spectra, x-ray photoelectron spectroscopy, powder x-ray diffraction, and transmission electron microscopy. The experimental results indicated that this facile synthesis route would provide a versatile approach for the preparation of other water-soluble sulfide NCs.

  12. Efficient hydrogen generation from sodium borohydride hydrolysis using silica sulfuric acid catalyst

    NASA Astrophysics Data System (ADS)

    Manna, Joydev; Roy, Binayak; Sharma, Pratibha

    2015-02-01

    A heterogeneous acid catalyst, silica sulfuric acid, was prepared from silica gel (SiO2) and sulfuric acid (H2SO4). Addition of SO3H functional group to SiO2 has been confirmed through various characterization techniques. The effect of this heterogeneous acid catalyst on hydrogen generation from sodium borohydride hydrolysis reaction was studied for different ratios of catalyst to NaBH4 and at different temperatures. The catalyst exhibited high catalytic activity towards sodium borohydride hydrolysis reaction. The activation energy of the NaBH4 hydrolysis reaction in the presence of silica sulfuric acid was calculated to be the lowest (17 kJ mol-1) among reported heterogeneous catalysts till date.

  13. Observation of neutral sulfuric acid-amine containing clusters in laboratory and ambient measurements

    SciTech Connect

    Kuang C.; Zhao, J.; Smith, J. N.; Eisele, F. L.; Chen, M.; McMurry, P. H.

    2011-11-02

    Recent ab initio calculations showed that amines can enhance atmospheric sulfuric acid-water nucleation more effectively than ammonia, and this prediction has been substantiated in laboratory measurements. Laboratory studies have also shown that amines can effectively displace ammonia in several types of ammonium clusters. However, the roles of amines in cluster formation and growth at a microscopic molecular scale (from molecular sizes up to 2 nm) have not yet been well understood. Processes that must be understood include the incorporation of amines into sulfuric acid clusters and the formation of organic salts in freshly nucleated particles, which contributes significantly to particle growth rates. We report the first laboratory and ambient measurements of neutral sulfuric acid-amine clusters using the Cluster CIMS, a recently-developed mass spectrometer designed for measuring neutral clusters formed in the atmosphere during nucleation. An experimental technique, which we refer to as Semi-Ambient Signal Amplification (SASA), was employed. Sulfuric acid was added to ambient air, and the concentrations and composition of clusters in this mixture were analyzed by the Cluster CIMS. This experimental approach led to significantly higher cluster concentrations than are normally found in ambient air, thereby increasing signal-to-noise levels and allowing us to study reactions between gas phase species in ambient air and sulfuric acid containing clusters. Mass peaks corresponding to clusters containing four H{sub 2}SO{sub 4} molecules and one amine molecule were clearly observed, with the most abundant sulfuric acid-amine clusters being those containing a C2- or C4-amine (i.e. amines with masses of 45 and 73 amu). Evidence for C3- and C5-amines (i.e. amines with masses of 59 and 87 amu) was also found, but their correlation with sulfuric acid tetramer was not as strong as was observed for the C2- and C4-amines. The formation mechanisms for those sulfuric acid

  14. Near infrared photochemistry of pyruvic acid in aqueous solution.

    PubMed

    Larsen, Molly C; Vaida, Veronica

    2012-06-21

    Recent experimental and theoretical results have suggested that organic acids such as pyruvic acid, can be photolyzed in the ground electronic state by the excitation of the OH stretch vibrational overtone. These overtones absorb in the near-infrared and visible regions of the spectrum where the solar photons are plentiful and could provide a reaction pathway for the organic acids and alcohols that are abundant in the earth's atmosphere. In this paper the overtone initiated photochemistry of aqueous pyruvic acid is investigated by monitoring the evolution of carbon dioxide. In these experiments CO(2) is being produced by excitation in the near-infrared, between 850 nm and ∼1150 nm (11,765-8696 cm(-1)), where the second OH vibrational overtone (Δν = 3) of pyruvic acid is expected to absorb. These findings show not only that the overtone initiated photochemical decarboxylation reaction occurs but also that in the aqueous phase it occurs at a lower energy than was predicted for the overtone initiated reaction of pyruvic acid in the gas phase (13,380 cm(-1)). A quantum yield of (3.5 ± 1.0) × 10(-4) is estimated, suggesting that although this process does occur, it does so with a very low efficiency.

  15. Acid deposition critical loads modeling for the simulation of sulfur exceedance and reduction in Guangdong, China.

    PubMed

    Qiu, Rongliang; Wang, Shizhong; Qiu, Hao; Wang, Xuemei; Liao, Jin; Zhang, Zhentian

    2009-01-01

    The current acid deposition critical loads in Guangdong, China were calculated using the PROFILE model with a 3 km x 3 km resolution. Calculations were carried out for critical loads of potential acidity, actual acidity, sulfur and nitrogen, with values in extents of 0-3.5, 0-14.0, 0-26.0 and 0-3.5 kmol/(hm2 x year), respectively. These values were comparable to previously reported results and reflected the influences of vegetation and soil characteristics on the soil acid buffering capacity. Simulations of SO2 emission and sulfur deposition in this study showed that sulfur deposition core areas mirrored SO2 emission centers. The prediction of sulfur deposition after 20% and 40% reduction of SO2 emission suggested that the reduction of area sources contributed greatly to the decrease of sulfur deposition. Thus, abatement of area source emissions could be the primary way to mitigate sulfur deposition in Guangdong to meet both the provincial and national regulations of air pollution control.

  16. Roles of sulfuric acid in elemental mercury removal by activated carbon and sulfur-impregnated activated carbon.

    PubMed

    Morris, Eric A; Kirk, Donald W; Jia, Charles Q; Morita, Kazuki

    2012-07-17

    This work addresses the discrepancy in the literature regarding the effects of sulfuric acid (H(2)SO(4)) on elemental Hg uptake by activated carbon (AC). H(2)SO(4) in AC substantially increased Hg uptake by absorption particularly in the presence of oxygen. Hg uptake increased with acid amount and temperature exceeding 500 mg-Hg/g-AC after 3 days at 200 °C with AC treated with 20% H(2)SO(4). In the absence of other strong oxidizers, oxygen was able to oxidize Hg. Upon oxidation, Hg was more readily soluble in the acid, greatly enhancing its uptake by acid-treated AC. Without O(2), S(VI) in H(2)SO(4) was able to oxidize Hg, thus making it soluble in H(2)SO(4). Consequently, the presence of a bulk H(2)SO(4) phase within AC pores resulted in an orders of magnitude increase in Hg uptake capacity. However, the bulk H(2)SO(4) phase lowered the AC pore volume and could block the access to the active surface sites and potentially hinder Hg uptake kinetics. AC treated with SO(2) at 700 °C exhibited a much faster rate of Hg uptake attributed to sulfur functional groups enhancing adsorption kinetics. SO(2)-treated carbon maintained its fast uptake kinetics even after impregnation by 20% H(2)SO(4).

  17. Influence of charge exchange in acidic aqueous and alcoholic titania dispersions on viscosity.

    PubMed

    Rosenholm, Jarl B; Dahlsten, Per

    2015-12-01

    Charging effects resulting from adsorption of acid, acid anions, and protons on titania (anatase) surfaces in anhydrous or mixed alcohol-water dispersions is summarized. The suddenly enhanced conductivity as compared to titania-free solutions has previously been modeled and explained as surface-induced electrolytic dissociation (SIED) of weak acids. This model and recently published results identifying concurrent surface-induced liquid (solvent) dissociation (SILD) are evaluated with experimentally determined conductivity and pH of solutions, zeta-potential of particles, and viscosity of dispersions. Titania (0-25wt%)-alcohol (methanol, ethanol, and propanol) dispersions mixed with (0-100wt%) water were acidified with oxalic, phosphoric, and sulfuric acids. It was found that the experimental results could in many cases be condensed to master curves representing extensive experimental results. These curves reveal that major properties of the systems appear within three concentration regions were different mechanisms (SILD, surface-induced liquid dissociation; SIAD, surface-induced acid dissociation) and charge rearrangement were found to be simultaneously active. In particular, zeta-potential - pH and viscosity - pH curves are in acidified non-polar solvents mirror images to those dependencies observed in aqueous dispersions to which hydroxyl is added. The results suggest that multiple dispersion and adsorption equilibria should be considered in order to characterize the presented exceptionally extensive and complex experimental results. Copyright © 2015 Elsevier B.V. All rights reserved.

  18. Dynamics and mass accommodation of HCl molecules on sulfuric acid-water surfaces.

    PubMed

    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.

  19. A sulfuric-lactic acid process for efficient purification of fungal chitosan with intact molecular weight.

    PubMed

    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.

  20. Cluster Formation of Sulfuric Acid with Dimethylamine or Diamines and Detection with Chemical Ionization

    NASA Astrophysics Data System (ADS)

    Jen, C. N.; McMurry, P. H.; Hanson, D. R.

    2015-12-01

    Chemical ionization (CI) mass spectrometers are used to study atmospheric nucleation by detecting clusters produced by reactions of sulfuric acid and various basic gases. These instruments typically use nitrate to chemically ionize clusters for detection. In this study, we compare measured cluster concentrations formed by reacting sulfuric acid vapor with dimethylamine, ethylene diamine, tetramethylethylene diamine, or butanediamine (also known as putrescine) using nitrate and acetate ions. We show from flow reactor measurements that nitrate is unable to chemically ionize clusters with weak acidities. In addition, we vary the ion-molecule reaction time to probe the chemical ionization processes and lifetimes of ions composed of sulfuric acid and base molecules. We then model the neutral and ion cluster formation pathways, including chemical ionization, ion-induced clustering, and ion decomposition, to better identify which cluster types cannot be chemically ionized by nitrate. Our results show that sulfuric acid dimer with two diamines and sulfuric acid trimer with 2 or more base molecules cannot be chemical ionized by nitrate. We conclude that cluster concentrations measured with acetate CI gives a better representation of both cluster abundancies and their base content than nitrate CI.

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

    NASA Astrophysics Data System (ADS)

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

    2014-06-01

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

  2. Lipoic Acid as a Possible Pharmacological Source of Hydrogen Sulfide/Sulfane Sulfur.

    PubMed

    Bilska-Wilkosz, Anna; Iciek, Małgorzata; Kowalczyk-Pachel, Danuta; Górny, Magdalena; Sokołowska-Jeżewicz, Maria; Włodek, Lidia

    2017-03-02

    The aim of the present study was to verify whether lipoic acid (LA) itself is a source of H₂S and sulfane sulfur. It was investigated in vitro non-enzymatically and enzymatically (in the presence of rat tissue homogenate). The results indicate that both H₂S and sulfane sulfur are formed from LA non-enzymatically in the presence of environmental light. These results suggest that H₂S is the first product of non-enzymatic light-dependent decomposition of LA that is, probably, next oxidized to sulfane sulfur-containing compound(s). The study performed in the presence of rat liver and kidney homogenate revealed an increase of H₂S level in samples containing LA and its reduced form dihydrolipoic acid (DHLA). It was accompanied by a decrease in sulfane sulfur level. It seems that, in these conditions, DHLA acts as a reducing agent that releases H₂S from an endogenous pool of sulfane sulfur compounds present in tissues. Simultaneously, it means that exogenous LA cannot be a direct donor of H₂S/sulfane sulfur in animal tissues. The present study is an initial approach to the question whether LA itself is a donor of H₂S/sulfane sulfur.

  3. Distribution of Hydrogen Peroxide, Carbon Dioxide, and Sulfuric Acid in Europa's Icy Crust

    NASA Technical Reports Server (NTRS)

    Carlson, R. W.

    2004-01-01

    Galileo's Near Infrared Mapping Spectrometer (NIMS) detected hydrogen peroxide, carbon dioxide and a hydrated material on Europa's surface, the latter interpreted as hydrated sulfuric acid (H2SO4*nH2O) or hydrated salts. Related compounds are molecular oxygen, sulfur dioxide, and two chromophores, one that is dark in the ultraviolet(UV) and concentrated on the trailing side, the other brighter in the UV and preferentially distributed in the leading hemisphere. The UV-dark material has been suggested to be sulfur.

  4. Distribution of Hydrogen Peroxide, Carbon Dioxide, and Sulfuric Acid in Europa's Icy Crust

    NASA Technical Reports Server (NTRS)

    Carlson, R. W.

    2004-01-01

    Galileo's Near Infrared Mapping Spectrometer (NIMS) detected hydrogen peroxide, carbon dioxide and a hydrated material on Europa's surface, the latter interpreted as hydrated sulfuric acid (H2SO4*nH2O) or hydrated salts. Related compounds are molecular oxygen, sulfur dioxide, and two chromophores, one that is dark in the ultraviolet(UV) and concentrated on the trailing side, the other brighter in the UV and preferentially distributed in the leading hemisphere. The UV-dark material has been suggested to be sulfur.

  5. The sulfuric acid leaching of Bayer electrofilter fines: A practical kinetical approach

    NASA Astrophysics Data System (ADS)

    Sancho Martínez, J. P.; Ayala, Espina J.; García Coque, M. P.; Fernández, Pérez B.; Costales, Alonso D.

    2006-08-01

    Electrofilter fines, which are by-products of the Bayer process for the production of alumina from bauxite, were characterized to evaluate the alumina that was potentially extractable with sulfuric acid. Acid leaching is carried out at different concentrations of sulfuric acid, at different temperatures, pulp densities, and times, to dissolve gibbsite and transition aluminas. The result is an aluminum sulfate solution. This article reports on a study of the kinetics of the leaching reaction at 90°C with two pulp densities: 10% and 30%.

  6. Picosecond pulse radiolysis of highly concentrated sulfuric acid solutions: evidence for the oxidation reactivity of radical cation H2O(•+).

    PubMed

    Ma, Jun; Schmidhammer, Uli; Mostafavi, Mehran

    2014-06-12

    Aqueous solution of sulfuric acid is used as a suitable system to investigate the reactivity of the short-lived radical cation H2O(•+) which is generated by radiation in water. Ten aqueous solutions containing sulfuric acid with concentration from 1 to 18 mol L(-1) are studied by picosecond pulse radiolysis. The absorbance of the secondary radical SO4(•-) (or HSO4(•)) formed within the 10 ps electron pulse is measured by a pulse-probe method in the visible range. The analysis of the kinetics show that the radicals of sulfuric acid are formed within the picosecond electron pulse via two parallel mechanisms: direct electron detachment by the electron pulse and oxidation by the radical cation of water H2O(•+). In highly concentrated solution when SO4(2-) is in contact with H2O(•+), the electron transfer becomes competitive against proton transfer with another water molecule. Therefore, H2O(•+) may act as an extremely strong oxidant. The maximum radiolytic yield of scavenged H2O(•+) is estimated to be 5.3 ± 0.1 × 10(-7) mol J(-1).

  7. Lung-cancer mortality in workers exposed to sulfuric acid mist and other acid mists in steel-pickling operations

    SciTech Connect

    Beaumont, J.J.; Leveton, J.; Knox, K.; Bloom, T.; McQuiston, T.

    1986-01-01

    A total of 1165 steel workers who had been exposed to sulfuric acid and other acid mists during steel-pickling operations were studied to determine whether there was any evidence of respiratory cancer which could be linked to these exposures. These workers had been employed at three large midwestern steel-manufacturing operations where acid was used to remove oxides from newly produced steel. Cancer of the trachea, bronchus, and lung showed increased mortality in this study. Deaths from buccal cavity, pharynx, and larynx cancers were at normal levels. Deaths from nonmalignant respiratory diseases were lower than normal rates. The excess lung-cancer cases occurred both in workers who had been exposed only to sulfuric-acid mists and in those exposed only to other acids. The authors conclude that there was an increased risk of lung cancer in workers exposed to sulfuric acid and in workers exposed to other acids. Continued monitoring of lung-cancer rates is recommended by the authors, since other acids have replaced sulfuric acid to a great degree.

  8. Ice core sulfur and methanesulfonic acid (MSA) records from southern Greenland document North American and European air pollution and suggest a decline in regional biogenic sulfur emissions.

    NASA Astrophysics Data System (ADS)

    Pasteris, D. R.; McConnell, J. R.; Burkhart, J. F.; Saltzman, E. S.

    2014-12-01

    Sulfate aerosols have an important cooling effect on the Earth because they scatter sunlight back to space and form cloud condensation nuclei. However, understanding of the atmospheric sulfur cycle is incomplete, leading to uncertainty in the assessment of past, present and future climate forcing. Here we use annually resolved observations of sulfur and methanesulfonic acid (MSA) concentration in an array of precisely dated Southern Greenland ice cores to assess the history of sulfur pollution emitted from North America and Europe and the history of biogenic sulfate aerosol derived from the North Atlantic Ocean over the last 250 years. The ice core sulfur time series is found to closely track sulfur concentrations in North American and European precipitation since records began in 1965, and also closely tracks estimated sulfur emissions since 1850 within the air mass source region as determined by back trajectory analysis. However, a decline to near-preindustrial sulfur concentrations in the ice cores after 1995 that is not so extensive in the source region emissions indicates that there has been a change in sulfur cycling over the last 150 years. The ice core MSA time series shows a decline of 60% since the 1860s, and is well correlated with declining sea ice concentrations around Greenland, suggesting that the phytoplankton source of biogenic sulfur has declined due to a loss of marginal sea ice zone habitat. Incorporating the implied decrease in biogenic sulfur in our analysis improves the match between the ice core sulfur record and the source region emissions throughout the last 150 years, and solves the problem of the recent return to near-preindustrial levels in the Greenland ice. These findings indicate that the transport efficiency of sulfur air pollution has been relatively stable through the industrial era and that biogenic sulfur emissions in the region have declined.

  9. Sulfuric acid nucleation: An experimental study of the effect of seven bases

    NASA Astrophysics Data System (ADS)

    Glasoe, W. A.; Volz, K.; Panta, B.; Freshour, N.; Bachman, R.; Hanson, D. R.; McMurry, P. H.; Jen, C.

    2015-03-01

    Nucleation of particles with sulfuric acid, water, and nitrogeneous bases was studied in a flow reactor. Sulfuric acid and water levels were set by flows over sulfuric acid and water reservoirs, respectively, and the base concentrations were determined from measured permeation rates and flow dilution ratios. Particle number distributions were measured with a nano-differential-mobility-analyzer system. Results indicate that the nucleation capability of NH3, methylamine, dimethylamine, and trimethylamine with sulfuric acid increases from NH3 as the weakest, methylamine next, and dimethylamine and trimethylamine the strongest. Three other bases were studied, and experiments with triethylamine showed that it is less effective than methylamine, and experiments with urea and acetamide showed that their capabilities are much lower than the amines with acetamide having basically no effect. When both NH3 and an amine were present, nucleation was more strongly enhanced than with just the amine present. Comparisons of nucleation rates to predictions and previous experimental work are discussed, and the sulfuric acid-base nucleation rates measured here are extrapolated to atmospheric conditions. The measurements suggest that atmospheric nucleation rates are significantly affected by synergistic interactions between ammonia and amines.

  10. Pretreatment of Sugar Beet Pulp with Dilute Sulfurous Acid is Effective for Multipurpose Usage of Carbohydrates.

    PubMed

    Kharina, M; Emelyanov, V; Mokshina, N; Ibragimova, N; Gorshkova, T

    2016-05-01

    Sulfurous acid was used for pretreatment of sugar beet pulp (SBP) in order to achieve high efficiency of both extraction of carbohydrates and subsequent enzymatic hydrolysis of the remaining solids. The main advantage of sulfurous acid usage as pretreatment agent is the possibility of its regeneration. Application of sulfurous acid as hydrolyzing agent in relatively low concentrations (0.6-1.0 %) during a short period of time (10-20 min) and low solid to liquid ratio (1:3, 1:6) allowed effective extraction of carbohydrates from SBP and provided positive effect on subsequent enzymatic hydrolysis. The highest obtained concentration of reducing substances (RS) in hydrolysates was 8.5 %; up to 33.6 % of all carbohydrates present in SBP could be extracted. The major obtained monosaccharides were arabinose and glucose (9.4 and 7.3 g/l, respectively). Pretreatment of SBP with sulfurous acid increased 4.6 times the yield of glucose during subsequent enzymatic hydrolysis of remaining solids with cellulase cocktail, as compared to the untreated SBP. Total yield of glucose during SBP pretreatment and subsequent enzymatic hydrolysis amounted to 89.4 % of the theoretical yield. The approach can be applied directly to the wet SBP. Hydrolysis of sugar beet pulp with sulfurous acid is recommended for obtaining of individual monosaccharides, as well as nutritional media.

  11. Homogenous nucleation of sulfuric acid and water at close to atmospherically relevant conditions

    NASA Astrophysics Data System (ADS)

    Brus, D.; Neitola, K.; Hyvärinen, A.-P.; Petäjä, T.; Vanhanen, J.; Sipilä, M.; Paasonen, P.; Kulmala, M.; Lihavainen, H.

    2011-06-01

    In this study the homogeneous nucleation rates in the system of sulfuric acid and water were measured by using a flow tube technique. The goal was to directly compare particle formation rates obtained from atmospheric measurements with nucleation rates of freshly nucleated particles measured with particle size magnifier (PSM) which has detection efficiency of unity for particles having mobility diameter of 1.5 nm. The gas phase sulfuric acid concentration in this study was measured with the chemical ionization mass spectrometer (CIMS), commonly used in field measurements. The wall losses of sulfuric acid were estimated from measured concentration profiles along the flow tube. The initial concentrations of sulfuric acid estimated from loss measurements ranged from 108 to 3 × 109 molecules cm-3. The nucleation rates obtained in this study cover about three orders of magnitude from 10-1 to 102 cm-3 s-1 for commercial ultrafine condensation particle counter (UCPC) TSI model 3025A and from 101 to 104 cm-3 s-1 for PSM. The nucleation rates and the slopes (dlnJ/dln [H2SO4]) show satisfactory agreement when compared to empirical kinetic and activation models and the latest atmospheric nucleation data. To the best of our knowledge, this is the first experimental work providing temperature dependent nucleation rate measurements using a high efficiency particle counter with a cut-off-size of 1.5 nm together with direct measurements of gas phase sulfuric acid concentration.

  12. Sulfuric acid speleogenesis (SAS) close to the water table: Examples from southern France, Austria, and Sicily

    NASA Astrophysics Data System (ADS)

    De Waele, Jo; Audra, Philippe; Madonia, Giuliana; Vattano, Marco; Plan, Lukas; D'Angeli, Ilenia M.; Bigot, Jean-Yves; Anoux, Catherine; Nobécourt, Jean-Claude

    2016-01-01

    Caves formed by rising sulfuric waters have been described from all over the world in a wide variety of climate settings, from arid regions to mid-latitude and alpine areas. H2S is generally formed at depth by reduction of sulfates in the presence of hydrocarbons and is transported in solution through the deep aquifers. In tectonically disturbed areas major fractures eventually allow these H2S-bearing fluids to rise to the surface where oxidation processes can become active producing sulfuric acid. This extremely strong acid reacts with the carbonate bedrock creating caves, some of which are among the largest and most spectacular in the world. Production of sulfuric acid mostly occurs at or close to the water table but also in subaerial conditions in moisture films and droplets in the cave environment. These caves are generated at or immediately above the water table, where condensation-corrosion processes are dominant, creating a set of characteristic meso- and micromorphologies. Due to their close connection to the base level, these caves can also precisely record past hydrological and geomorphological settings. Certain authigenic cave minerals, produced during the sulfuric acid speleogenesis (SAS) phase, allow determination of the exact timing of speleogenesis. This paper deals with the morphological, geochemical and mineralogical description of four very typical sulfuric acid water table caves in Europe: the Grotte du Chat in the southern French Alps, the Acqua Fitusa Cave in Sicily (Italy), and the Bad Deutsch Altenburg and Kraushöhle caves in Austria.

  13. New insights into sulfur amino acids function in gut health and disease

    USDA-ARS?s Scientific Manuscript database

    The gastrointestinal tract (GIT) is a metabolically significant site of sulfur amino acids (SAAs) metabolism in the body. Aside from their role in protein synthesis, methionine and cysteine are involved in many biological functions and diseases. Methionine (MET) is an indispensable amino acid and is...

  14. Death of a toddler due to ingestion of sulfuric acid at a clandestine home methamphetamine laboratory.

    PubMed

    Burge, Meredith; Hunsaker, John C; Davis, Gregory J

    2009-12-01

    Exposure to strong acids such as sulfuric acid to either the skin or the gastrointestinal or respiratory mucosa will result respectively in significant-occasionally fatal-cutaneous chemical burns as well as devastating corrosive damage to the respiratory and gastrointestinal tracts. Most injuries are accidental, but there are reports of using acids as weapons or as a means of suicide. The primary mechanism of acid injury is coagulative necrosis of the tissues. Sulfuric acid is a chemical often used in industrial and chemical laboratories, and it is an ingredient in household products like drain cleaner. Easily accessible, over-the-counter, household drain cleaner is one of several common materials used to manufacture methamphetamine. With increasing clandestine methamphetamine laboratories in the United States, exposure to methamphetamine and the toxic chemicals used for its production is a growing problem. In many instances, children living in these laboratories qua homes are at risk for injury and death. We report the death of an unattended toddler, who ingested sulfuric acid drain cleaner in his home. The gross and histopathological autopsy findings in this case are similar to those of previously described cases of sulfuric acid injury.

  15. Process for recovery of sulfur from acid gases

    DOEpatents

    Towler, Gavin P.; Lynn, Scott

    1995-01-01

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

  16. Heavy metal extraction from PCB wastewater treatment sludge by sulfuric acid.

    PubMed

    Kuan, Yu-Chung; Lee, I-Hsien; Chern, Jia-Ming

    2010-05-15

    Heavy metals contaminated wastewater sludge is classified as hazardous solid waste and needs to be properly treated to prevent releasing heavy metals to the environment. In this study, the wastewater treatment sludge from a printed circuit board manufacturing plant was treated in a batch reactor by sulfuric acid to remove the contained heavy metals. The effects of sulfuric acid concentration and solid to liquid ratio on the heavy metal removal efficiencies were investigated. The experimental results showed that the total and individual heavy metal removal efficiencies increased with increasing sulfuric acid concentration, but decreased with increasing solid to liquid ratio. A mathematical model was developed to predict the residual sludge weights at varying sulfuric concentrations and solid to liquid ratios. The trivalent heavy metal ions, iron and chromium were more difficult to be removed than the divalent ions, copper, zinc, nickel, and cadmium. For 5 g/L solid to liquid ratio, more than 99.9% of heavy metals can be removed from the sludge by treating with 0.5M sulfuric acid in 2h. Copyright (c) 2010 Elsevier B.V. All rights reserved.

  17. Effect of various alkaline metal ions on electrochemical behavior of lead electrode in sulfuric acid solution

    NASA Astrophysics Data System (ADS)

    Hirai, Nobumitsu; Yamamoto, Yui

    2015-10-01

    The effect of various alkaline metal ions on electrochemical behavior of lead electrode in sulfuric acid solution has been investigated. It was found that ;the specific anodic oxidation peak; appears at the cathodic scan in cyclic voltammogram of lead electrode in sulfuric acid solution containing Li2SO4, K2SO4, Na2SO4, Rb2SO4, or Cs2SO4. The height of the specific anodic oxidation peak varies with the alkaline sulfate in the solution; K2SO4 >> Na2SO4 > Cs2SO4 > Rb2SO4 > Li2SO4. It should be note that alkaline ions exist in lead sulfate formed on lead electrode in sulfuric acid solution containing potassium sulfate when the electrode was immersed in the solution at the rest potential for more than 1 h.

  18. Diamine-sulfuric acid reactions are a potent source of new particle formation

    NASA Astrophysics Data System (ADS)

    Jen, Coty N.; Bachman, Ryan; Zhao, Jun; McMurry, Peter H.; Hanson, David R.

    2016-01-01

    Atmospheric nucleation from sulfuric acid depends on the concentrations and the stabilizing effect of other trace gases, such as ammonia and amines. Diamines are an understudied class of atmospherically relevant compounds, and we examine how they affect sulfuric acid nucleation in both flow reactor experiments and the atmosphere. The number of particles produced from sulfuric acid and diamines in the flow reactor was equal to or greater than the number formed from monoamines, implying that diamines are more effective nucleating agents. Upper limits of diamine abundance were also monitored during three field campaigns: Lamont, OK (2013); Lewes, DE (2012); and Atlanta, GA (2009). Mixing ratios were measured as high as tens of parts per trillion by volume (GA and OK). Laboratory results suggest that diamines at these levels are important for atmospheric nucleation. Diamines likely participate in atmospheric nucleation and should be considered in nucleation measurements and models.

  19. Reevaluating the contribution of sulfuric acid and the origin of organic compounds in atmospheric nanoparticle growth

    NASA Astrophysics Data System (ADS)

    Vakkari, Ville; Tiitta, Petri; Jaars, Kerneels; Croteau, Philip; Beukes, Johan Paul; Josipovic, Miroslav; Kerminen, Veli-Matti; Kulmala, Markku; Venter, Andrew D.; Zyl, Pieter G.; Worsnop, Douglas R.; Laakso, Lauri

    2015-12-01

    Aerosol particles formed in the atmosphere are important to the Earth's climate system due to their ability to affect cloud properties. At present, little is known about the atmospheric chemistry responsible for the growth of newly formed aerosol particles to climate-relevant sizes. Here combining detailed aerosol measurements with a theoretical framework we found that depending on the gaseous precursors and size of the newly formed particles, the growth was dominated by either sulfuric acid accompanied by ammonium or organic compounds originating in either biogenic emissions or savannah fires. The contribution of sulfuric acid was larger during the early phases of the growth, but in clean conditions organic compounds dominated the growth from 1.5 nm up to climatically relevant sizes. Furthermore, our analysis indicates that in polluted environments the contribution of sulfuric acid to the growth may have been underestimated by up to a factor of 10.

  20. Adsorption of Crystal violet on raw and acid-treated montmorillonite, K10, in aqueous suspension.

    PubMed

    Sarma, Gautam Kumar; Sen Gupta, Susmita; Bhattacharyya, Krishna G

    2016-04-15

    Crystal violet is used as a dye in cotton and silk textiles, paints and printing ink. The dye is hazardous and exposure to it may cause permanent injury to the cornea and conjunctiva including permanent blindness, and in severe cases, may lead to respiratory and kidney failure. The present work describes removal of Crystal violet from aqueous solution by adsorption on raw and acid-treated montmorillonite, K10. The clay mineral was treated with 0.25 and 0.50 M sulfuric acid and the resulting materials were characterized by XRD, zeta potential, SEM, FTIR, cation exchange capacity, BET surface area and pore volume measurements. The influences of pH, interaction time, adsorbent amount, and temperature on adsorption were monitored and explained on the basis of physico-chemical characteristics of the materials. Basic pH generally favors adsorption but considerable removal was possible even under neutral conditions. Adsorption was very rapid and equilibrium could be attained in 180 min. The kinetics conformed to second order model. Langmuir monolayer adsorption capacity of raw montmorillonite K10 was 370.37 mg g(-1) whereas 0.25 M and 0.50 M acid treated montmorillonite K10 had capacities of 384.62 and 400.0 mg g(-1) respectively at 303 K. Adsorption was exothermic and decreased in the temperature range of 293-323 K. Thermodynamically, the process was spontaneous with Gibbs energy decreasing with rise in temperature. The results suggest that montmorillonite K10 and its acid treated forms would be suitable for removing Crystal violet from aqueous solution.

  1. Biomediated Precipitation of Calcium Carbonate and Sulfur in a Faintly Acidic Hot Spring

    NASA Astrophysics Data System (ADS)

    Jiang, L.; Peng, X.; Qiao, H.

    2014-12-01

    A faintly acidic hot spring named "female Tower" (T=73.5 ℃, pH=6.64 ) is located in the Jifei Geothermal Field,Yunnan province, Southwest China. The precipitates in the hot spring are composed of large amounts of calcite and sulfur, as reveals by XRD analysis. Scanning electron microscopy (SEM) analysis show the microbial mats are formed of various coccoid, rod and filamentous microbes. Transmission electron microscopy (TEM) analysis show that intracellular sulfur granules are commonly associated with these microbes. Energy dispersive X-ray spectrometer (EDS) analysis shows that the surface of microbes are mainly composed of Ca, C, O and S. A culture-independent molecular phylogenetic analysis demonstrates the majority of bacteria in the spring are sulfur-oxidizing bacteria. In the spring water, H2S concentration was up to 60 ppm, while SO42- concentration was only about 10 ppm. We suggest that H2S might be utilized by sulfur-oxidizing bacteria in this hot spring water, leading to the formation of sulfur granules intracellularly and extracellularly. In the meantime, this reaction increases the pH in ambient environments, which fosters the precipitation of calcium carbonate precipitation in the microbial mats. This study suggests that the sulfur-oxidizing bacteria could play an important role in calcium carbonate precipitation in faintly acidic hot spring environments.

  2. Relative contributions of sulfuric and nitric acids in acid rain to the acidification of the ecosystem: implications for control strategies

    SciTech Connect

    McLean, R.A.N.

    1981-11-01

    Much of northeastern North America has been receiving precipitation of pH 4.6 or less, i.e. more than ten times more acid than normal rain (pH = 5.6) for at least the past 20 to 30 years. Originally, this acidity was almost totally due to sulfuric acid. These inputs of sulfuric acid in the very acid sensitive Adirondacks may have removed much of the neutralizing and nitrate-utilizing ability of the soils and water. Thus, this area may now be more sensitive to atmospheric inputs of nitric acid. Further work is required on the impact of acid nitrate deposition on the ecosystem but with equal certainty it can be stated that sulfur deposition remains the princpial long term threat to acid sensitive ecosystems. It can be concluded that: much of the nitric acid in acid rain is decomposed in the soils and waterway, and is not a significant contributor to long-term acidification of soils and waters; although in the long term, nitric acid in atmospheric deposition is not likely to be contributing to the overall acidification of the environment, during the spring thaw, in areas which have been heavily impacted by acid rain for a number of years, nitric acid which has concentrated in the snow pack over the winter may cause ecological damage, especially to fish populations; though there is little doubt that tighter control strategies are necessary to diminish the effects of acid rain on remote ecosystems the existing control strategies, which have put more emphasis on the control of emissions of sulfur oxides than nitrogen oxides, have a reasonable scientific basis given our present limited knowledge of their effects on the ecosystem.

  3. Dental erosion in workers exposed to sulfuric acid in lead storage battery manufacturing facility.

    PubMed

    Suyama, Yuji; Takaku, Satoru; Okawa, Yoshikazu; Matsukubo, Takashi

    2010-01-01

    Dental erosion, and specifically its symptoms, has long been studied in Japan as an occupational dental disease. However, in recent years, few studies have investigated the development of this disease or labor hygiene management aimed at its prevention. As a result, interest in dental erosion is comparatively low, even among dental professionals. Our investigation at a lead storage battery factory in 1991 found that the work environmental sulfuric acid density was above the tolerable range (1.0mg/m(3)) and that longterm workers had dental erosion. Therefore, workers handling sulfuric acid were given an oral examination and rates of dental erosion by tooth type, rates of erosion by number of working years and rates of erosion by sulfuric acid density in the work environment investigated. Where dental erosion was diagnosed, degree of erosion was identified according to a diagnostic criterion. No development of dental erosion was detected in the maxillary teeth, and erosion was concentrated in the anterior mandibular teeth. Its prevalence was as high as 20%. Rates of dental erosion rose precipitously after 10 working years. The percentages of workers with dental erosion were 42.9% for 10-14 years, 57.1% for 15-19 years and 66.7% for over 20 years with 22.5% for total number of workers. The percentages of workers with dental erosion rose in proportion to work environmental sulfuric acid density: 17.9% at 0.5-1.0, 25.0% at 1.0-4.0 and 50.0% at 4.0-8.0mg/m(3). This suggests that it is necessary to evaluate not only years of exposure to sulfuric acid but also sulfuric acid density in the air in factory workers.

  4. Effect of dimethylamine on the gas phase sulfuric acid concentration measured by Chemical Ionization Mass Spectrometry

    NASA Astrophysics Data System (ADS)

    Rondo, L.; Ehrhart, S.; Kürten, A.; Adamov, A.; Bianchi, F.; Breitenlechner, M.; Duplissy, J.; Franchin, A.; Dommen, J.; Donahue, N. M.; Dunne, E. M.; Flagan, R. C.; Hakala, J.; Hansel, A.; Keskinen, H.; Kim, J.; Jokinen, T.; Lehtipalo, K.; Leiminger, M.; Praplan, A.; Riccobono, F.; Rissanen, M. P.; Sarnela, N.; Schobesberger, S.; Simon, M.; Sipilä, M.; Smith, J. N.; Tomé, A.; Tröstl, J.; Tsagkogeorgas, G.; Vaattovaara, P.; Winkler, P. M.; Williamson, C.; Wimmer, D.; Baltensperger, U.; Kirkby, J.; Kulmala, M.; Petäjä, T.; Worsnop, D. R.; Curtius, J.

    2016-03-01

    Sulfuric acid is widely recognized as a very important substance driving atmospheric aerosol nucleation. Based on quantum chemical calculations it has been suggested that the quantitative detection of gas phase sulfuric acid (H2SO4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased in the presence of gas phase amines such as dimethylamine (DMA). An experiment (CLOUD7 campaign) was set up at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber to investigate the quantitative detection of H2SO4 in the presence of dimethylamine by CIMS at atmospherically relevant concentrations. For the first time in the CLOUD experiment, the monomer sulfuric acid concentration was measured by a CIMS and by two CI-APi-TOF (Chemical Ionization-Atmospheric Pressure interface-Time Of Flight) mass spectrometers. In addition, neutral sulfuric acid clusters were measured with the CI-APi-TOFs. The CLOUD7 measurements show that in the presence of dimethylamine (<5 to 70 pptv) the sulfuric acid monomer measured by the CIMS represents only a fraction of the total H2SO4, contained in the monomer and the clusters that is available for particle growth. Although it was found that the addition of dimethylamine dramatically changes the H2SO4 cluster distribution compared to binary (H2SO4-H2O) conditions, the CIMS detection efficiency does not seem to depend substantially on whether an individual H2SO4 monomer is clustered with a DMA molecule. The experimental observations are supported by numerical simulations based on A Self-contained Atmospheric chemistry coDe coupled with a molecular process model (Sulfuric Acid Water NUCleation) operated in the kinetic limit.

  5. Effect of dimethylamine on the gas phase sulfuric acid concentration measured by Chemical Ionization Mass Spectrometry.

    PubMed

    Rondo, L; Ehrhart, S; Kürten, A; Adamov, A; Bianchi, F; Breitenlechner, M; Duplissy, J; Franchin, A; Dommen, J; Donahue, N M; Dunne, E M; Flagan, R C; Hakala, J; Hansel, A; Keskinen, H; Kim, J; Jokinen, T; Lehtipalo, K; Leiminger, M; Praplan, A; Riccobono, F; Rissanen, M P; Sarnela, N; Schobesberger, S; Simon, M; Sipilä, M; Smith, J N; Tomé, A; Tröstl, J; Tsagkogeorgas, G; Vaattovaara, P; Winkler, P M; Williamson, C; Wimmer, D; Baltensperger, U; Kirkby, J; Kulmala, M; Petäjä, T; Worsnop, D R; Curtius, J

    2016-03-27

    Sulfuric acid is widely recognized as a very important substance driving atmospheric aerosol nucleation. Based on quantum chemical calculations it has been suggested that the quantitative detection of gas phase sulfuric acid (H2SO4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased in the presence of gas phase amines such as dimethylamine (DMA). An experiment (CLOUD7 campaign) was set up at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber to investigate the quantitative detection of H2SO4 in the presence of dimethylamine by CIMS at atmospherically relevant concentrations. For the first time in the CLOUD experiment, the monomer sulfuric acid concentration was measured by a CIMS and by two CI-APi-TOF (Chemical Ionization-Atmospheric Pressure interface-Time Of Flight) mass spectrometers. In addition, neutral sulfuric acid clusters were measured with the CI-APi-TOFs. The CLOUD7 measurements show that in the presence of dimethylamine (<5 to 70 pptv) the sulfuric acid monomer measured by the CIMS represents only a fraction of the total H2SO4, contained in the monomer and the clusters that is available for particle growth. Although it was found that the addition of dimethylamine dramatically changes the H2SO4 cluster distribution compared to binary (H2SO4-H2O) conditions, the CIMS detection efficiency does not seem to depend substantially on whether an individual H2SO4 monomer is clustered with a DMA molecule. The experimental observations are supported by numerical simulations based on A Self-contained Atmospheric chemistry coDe coupled with a molecular process model (Sulfuric Acid Water NUCleation) operated in the kinetic limit.

  6. Sulfur amino acid metabolism in doxorubicin-resistant breast cancer cells.

    PubMed

    Ryu, Chang Seon; Kwak, Hui Chan; Lee, Kye Sook; Kang, Keon Wook; Oh, Soo Jin; Lee, Ki Ho; Kim, Hwan Mook; Ma, Jin Yeul; Kim, Sang Kyum

    2011-08-15

    Although methionine dependency is a phenotypic characteristic of tumor cells, it remains to be determined whether changes in sulfur amino acid metabolism occur in cancer cells resistant to chemotherapeutic medications. We compared expression/activity of sulfur amino acid metabolizing enzymes and cellular levels of sulfur amino acids and their metabolites between normal MCF-7 cells and doxorubicin-resistant MCF-7 (MCF-7/Adr) cells. The S-adenosylmethionine/S-adenosylhomocysteine ratio, an index of transmethylation potential, in MCF-7/Adr cells decreased to ~10% relative to that in MCF-7 cells, which may have resulted from down-regulation of S-adenosylhomocysteine hydrolase. Expression of homocysteine-clearing enzymes, such as cystathionine beta-synthase, methionine synthase/methylene tetrahydrofolate reductase, and betaine homocysteine methyltransferase, was up-regulated in MCF-7/Adr cells, suggesting that acquiring doxorubicin resistance attenuated methionine-dependence and activated transsulfuration from methionine to cysteine. Homocysteine was similar, which is associated with a balance between the increased expressions of homocysteine-clearing enzymes and decreased extracellular homocysteine. Despite an elevation in cysteine, cellular GSH decreased in MCF-7/Adr cells, which was attributed to over-efflux of GSH into the medium and down-regulation of the GSH synthesis enzyme. Consequently, MCF-7/Adr cells were more sensitive to the oxidative stress induced by bleomycin and menadione than MCF-7 cells. In conclusion, our results suggest that regulating sulfur amino acid metabolism may be a possible therapeutic target for chemoresistant cancer cells. These results warrant further investigations to determine the role of sulfur amino acid metabolism in acquiring anticancer drug resistance in cancer cells using chemical and biological regulators involved in sulfur amino acid metabolism. Copyright © 2011 Elsevier Inc. All rights reserved.

  7. Effect of dimethylamine on the gas phase sulfuric acid concentration measured by Chemical Ionization Mass Spectrometry

    PubMed Central

    Ehrhart, S.; Kürten, A.; Adamov, A.; Bianchi, F.; Breitenlechner, M.; Duplissy, J.; Franchin, A.; Dommen, J.; Donahue, N. M.; Dunne, E. M.; Flagan, R. C.; Hakala, J.; Hansel, A.; Keskinen, H.; Kim, J.; Jokinen, T.; Lehtipalo, K.; Leiminger, M.; Praplan, A.; Riccobono, F.; Rissanen, M. P.; Sarnela, N.; Schobesberger, S.; Simon, M.; Sipilä, M.; Smith, J. N.; Tomé, A.; Tröstl, J.; Tsagkogeorgas, G.; Vaattovaara, P.; Winkler, P. M.; Williamson, C.; Wimmer, D.; Baltensperger, U.; Kirkby, J.; Kulmala, M.; Petäjä, T.; Worsnop, D. R.; Curtius, J.

    2016-01-01

    Abstract Sulfuric acid is widely recognized as a very important substance driving atmospheric aerosol nucleation. Based on quantum chemical calculations it has been suggested that the quantitative detection of gas phase sulfuric acid (H2SO4) by use of Chemical Ionization Mass Spectrometry (CIMS) could be biased in the presence of gas phase amines such as dimethylamine (DMA). An experiment (CLOUD7 campaign) was set up at the CLOUD (Cosmics Leaving OUtdoor Droplets) chamber to investigate the quantitative detection of H2SO4 in the presence of dimethylamine by CIMS at atmospherically relevant concentrations. For the first time in the CLOUD experiment, the monomer sulfuric acid concentration was measured by a CIMS and by two CI‐APi‐TOF (Chemical Ionization‐Atmospheric Pressure interface‐Time Of Flight) mass spectrometers. In addition, neutral sulfuric acid clusters were measured with the CI‐APi‐TOFs. The CLOUD7 measurements show that in the presence of dimethylamine (<5 to 70 pptv) the sulfuric acid monomer measured by the CIMS represents only a fraction of the total H2SO4, contained in the monomer and the clusters that is available for particle growth. Although it was found that the addition of dimethylamine dramatically changes the H2SO4 cluster distribution compared to binary (H2SO4‐H2O) conditions, the CIMS detection efficiency does not seem to depend substantially on whether an individual H2SO4 monomer is clustered with a DMA molecule. The experimental observations are supported by numerical simulations based on A Self‐contained Atmospheric chemistry coDe coupled with a molecular process model (Sulfuric Acid Water NUCleation) operated in the kinetic limit. PMID:27610289

  8. Contribution of sulfuric acid and oxidized organic compounds to particle formation and growth

    NASA Astrophysics Data System (ADS)

    Riccobono, F.; Rondo, L.; Sipilä, M.; Barmet, P.; Curtius, J.; Dommen, J.; Ehn, M.; Ehrhart, S.; Kulmala, M.; Kürten, A.; Mikkilä, J.; Petäjä, T.; Weingartner, E.; Baltensperger, U.

    2012-05-01

    Lack of knowledge about the mechanisms underlying new particle formation and their subsequent growth is one of the main causes for the large uncertainty in estimating the radiative forcing of atmospheric aerosols in global models. We performed chamber experiments designed to study the contributions of sulfuric acid and organic vapors to formation and to the early growth of nucleated particles, respectively. Distinct experiments in the presence of two different organic precursors (1,3,5-trimethylbenzene and α-pinene) showed the ability of these compounds to reproduce the formation rates observed in the low troposphere. These results were obtained measuring the sulfuric acid concentrations with two Chemical Ionization Mass Spectrometers confirming the results of a previous study which modeled the sulfuric acid concentrations in presence of 1,3,5-trimethylbenzene. New analysis methods were applied to the data collected with a Condensation Particle Counter battery and a Scanning Mobility Particle Sizer, allowing the assessment of the size resolved growth rates of freshly nucleated particles. The effect of organic vapors on particle growth was investigated by means of the growth rate enhancement factor (Γ), defined as the ratio between the measured growth rate in the presence of α-pinene and the kinetically limited growth rate of the sulfuric acid and water system. The observed Γ values indicate that the growth is dominated by organic compounds already at particle diameters of 2 nm. Both the absolute growth rates and Γ showed a strong dependence on particle size supporting the nano-Köhler theory. Moreover, the separation of the contributions from sulfuric acid and organic compounds to particles growth reveals that the organic contribution seems to be enhanced by the sulfuric acid concentration. The size resolved growth analysis finally indicates that both condensation of oxidized organic compounds and reactive uptake contribute to particle growth.

  9. Contribution of sulfuric acid and oxidized organic compounds to particle formation and growth

    NASA Astrophysics Data System (ADS)

    Riccobono, F.; Rondo, L.; Sipilä, M.; Barmet, P.; Curtius, J.; Dommen, J.; Ehn, M.; Ehrhart, S.; Kulmala, M.; Kürten, A.; Mikkilä, J.; Paasonen, P.; Petäjä, T.; Weingartner, E.; Baltensperger, U.

    2012-10-01

    Lack of knowledge about the mechanisms underlying new particle formation and their subsequent growth is one of the main causes for the large uncertainty in estimating the radiative forcing of atmospheric aerosols in global models. We performed chamber experiments designed to study the contributions of sulfuric acid and organic vapors to the formation and early growth of nucleated particles. Distinct experiments in the presence of two different organic precursors (1,3,5-trimethylbenzene and α-pinene) showed the ability of these compounds to reproduce the formation rates observed in the low troposphere. These results were obtained measuring the sulfuric acid concentrations with two chemical ionization mass spectrometers confirming the results of a previous study which modeled the sulfuric acid concentrations in presence of 1,3,5-trimethylbenzene. New analysis methods were applied to the data collected with a condensation particle counter battery and a scanning mobility particle sizer, allowing the assessment of the size resolved growth rates of freshly nucleated particles. The effect of organic vapors on particle growth was investigated by means of the growth rate enhancement factor (Γ), defined as the ratio between the measured growth rate in the presence of α-pinene and the kinetically limited growth rate of the sulfuric acid and water system. The observed Γ values indicate that the growth is already dominated by organic compounds at particle diameters of 2 nm. Both the absolute growth rates and Γ showed a strong dependence on particle size, supporting the nano-Köhler theory. Moreover, the separation of the contributions from sulfuric acid and organic compounds to particle growth reveals that the organic contribution seems to be enhanced by the sulfuric acid concentration. Finally, the size resolved growth analysis indicates that both condensation of oxidized organic compounds and reactive uptake contribute to particle growth.

  10. Age-Related Changes in Sulfur Amino Acid Metabolism in Male C57bl/6 Mice.

    PubMed

    Jeon, Jang Su; Oh, Jeong-Ja; Kwak, Hui Chan; Yun, Hwi-Yeol; Kim, Hyoung Chin; Kim, Young-Mi; Oh, Soo Jin; Kim, Sang Kyum

    2017-06-14

    Alterations in sulfur amino acid metabolism are associated with an increased risk of a number of common late-life diseases, which raises the possibility that metabolism of sulfur amino acids may change with age. The present study was conducted to understand the age-related changes in hepatic metabolism of sulfur amino acids in 2-, 6-, 18- and 30-month-old male C57BL/6 mice. For this purpose, metabolite profiling of sulfur amino acids from methionine to taurine or glutathione (GSH) was performed. The levels of sulfur amino acids and their metabolites were not significantly different among 2-, 6- and 18-month-old mice, except for plasma GSH and hepatic homocysteine. Plasma total GSH and hepatic total homocysteine levels were significantly higher in 2-month-old mice than those in the other age groups. In contrast, 30-month-old mice exhibited increased hepatic methionine and cysteine, compared with all other groups, but decreased hepatic S-adenosylmethionine (SAM), S-adenosylhomocysteine and homocysteine, relative to 2-month-old mice. No differences in hepatic reduced GSH, GSH disulfide, or taurine were observed. The hepatic changes in homocysteine and cysteine may be attributed to upregulation of cystathionine β-synthase and down-regulation of γ-glutamylcysteine ligase in the aged mice. The elevation of hepatic cysteine levels may be involved in the maintenance of hepatic GSH levels. The opposite changes of methionine and SAM suggest that the regulatory role of SAM in hepatic sulfur amino acid metabolism may be impaired in 30-month-old mice.

  11. Dephosphorization of Steelmaking Slag by Leaching with Acidic Aqueous Solution

    NASA Astrophysics Data System (ADS)

    Qiao, Yong; Diao, Jiang; Liu, Xuan; Li, Xiaosa; Zhang, Tao; Xie, Bing

    2016-09-01

    In the present paper, dephosphorization of steelmaking slag by leaching with acidic aqueous solution composed of citric acid, sodium hydroxide, hydrochloric acid and ion-exchanged water was investigated. The buffer solution of C6H8O7-NaOH-HCl system prevented changes in the pH values. Kinetic parameters including leaching temperature, slag particle size and pH values of the solution were optimized. The results showed that temperature has no obvious effect on the dissolution ratio of phosphorus. However, it has a significant effect on the dissolution ratio of iron. The dephosphorization rate increases with the decrease of slag particle size and the pH value of the solution. Over 90% of the phosphorus can be dissolved in the solution while the corresponding leaching ratio of iron was only 30% below the optimal condition. Leaching kinetics of dephosphorization follow the unreacted shrinking core model with a rate controlled step by the solid diffusion layer, the corresponding apparent activation energy being 1.233 kJ mol-1. A semiempirical kinetic equation was established. After leaching, most of the nC2S-C3P solid solution in the steelmaking slag was selectively dissolved in the aqueous solution and the iron content in the solid residue was correspondingly enriched.

  12. Dynamic behavior of the bray-liebhafsky oscillatory reaction controlled by sulfuric acid and temperature

    NASA Astrophysics Data System (ADS)

    Pejić, N.; Vujković, M.; Maksimović, J.; Ivanović, A.; Anić, S.; Čupić, Ž.; Kolar-Anić, Lj.

    2011-12-01

    The non-periodic, periodic and chaotic regimes in the Bray-Liebhafsky (BL) oscillatory reaction observed in a continuously fed well stirred tank reactor (CSTR) under isothermal conditions at various inflow concentrations of the sulfuric acid were experimentally studied. In each series (at any fixed temperature), termination of oscillatory behavior via saddle loop infinite period bifurcation (SNIPER) as well as some kind of the Andronov-Hopf bifurcation is presented. In addition, it was found that an increase of temperature, in different series of experiments resulted in the shift of bifurcation point towards higher values of sulfuric acid concentration.

  13. Molecular steps of neutral sulfuric acid and dimethylamine nucleation in CLOUD

    NASA Astrophysics Data System (ADS)

    Jokinen, Tuija; Sarnela, Nina; Sipilä, Mikko; Junninen, Heikki; Lehtipalo, Katrianne; Duplissy, Jonathan; Cloud Collaboration

    2013-05-01

    We have run a set of experiments in the CLOUD chamber at CERN, Switzerland, studying the effect of dimethylamine (DMA) on sulfuric acid (SA)-water nucleation using a nitrate based Chemical Ionization Atmospheric Pressure ionization Time-Of-Flight Mass Spectrometer (CI-APi-TOF). Experiment was designed to produce neutral high m/z SA-DMA clusters in close to atmospherically relevant conditions to be detected and characterized by the CI-APi-TOF. We aimed in filling up the gap in measurement techniques from molecular level up to climatically relevant aerosol particles and thus improve our understanding of the role of sulfuric acid and DMA in atmospheric nucleation.

  14. On the prolonged lifetime of the El Chichon sulfuric acid aerosol cloud

    NASA Technical Reports Server (NTRS)

    Hofmann, D. J.; Rosen, J. M.

    1987-01-01

    The observed decay of the aerosol mixing ratio following the eruption of El Chichon appears to have been 20-30 percent slower than that following the eruption of Fuego in 1974, even though the sulfuric acid droplets were observed to grow to considerably larger sizes after El Chichon. This suggests the possible presence of a condensation nuclei and sulfuric acid vapor source and continued growth phenomena occurring well after the El Chichon eruption. It is proposed that the source of these nuclei and the associated vapor may be derived from annual evaporation and condensation of aerosol in the high polar regions during stratospheric warming events, with subsequent spreading to lower latitudes.

  15. Supercritical aqueous fluids in subduction zones carrying carbon and sulfur: oxidants for the mantle wedge?

    NASA Astrophysics Data System (ADS)

    Sverjensky, Dimitri; Manning, Craig

    2014-05-01

    Much speculation surrounds the nature of aqueous fluids in subduction zones. Aqueous fluids likely trigger partial melting in the mantle wedge, influencing the chemistry of the magmas that erupt in island arcs. They also may play a role in transporting elements that could metasomatize and oxidize the overlying mantle wedge, most importantly C, S and Fe. However, full coupling of aqueous fluid chemistry with the silicate, carbonate, C, sulfide and sulfate minerals has remained limited to pressures of 0.5 GPa because of limitations on the HKF aqueous ion equation of state. Recent progress in developing a Deep Earth Water model (Sverjensky et al., 2014), calibrated with new experimental data, now enables a detailed evaluation of the evolution of aqueous fluid chemistry to a pressure of 6 GPa, well into subduction zone conditions. We report aqueous speciation models for eclogitic aqueous fluids constrained by model mineral assemblages that give preliminary indications of the solubilities of elements that could contribute to mass transfer and redox changes in the mantle wedge. For example, at 600 °C and 2.5 GPa, an aqueous fluid in equilibrium with jadeite, paragonite, muscovite, quartz, lawsonite, almandine, talc, magnesite and pyrite at QFM oxidation state with 0.1 molal total Cl, contains 5.5 molal C, 0.04 molal S, and 9 micromolal Fe. The fluid has a pH of 4.7, much greater than the neutral pH of 3.3; the predominant species and molalities are CO2 (5.0), Na+ (0.44), Si(OH)4 (0.36), HCO3- (0.26), H3SiO4- (0.23), CaHCO3+ (0.18), silica dimer (0.10), Cl- (0.09), K+ (0.08), HCOO- (0.06), H2S (0.03). Calculations for model eclogitic fluids at the higher pressures and temperatures of subarc conditions also show that the solubility of C is much greater than either S or Fe at QFM. However, in subarc eclogitic fluids of higher oxidation state (QFM +3 to +4) in equilibrium with hematite, anhydrite, jadeite, kyanite, phlogopite, coesite, lawsonite, almandine-pyrope, and

  16. Ammonia Catalyzed Formation of Sulfuric Acid in Troposphere: The Curious Case of a Base Promoting Acid Rain.

    PubMed

    Bandyopadhyay, Biman; Kumar, Pradeep; Biswas, Partha

    2017-04-27

    Electronic structure calculations have been performed to investigate the role of ammonia in catalyzing the formation of sulfuric acid through hydrolysis of SO3 in Earth's atmosphere. The uncatalyzed process involves a high activation barrier and, until date, is mainly known to occur in Earth's atmosphere only when catalyzed by water and acids. Here we show that hydrolysis of SO3 can be very efficiently catalyzed by ammonia, the most abundant basic component in Earth's atmosphere. It was found, based on magnitude of relative potential energies as well as rate coefficients, that ammonia is the best among all the catalysts studied until now (water and acids) and could be a considerable factor in formation of sulfuric acid in troposphere. The calculated rate coefficient (at 298 K) of ammonia catalyzed reaction has been found to be ∼10(5)-10(7) times greater than that for water catalyzed ones. It was found, based on relative rates of ammonia and water catalyzed processes, that in troposphere ammonia, together with water, could be the key factor in determining the rate of formation of sulfuric acid. In fact, ammonia could surpass water in catalyzing sulfuric acid formation via hydrolysis of SO3 at various altitudes in troposphere depending upon their relative concentrations.

  17. Fermentation of aqueous plant seed extracts by lactic acid bacteria

    SciTech Connect

    Schafner, D.W.; Beuchat, R.L.

    1986-05-01

    The effects of lactic acid bacterial fermentation on chemical and physical changes in aqueous extracts of cowpea (Vigna unguiculata), peanut (Arachis hypogea), soybean (Glycine max), and sorghum (Sorghum vulgare) were studied. The bacteria investigated were Lactobacillus helveticus, L. delbrueckii, L. casei, L. bulgaricus, L. acidophilus, and Streptococcus thermophilus. Organisms were inoculated individually into all of the seed extracts; L. bulgaricus and S. thermophilus were also evaluated together as inocula for fermenting the legume extracts. During fermentation, bacterial population and changes in titratable acidity, pH, viscosity, and color were measured over a 72 h period at 37 degrees C. Maximum bacterial populations, titratable acidity, pH, and viscosity varied depending upon the type of extract and bacterial strain. The maximum population of each organism was influenced by fermentable carbohydrates, which, in turn, influenced acid production and change in pH. Change in viscosity was correlated with the amount of protein and titratable acidity of products. Color was affected by pasteurization treatment and fermentation as well as the source of extract. In the extracts inoculated simultaneously with L. bulgaricus and S. thermophilus, a synergistic effect resulted in increased bacterial populations, titratable acidity, and viscosity, and decreased pH in all the legume extracts when compared to the extracts fermented with either of these organisms individually. Fermented extracts offer potential as substitutes for cultured dairy products. 24 references.

  18. Electrical charging changes the composition of sulfuric acid-ammonia/dimethylamine clusters

    NASA Astrophysics Data System (ADS)

    Ortega, I. K.; Olenius, T.; Kupiainen-Määttä, O.; Loukonen, V.; Kurtén, T.; Vehkamäki, H.

    2014-01-01

    Sulfuric acid clusters stabilized by base molecules are likely to have a significant role in atmospheric new particle formation. Recent advances in mass spectrometry techniques have permitted the detection of electrically charged clusters. However, direct measurement of electrically neutral clusters is not possible. Mass spectrometry instruments can be combined with a charger, but the possible effect of charging on the composition of neutral clusters must be addressed before the measured data can be linked to properties of neutral clusters. In the present work we have used formation free energies from quantum chemical methods to calculate the evaporation rates of electrically charged (both positive and negative) sulfuric acid-ammonia/dimethylamine clusters. To understand how charging will affect the composition of these clusters, we have compared the evaporation rates of charged clusters with those of the corresponding neutral clusters. We found that the only cluster studied in this paper which will retain its composition is H2SO4 · NH3 when charged positively; all other clusters will be altered by both positive and negative charging. In the case of charging clusters negatively, base molecules will completely evaporate from clusters with 1 to 3 sulfuric acid molecules in the case of ammonia, and from clusters with 1 or 2 sulfuric acid molecules in the case of dimethylamine. Larger clusters will maintain some base molecules, but the H2SO4 : base ratio will increase. In the case of positive charging, some of the acid molecules will evaporate, decreasing the H2SO4 : base ratio.

  19. Mechanisms of volatile production from sulfur-containing amino acids by irradiation

    NASA Astrophysics Data System (ADS)

    Uk Ahn, Dong; Joo Lee, Eun; Feng, Xi; Zhang, Wangang; Lee, Ji Hwan; Jo, Cheorun; Nam, Kichang

    2016-02-01

    Sulfur-containing amino acids were used to study the mechanisms of off-odor production in meat by irradiation. Irradiation not only increased the amounts of volatiles but also produced many new volatiles from sulfur-containing amino acid monomers. We speculate that the majority of the volatiles were the direct radiolytic products of the side chains, but Strecker degradation as well as deamination and decarboxylation of radiolytic products were also involved in the production of volatile compounds from sulfur amino acids. The volatile compounds produced in amino acids were not only the primary products of irradiation, but also the products of secondary chemical reactions after the primary compounds were produced. Cysteine and methionine produced odor characteristics similar to that of the irradiated meat, but the amounts of sulfur volatiles from methionine were far greater than that of cysteine. Although the present study was carried out using an amino acid model system, the information can be applied to the quality indexes of irradiated meats as well as other food products.

  20. Autotrophic, sulfur-oxidizing actinobacteria in acidic environments.

    PubMed

    Norris, Paul R; Davis-Belmar, Carol S; Brown, Carly F; Calvo-Bado, Leonides A

    2011-03-01

    Some novel actinobacteria from geothermal environments were shown to grow autotrophically with sulfur as an energy source. These bacteria have not been formally named and are referred to here as "Acidithiomicrobium" species, as the first of the acidophilic actinobacteria observed to grow on sulfur. They are related to Acidimicrobium ferrooxidans with which they share a capacity for ferrous iron oxidation. Ribulose bisphosphate carboxylase/oxygenase (RuBisCO) is active in CO(2) fixation by Acidimicrobium ferrooxidans, which appears to have acquired its RuBisCO-encoding genes from the proteobacterium Acidithiobacillus ferrooxidans or its ancestor. This lateral transfer of RuBisCO genes between a proteobacterium and an actinobacterium would add to those noted previously among proteobacteria, between proteobacteria and cyanobacteria and between proteobacteria and plastids. "Acidithiomicrobium" has RuBisCO-encoding genes which are most closely related to those of Acidimicrobium ferrooxidans and Acidithiobacillus ferrooxidans, and has additional RuBisCO genes of a different lineage. 16S rRNA gene sequences from "Acidithiomicrobium" species dominated clone banks of the genes extracted from mixed cultures of moderate thermophiles growing on copper sulfide and polymetallic sulfide ores in ore leaching columns.

  1. Energy concentration and positional stability of sonoluminescent bubbles in sulfuric acid for different static pressures.

    PubMed

    Rosselló, Juan Manuel; Dellavale, Damián; Bonetto, Fabián José

    2013-09-01

    In this study we report several experimental and numerical results on the influence of static pressure (P_{0}) over the main parameters in single bubble sonoluminescence (SBSL), using a sulfuric acid aqueous solution (SA) with low concentrations of argon gas dissolved. Bifrequency driving was used in the experiments to enhance spatial stability of the bubbles. The experimental results were compared with simulations provided by a numerical code that models the radial dynamics of the bubbles. The results showed that an increase on the static pressure of the system shifts the Bjerknes instability threshold, allowing the bubble to access higher acoustic pressures (P_{Ac}^{}). Furthermore, a decrease in the measured ambient radius R_{0} and the calculated relative gas concentration c_{∞}/c_{0} were observed. A notorious increment in the bubble collapse violence and energy focusing for P_{0} above 1 bar was achieved. These were mainly indicated by the growth of the bubble expansion ratio (R_{max}/R_{0}), the bubble mechanical energy density, and the maximum bubble wall velocity dR/dt. In agreement with the previous statement, the maximum temperature during the bubble collapse predicted by the model is augmented as well. The use of different harmonics in the ultrasound pressure field regarding energy focusing is also discussed. Finally, we analyzed the stability regions of the R_{0}-P_{Ac}^{} parameter space via numerical predictions for P_{0} above the measured, identifying the shape instabilities as the main limiting agent to obtain further energy concentration in SA systems at high static pressures.

  2. [Photo-chemical decomposition of perfluorooctanoic acids in aqueous periodate].

    PubMed

    Cao, Meng-Hua; Wang, Bei-Bei; Zhu, Hu-Di; Tan, Zhen-Ji; Zeng, You-Shi; Wang, Lin-Ling; Yuan, Song-Hu; Chen, Jing

    2011-01-01

    The influence of reaction atmosphere and TiO2 on photochemical decomposition of perfluorooctanoic acid (PFOA) in aqueous periodate was investigated using a type of low-pressure mercury lamps emitted at 254 nm. PFOA photolysis was slight with 254 nm light irradiation under nitrogen, whereas significant decomposition PFOA obtained with the addition of IO4-. In addition, oxygen restrained photochemical decomposition of PFOA. In UV/TiO2/IO4- system, PFOA degradation ratio was 54%, 15% lower than that for UV/IO4- system. *OH radicals generated from UV/TiO2 system exhausted a lot of IO4-, resulting in lower degree of IO3* production. IO3* was high reactive radical which great excitated PFOA decomposition. The accumulation of short-chain perfluorocarbonxylic acids (PFCAs) as products were identified with HPLC/MS. PFCAs bearing shorter perfluoroalkyl groups were formed in a stepwise way from PFCAs that bear longer perfluoroalkyl groups.

  3. Adsorption of citric acid from dilute aqueous solutions by hydroxyapatite.

    PubMed

    Vega, Enrique D; Narda, Griselda E; Ferretti, Ferdinando H

    2003-12-01

    The role of citric acid in the demineralization of dental enamel, which is mainly constituted by hydroxyapatite, is important for periodontal regeneration and in the conditioning of enamel or dentin for bonding restorative resins. The adsorption of citric acid from aqueous solutions onto synthetic hydroxyapatite at 278, 288, 298, and 308 K and pH 4.8 has been studied by means of UV spectroscopy. The adsorption reaction, which takes place by an interaction between phosphate groups and citrate anions at the solid-solution interface, yields an adsorbate-adsorbent complex of high stability. The adsorption isotherms fit the Langmuirian shape. The proposed adsorption model, where citrate species interact in a bidentate manner (one citrate ion links two phosphate sites), is coherent with the experimental data. The activation standard heat and activation standard entropy were calculated. All the thermodynamic and kinetic parameters were in concordance with the adsorption reaction proposed in this work.

  4. Photosynthetic and growth responses of Schima superba seedlings to sulfuric and nitric acid depositions.

    PubMed

    Yao, Fang-Fang; Ding, Hui-Ming; Feng, Li-Li; Chen, Jing-Jing; Yang, Song-Yu; Wang, Xi-Hua

    2016-05-01

    A continuing rise in acid deposition can cause forest degradation. In China, acid deposition has converted gradually from sulfuric acid deposition (SAD) to nitric acid deposition (NAD). However, the differing responses of photosynthesis and growth to depositions of sulfuric vs. nitric acid have not been well studied. In this study, 1-year-old seedlings of Schima superba, a dominant species in subtropical forests, were treated with two types of acid deposition SO4 (2-)/NO3 (-) ratios (8:1 and 0.7:1) with two applications (foliar spraying and soil drenching) at two pH levels (pH 3.5 and pH 2.5) over a period of 18 months. The results showed that the intensity, acid deposition type, and spraying method had significant effects on the physiological characteristics and growth performance of seedlings. Acid deposition at pH 2.5 via foliar application reduced photosynthesis and growth of S. superba, especially in the first year. Unlike SAD, NAD with high acidity potentially alleviated the negative effects of acidity on physiological properties and growth, probably due to a fertilization effect that improved foliar nitrogen and chlorophyll contents. Our results suggest that trees were damaged mainly by direct acid stress in the short term, whereas in the long term, soil acidification was also likely to be a major risk to forest ecosystems. Our data suggest that the shift in acid deposition type may complicate the ongoing challenge of anthropogenic acid deposition to ecosystem stability.

  5. Polymerization of Pu(IV) in aqueous nitric acid solutions

    SciTech Connect

    Toth, L.M.; Friedman, H.A.; Osborne, M.M.

    1980-10-01

    The polymerization of Pu(IV) in aqueous nitric acid solutions has been studied spectrophotometrically both to establish the influence of large UO{sub 2}(NO{sub 3}){sub 2} concentrations on the polymerization rates and, more generally, to review the influence of the major parameters on the polymer reaction. Typically, experiments have been performed at 50{sup 0}C and with 0.05 M Pu in nitric acid solutions that vary in acidity from 0.07 to 0.4 M. An induction period usually precedes the polymer growth stage during which time nucleation of primary hydrolysis products occurs. Uranyl nitrate retards the polymerization reaction by approximately 35% in spite of the counteracting influence of the nitrate ions associated with this solute. The rate of polymer formation, expressed as d(percent polymer)/dt, has been shown to depend on the total plutonium concentration in reactions where the Pu(IV) concentration remained constant; and it is therefore suggested that the polymer reaction rate is not first order with respect to the concentration of plutonium as was previously thought. It has been shown further that accurate acid determinations on stock reagents are essential in order to obtain reliable polymerization experiments. Satisfactory procedures for these analyses did not exist, so appropriate modifications to the iodate precipitation methods were developed. The most ideal plutonium reagent material has been shown to be crystalline Pu(IV) nitrate because it can be added directly to acid solutions without the occurrence of unintentional hydrolysis reactions.

  6. Revealing biogenic sulfuric acid corrosion in sludge digesters: detection of sulfur-oxidizing bacteria within full-scale digesters.

    PubMed

    Huber, B; Drewes, J E; Lin, K C; König, R; Müller, E

    2014-01-01

    Biogenic sulfuric acid corrosion (BSA) is a costly problem affecting both sewerage infrastructure and sludge handling facilities such as digesters. The aim of this study was to verify BSA in full-scale digesters by identifying the microorganisms involved in the concrete corrosion process, that is, sulfate-reducing (SRB) and sulfur-oxidizing bacteria (SOB). To investigate the SRB and SOB communities, digester sludge and biofilm samples were collected. SRB diversity within digester sludge was studied by applying polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) targeting the dsrB-gene (dissimilatory sulfite reductase beta subunit). To reveal SOB diversity, cultivation dependent and independent techniques were applied. The SRB diversity studies revealed different uncultured SRB, confirming SRB activity and H2S production. Comparable DGGE profiles were obtained from the different sludges, demonstrating the presence of similar SRB species. By cultivation, three pure SOB strains from the digester headspace were obtained including Acidithiobacillus thiooxidans, Thiomonas intermedia and Thiomonas perometabolis. These organisms were also detected with PCR-DGGE in addition to two new SOB: Thiobacillus thioparus and Paracoccus solventivorans. The SRB and SOB responsible for BSA were identified within five different digesters, demonstrating that BSA is a problem occurring not only in sewer systems but also in sludge digesters. In addition, the presence of different SOB species was successfully associated with the progression of microbial corrosion.

  7. Free sulfurous acid (FSA) inhibition of biological thiosulfate reduction (BTR) in the sulfur cycle-driven wastewater treatment process.

    PubMed

    Qian, Jin; Wang, Lianlian; Wu, Yaoguo; Bond, Philip L; Zhang, Yuhan; Chang, Xing; Deng, Baixue; Wei, Li; Li, Qin; Wang, Qilin

    2017-06-01

    A sulfur cycle-based bioprocess for co-treatment of wet flue gas desulfurization (WFGD) wastes with freshwater sewage has been developed. In this process the removal of organic carbon is mainly associated with biological sulfate or sulfite reduction. Thiosulfate is a major intermediate during biological sulfate/sulfite reduction, and its reduction to sulfide is the rate-limiting step. In this study, the impacts of saline sulfite (the ionized form: HSO3(-) + SO3(2-)) and free sulfurous acid (FSA, the unionized form: H2SO3) sourced from WGFD wastes on the biological thiosulfate reduction (BTR) activities were thoroughly investigated. The BTR activity and sulfate/sulfite-reducing bacteria (SRB) populations in the thiosulfate-reducing up-flow anaerobic sludge bed (UASB) reactor decreased when the FSA was added to the UASB influent. Batch experiment results confirmed that FSA, instead of saline sulfite, was the true inhibitor of BTR. And BTR activities dropped by 50% as the FSA concentrations were increased from 8.0 × 10(-8) to 2.0 × 10(-4) mg H2SO3-S/L. From an engineering perspective, the findings of this study provide some hints on how to ensure effective thiosulfate accumulation in biological sulfate/sulfite reduction for the subsequent denitrification/denitritation. Such manipulation would result in higher nitrogen removal rates in this co-treatment process of WFGD wastes with municipal sewage.

  8. Assessment of nanofiltration and reverse osmosis potentialities to recover metals, sulfuric acid, and recycled water from acid gold mining effluent.

    PubMed

    Ricci, Bárbara C; Ferreira, Carolina D; Marques, Larissa S; Martins, Sofia S; Amaral, Míriam C S

    This work assessed the potential of nanofiltration (NF) and reverse osmosis (RO) to treat acid streams contaminated with metals, such as effluent from the pressure oxidation process (POX) used in refractory gold ore processing. NF and RO were evaluated in terms of rejections of sulfuric acid and metals. Regarding NF, high sulfuric acid permeation (∼100%), was observed, while metals were retained with high efficiencies (∼90%), whereas RO led to high acid rejections (<88%) when conducted in pH values higher than 1. Thus, sequential use of NF and RO was proved to be a promising treatment for sulfuric acid solutions contaminated by metals, such as POX effluent. In this context, a purified acid stream could be recovered in NF permeate, which could be further concentrated in RO. Recovered acid stream could be reused in the gold ore processing or commercialized. A metal-enriched stream could be also recovered in NF retentate and transferred to a subsequent metal recovery stage. In addition, considering the high acid rejection obtained through the proposed system, RO permeate could be used as recycling water.

  9. Impact of Sulfuric Acid Treatment of Halloysite on Physico-Chemic Property Modification.

    PubMed

    Gaaz, Tayser Sumer; Sulong, Abu Bakar; Kadhum, Abdul Amir H; Nassir, Mohamed H; Al-Amiery, Ahmed A

    2016-07-26

    Halloysite (HNT) is treated with sulfuric acid and the physico-chemical properties of its morphology, surface activity, physical and chemical properties have been investigated when HNT is exposed to sulfuric acid with treatment periods of 1 h (H1), 3 h (H3), 8 h (H8), and 21 h (H21). The significance of this and similar work lies in the importance of using HNT as a functional material in nanocomposites. The chemical structure was characterized by Fourier transform infrared spectroscopy (FTIR). The spectrum demonstrates that the hydroxyl groups were active for grafting modification using sulfuric acid, promoting a promising potential use for halloysite in ceramic applications as filler for novel clay-polymer nanocomposites. From the X-ray diffraction (XRD) spectrum, it can be seen that the sulfuric acid breaks down the HNT crystal structure and alters it into amorphous silica. In addition, the FESEM images reveal that the sulfuric acid treatment dissolves the AlO₆ octahedral layers and induces the disintegration of SiO₄ tetrahedral layers, resulting in porous nanorods. The Bruncher-Emmett-Teller (BET) surface area and total pore volume of HNTs showed an increase. The reaction of the acid with both the outer and inner surfaces of the nanotubes causes the AlO₆ octahedral layers to dissolve, which leads to the breakdown and collapse of the tetrahedral layers of SiO₄. The multi-fold results presented in this paper serve as a guide for further HNT functional treatment for producing new and advanced nanocomposites.

  10. Impact of Sulfuric Acid Treatment of Halloysite on Physico-Chemic Property Modification

    PubMed Central

    Gaaz, Tayser Sumer; Sulong, Abu Bakar; Kadhum, Abdul Amir H.; Nassir, Mohamed H.; Al-Amiery, Ahmed A.

    2016-01-01

    Halloysite (HNT) is treated with sulfuric acid and the physico-chemical properties of its morphology, surface activity, physical and chemical properties have been investigated when HNT is exposed to sulfuric acid with treatment periods of 1 h (H1), 3 h (H3), 8 h (H8), and 21 h (H21). The significance of this and similar work lies in the importance of using HNT as a functional material in nanocomposites. The chemical structure was characterized by Fourier transform infrared spectroscopy (FTIR). The spectrum demonstrates that the hydroxyl groups were active for grafting modification using sulfuric acid, promoting a promising potential use for halloysite in ceramic applications as filler for novel clay-polymer nanocomposites. From the X-ray diffraction (XRD) spectrum, it can be seen that the sulfuric acid breaks down the HNT crystal structure and alters it into amorphous silica. In addition, the FESEM images reveal that the sulfuric acid treatment dissolves the AlO6 octahedral layers and induces the disintegration of SiO4 tetrahedral layers, resulting in porous nanorods. The Bruncher-Emmett-Teller (BET) surface area and total pore volume of HNTs showed an increase. The reaction of the acid with both the outer and inner surfaces of the nanotubes causes the AlO6 octahedral layers to dissolve, which leads to the breakdown and collapse of the tetrahedral layers of SiO4. The multi-fold results presented in this paper serve as a guide for further HNT functional treatment for producing new and advanced nanocomposites. PMID:28773741

  11. Levulinic acid production by two-step acid-catalyzed treatment of Quercus mongolica using dilute sulfuric acid.

    PubMed

    Jeong, Hanseob; Jang, Soo-Kyeong; Hong, Chang-Young; Kim, Seon-Hong; Lee, Su-Yeon; Lee, Soo Min; Choi, Joon Weon; Choi, In-Gyu

    2017-02-01

    The objectives of this research were to produce a levulinic acid by two-step acid-catalyzed treatment of Quercus mongolica and to investigate the effect of treatment parameter (reaction temperature range: 100-230°C; sulfuric acid (SA) concentration range: 0-2%) on the levulinic acid yield. After 1(st) step acid-catalyzed treatment, most of the hemicellulosic C5 sugars (15.6gg/100gbiomass) were released into the liquid hydrolysate at the reaction temperature of 150°C in 1% SA; the solid fraction, which contained 53.5% of the C6 sugars, was resistant to further loss of C6 sugars. Subsequently, 2(nd) step acid-catalyzed treatment of the solid fractions was performed under more severe conditions. Finally, 16.5g/100g biomass of levulinic acid was produced at the reaction temperature of 200°C in 2% SA, corresponding to a higher conversion rate than during single-step treatment. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. Seed storage protein deficiency improves sulfur amino acid content in common bean (Phaseolus vulgaris L.): redirection of sulfur from gamma-glutamyl-S-methyl-cysteine.

    PubMed

    Taylor, Meghan; Chapman, Ralph; Beyaert, Ronald; Hernández-Sebastià, Cinta; Marsolais, Frédéric

    2008-07-23

    The contents of sulfur amino acids in seeds of common bean ( Phaseolus vulgaris L.) are suboptimal for nutrition. They accumulate large amounts of a gamma-glutamyl dipeptide of S-methyl-cysteine, a nonprotein amino acid that cannot substitute for methionine or cysteine in the diet. Protein accumulation and amino acid composition were characterized in three genetically related lines integrating a progressive deficiency in major seed storage proteins, phaseolin, phytohemagglutinin, and arcelin. Nitrogen, carbon, and sulfur contents were comparable among the three lines. The contents of S-methyl-cysteine and gamma-glutamyl-S-methyl-cysteine were progressively reduced in the mutants. Sulfur was shifted predominantly to the protein cysteine pool, while total methionine was only slightly elevated. Methionine and cystine contents (mg per g protein) were increased by up to ca. 40%, to levels slightly above FAO guidelines on amino acid requirements for human nutrition. These findings may be useful to improve the nutritional quality of common bean.

  13. Sulfur amino acid deficiency upregulates intestinal methionine cycle activity and suppresses epithelial growth in neonatal pigs.

    USDA-ARS?s Scientific Manuscript database

    We recently showed that the developing gut is a significant site of methionine transmethylation to homocysteine and transsulfuration to cysteine. We hypothesized that sulfur amino acid (SAA) deficiency would preferentially reduce mucosal growth and antioxidant function in neonatal pigs. Neonatal pi...

  14. Improved process for the production of cellulose sulfate using sulfuric acid/ethanol solution.

    PubMed

    Chen, Guo; Zhang, Bin; Zhao, Jun; Chen, Hongwen

    2013-06-05

    An improved process for production of cellulose sulfate (CS) was developed by using sulfuric acid/ethanol solution as sulfonating agent and Na2SO4 as water absorbent. The FTIR, SEM and TG analysis were used to characterize the CS prepared. The total degree of substitution and viscosity of the product solution (2%, w/v) were ranging from 0.28 to 0.77 and from 115 to 907 mPa s, respectively, by changing the process parameters such as the amount of Na2SO4, the reaction time, the temperature, the sulfuric acid/alcohol ratio and liquid/solid ratio. The results indicated that the product with DS (0.28-0.77) and η2% (115-907) mPa s could be produced by using this improved process and more cellulose sulfate could be produced when cellulose was sulfonated for 3-4 h at -2 °C in sulfuric acid/ethanol (1.4-1.6) solution with addition of 0.8 g Na2SO4. The (13)C NMR indicated that the sulfate group of CS produced using sulfuric acid/ethanol solution was at C6 position. Copyright © 2013 Elsevier Ltd. All rights reserved.

  15. The role of cluster energy nonaccommodation in atmospheric sulfuric acid nucleation

    SciTech Connect

    Kurten, T.; Kuang, C.; Gomez, P.; McMurry, P. H.; Vehkamaki, H.; Ortega, I.; Noppel, M.; Kulmala, M.

    2010-01-11

    We discuss the possible role of energy nonaccommodation (monomer-cluster collisions that do not result in stable product formation due to liberated excess energy) in atmospheric nucleation processes involving sulfuric acid. Qualitative estimates of the role of nonaccommodation are computed using quantum Rice-Ramsberger-Kassel theory together with quantum chemically calculated vibrational frequencies and anharmonic coupling constants for small sulfuric acid-containing clusters. We find that energy nonaccommodation effects may, at most, decrease the net formation rate of sulfuric acid dimers by up to a factor of 10 with respect to the hard-sphere collision rate. A decrease in energy nonaccommodation due to an increasing number of internal degrees of freedom may kinetically slightly favor the participation of amines rather than ammonia as stabilizing agents in sulfuric acid nucleation, though the kinetic enhancement factor is likely to be less than three. However, hydration of the clusters (which always occurs in ambient conditions) is likely to increase the energy accommodation factor, reducing the role that energy nonaccommodation plays in atmospheric nucleation.

  16. New insights into sulfur amino acid function in gut health and disease

    USDA-ARS?s Scientific Manuscript database

    The gastrointestinal tract (GIT) is a metabolically significant site of sulfur amino acids (SAA) metabolism in the body. Aside from their role in protein synthesis, methionine and cysteine are involved in many biological functions and diseases. Methionine (MET) is an indispensable AA and is transmet...

  17. Sulfur amino acids are necessary for normal intestinal mucosal growth in neonatal piglets

    USDA-ARS?s Scientific Manuscript database

    Sulfur amino acids (SAAs) methionine and cysteine play important metabolic and functional role in human health and disease. Gastrointestinal tract is an important site of transmethylation and transsulfuration of methionine and metabolizes approx. 20% of the dietary methionine intake (Riedijk et al. ...

  18. Kinetics of sulfuric acid leaching of cadmium from Cd-Ni zinc plant residues.

    PubMed

    Safarzadeh, Mohammad Sadegh; Moradkhani, Davood; Ojaghi-Ilkhchi, Mehdi

    2009-04-30

    Cd-Ni filtercakes are produced continuously at the third purification step in the electrolytic production of zinc in the National Iranian Lead and Zinc Company (NILZ) in northwestern Iran. In this research, the dissolution kinetics of cadmium from Cd-Ni residues produced in NILZ plant has been investigated. Hence, the effects of temperature, sulfuric acid concentration, particle size and stirring speed on the kinetics of cadmium dissolution in sulfuric acid were studied. The dissolution kinetics at 25-55 degrees C and tsulfuric acid concentration, solid/liquid ratio and particle size were also achieved. The rate of reaction at first 5 min based on diffusion-controlled process can be expressed by a semi-empirical equation as:It was determined that the dissolution rate increased with increasing sulfuric acid concentration and decreasing particle size.

  19. Chemical ionization of clusters formed from sulfuric acid and dimethylamine or diamines

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

    Chemical ionization (CI) mass spectrometers are used to study atmospheric nucleation by detecting clusters produced by reactions of sulfuric acid and various basic gases. These instruments typically use nitrate to deprotonate and thus chemically ionize the clusters. In this study, we compare cluster concentrations measured using either nitrate or acetate. Clusters were formed in a flow reactor from vapors of sulfuric acid and dimethylamine, ethylene diamine, tetramethylethylene diamine, or butanediamine (also known as putrescine). These comparisons show that nitrate is unable to chemically ionize clusters with high base content. In addition, we vary the ion-molecule reaction time to probe ion processes which include proton-transfer, ion-molecule clustering, and decomposition of ions. Ion decomposition upon deprotonation by acetate/nitrate was observed. More studies are needed to quantify to what extent ion decomposition affects observed cluster content and concentrations, especially those chemically ionized with acetate since it deprotonates more types of clusters than nitrate.Model calculations of the neutral and ion cluster formation pathways are also presented to better identify the cluster types that are not efficiently deprotonated by nitrate. Comparison of model and measured clusters indicate that sulfuric acid dimers with two diamines and sulfuric acid trimers with two or more base molecules are not efficiently chemical ionized by nitrate. We conclude that acetate CI provides better information on cluster abundancies and their base content than nitrate CI.

  20. Homogenous nucleation of sulfuric acid and water at atmospherically relevant conditions

    NASA Astrophysics Data System (ADS)

    Brus, D.; Neitola, K.; Petäjä, T.; Vanhanen, J.; Hyvärinen, A.-P.; Sipilä, M.; Paasonen, P.; Lihavainen, H.; Kulmala, M.

    2010-11-01

    In this study the homogeneous nucleation rates of sulfuric acid and water were measured by using a flow tube technique. The goal was to directly compare particle formation rates obtained from atmospheric measurements with nucleation rates of freshly nucleated particles measured with particle size magnifier (PSM) which has detection efficiency of unity for particles having mobility diameter of 1.5 nm. The gas phase sulfuric acid concentration in this study was measured with the chemical ionization mass spectrometer (CIMS), commonly used in field measurements. The wall losses of sulfuric acid were estimated from measured concentration profiles along the flow tube. The initial concentrations of sulfuric acid estimated from loss measurements ranged from 108 to 3×109 molecules cm-3. The nucleation rates obtained in this study cover about three orders of magnitude from 10-1 to 102 cm3 s-1 for commercial ultrafine condensation particle counter (UCPC) TSI model 3025A and from 101 to 104 cm3 s-1 for PSM. The nucleation rates and the slopes (dlnJ/dln[H2SO4]) show satisfactory agreement when compared to empirical kinetic and activation models and the latest atmospheric nucleation data.

  1. Uptake of HCl and HOCl onto sulfuric acid. Solubilities, diffusivities, and reaction

    SciTech Connect

    Hanson, D.R.; Ravishankara, A.R. Univ. of Colorado, Boulder, CO )

    1993-11-25

    The interaction of HOCl and HCl vapors with liquid sulfuric acid surfaces was studied in a flow tube equipped with chemical ionization mass spectrometry detection. Time-dependent uptake of HCl and HOCl was measured. A methodology for deriving the value of the quantity H[radical]D[sub 1], (the product of the Henry's law coefficient and the square root of the liquid-phase diffusion coefficient) is discussed. The partial pressures of HCl over HCl-doped sulfuric acid solutions were also measured to directly determine H for HCl (H[sub HCl]*). Using the measured values of H[sub HCl]* and H[sub HCl]*[radical]D[sub 1], the value of D[sub 1] for HCl in 50 wt % sulfuric acid was extracted. Values for H[sub HOCl] and for the second-order rate coefficient for the reaction between dissolved HOCl and HCl were also obtained. The application of these results to modeling stratospheric heterogeneous processes in sulfuric acid aerosols is discussed. 31 refs., 14 refs., 3 tabs.

  2. Response of DOC in acid-sensitive Maine lakes to decreasing sulfur deposition (1993 - 2009)

    EPA Science Inventory

    In response to the Clean Air Act Amendments of 1990, sulfur deposition has decreased across the northeastern United States. As a result, sulfate concentrations in lakes and streams have also decreased and many surface waters have become less acidic. Over the same time period, th...

  3. Response of DOC in acid-sensitive Maine lakes to decreasing sulfur deposition (1993 - 2009)

    EPA Science Inventory

    In response to the Clean Air Act Amendments of 1990, sulfur deposition has decreased across the northeastern United States. As a result, sulfate concentrations in lakes and streams have also decreased and many surface waters have become less acidic. Over the same time period, th...

  4. Pressure leaching of metals from waste printed circuit boards using sulfuric acid

    NASA Astrophysics Data System (ADS)

    Jha, Manis K.; Lee, Jae-Chun; Kumari, Archana; Choubey, Pankaj K.; Kumar, Vinay; Jeong, Jinki

    2011-08-01

    Printed circuit boards (PCBs) are essential components of electronic equipments which contain various metallic values. This paper reports a hydrometallurgical recycling process for waste PCBs, which consists of the novel pretreatment consisting of organic swelling of PCBs followed by sulfuric acid leaching of metals from waste PCBs. To recycle the waste PCBs, experiments were carried out for the recovery of copper from the crushed and organic swelled materials of waste PCBs using sulfuric acid leaching in presence of hydrogen peroxide under atmospheric and pressure condition. The leaching of PCBs at 90°C, pulp density 100 g/L under atmospheric condition, using 6M sulfuric acid resulted in the dissolution of a minor amount of copper due to the presence of plastic coating on the surface of metallic layers. On the other hand, when the liberated metal sheets from organic swelled PCBs were treated with dilute sulfuric acid of concentration 2M along with hydrogen peroxide in an autoclave under oxygen atmosphere, the percentage recovery of copper was found to increase from 59.63% to 97.01% with an increase in hydrogen peroxide concentration from 5 to 15% (v/v) keeping constant pulp density 30 g/L.

  5. Two-stage, dilute sulfuric acid hydrolysis of wood : an investigation of fundamentals

    Treesearch

    John F. Harris; Andrew J. Baker; Anthony H. Conner; Thomas W. Jeffries; James L. Minor; Roger C. Pettersen; Ralph W. Scott; Edward L Springer; Theodore H. Wegner; John I. Zerbe

    1985-01-01

    This paper presents a fundamental analysis of the processing steps in the production of methanol from southern red oak (Quercus falcata Michx.) by two-stage dilute sulfuric acid hydrolysis. Data for hemicellulose and cellulose hydrolysis are correlated using models. This information is used to develop and evaluate a process design.

  6. The influence of hydroxyl volatile organic compounds on the oxidation of aqueous sulfur dioxide by oxygen.

    PubMed

    Dhayal, Yogpal; Chandel, C P S; Gupta, K S

    2014-01-01

    Although the effect of volatile organic compounds (VOCs) on the oxidation of dissolved sulfur dioxide by oxygen has been the subject of many investigations, this is the first study which examines the effect of a large number of precisely 16 hydroxy compounds. The kinetics both in the absence and the presence of VOCs was defined by rate laws (A and B): -d[S(IV)]dt = R₀ = k₀[S(IV)] (A) -d[S(IV)]dt = R(i) = k(i)[S(IV)] (B) where R₀ and k₀ are the initial rate and first-order rate constant, respectively, in the absence of VOCs, R(i), and k(i) are the initial rate and the first-order rate constant, respectively, in the presence of VOCs, and [S(IV)] is the concentration of dissolved sulfur dioxide, sulfur(IV). The nature of the dependence of k(i) on the concentration of inhibitor, [Inh], was defined by Eq. (C). [k(i) = k₀/(1 + B[Inh]) (C) where B is an empirical inhibition parameter. The values of B have been determined from the plots of 1/k(i) versus [Inh]. Among aliphatic and aromatic hydroxy compounds studied, t-butyl alcohol and pinacol were without any inhibition effect due to the absence of secondary or tertiary hydrogen. The values of inhibition parameter, B, were related to k(inh), the rate constant for the reaction of SO₄(-) radical with the inhibitor, by Eq. (D). B = (9 ± 2) x 10⁻⁴ x k(inh) (D) Equation (D) may be used to calculate the values of either of B or k(inh) provided that the other is known. The extent of inhibition depends on the value of the composite term, B[Inh]. However, in accordance with Eq. (C), the extent of inhibition would be sizeable and measurable when B[Inh] > 0.1 and oxidation of S(IV) would be almost completely stopped when B[Inh] ≥ 10. B[Inh] value can be used as a guide whether the reaction step: SO4 (-) + organics → SO₄(2-) + non-chain products: should be included in the multiphase models or not.

  7. Competitive Oxidation Kinetics and Microbial Ecology: Intermediate Sulfur Transformations in Acid Mine Drainage Environments

    NASA Astrophysics Data System (ADS)

    Druschel, G. K.; Hamers, R. J.; Banfield, J. F.

    2001-12-01

    Experimental studies have demonstrated that oxidation of pyrite proceeds through several intermediate sulfur species, notably elemental sulfur, thiosulfate, and polythionates (Schippers et al., 1996). However, detailed sampling and analysis of flowing waters and pore waters failed to detect intermediate sulfur species in the 5-way area of the Richmond metal sulfide deposit at the Iron Mountain Mine in northern California. Potential energy available from the oxidation of intermediate sulfur species is considerable, so microbial activity may explain absence of intermediate sulfur compounds at the site. However, the abundance of sulfur-oxidizing microorganisms in areas of active pyrite oxidation at the 5-way is generally low (Bond et al. 2000). Rapid inorganic oxidation rates may prevent microorganisms from utilizing these intermediate sulfur species, thus shaping the structure of microbial communities in acid mine drainage (AMD) environments. Rates and mechanisms of oxidation for tetrathionate and elemental sulfur have been experimentally determined. Batch and flow-through experiments have indicated very slow oxidation of elemental sulfur in inorganic solutions analogous to AMD environments. Results for tetrathionate indicate the importance of non-metabolic and inorganic processes, including surface catalysis and the generation of hydroxyl radicals. Surface catalysis occurs through trithionate on iron oxide surfaces. Hydroxyl radicals may be formed directly by microbes living in proximity to pyrite surfaces, or at pyrite surfaces undergoing wetting and drying cycles. Further experiments investigating the importance of organic compounds associated with iron-oxidizing microorganisms acting as electron transport shuttles and/or wetting agents and ab initio calculations of the electronic structure of potential reactants and intermediates are currently being performed. It is suggested that inorganic processes involved with seasonal wetting and drying of pyritic sediment

  8. Sulfur amino acid metabolism in doxorubicin-resistant breast cancer cells

    SciTech Connect

    Ryu, Chang Seon; Kwak, Hui Chan; Lee, Kye Sook; Kang, Keon Wook; Oh, Soo Jin; Lee, Ki Ho; Kim, Hwan Mook; Ma, Jin Yeul; Kim, Sang Kyum

    2011-08-15

    Although methionine dependency is a phenotypic characteristic of tumor cells, it remains to be determined whether changes in sulfur amino acid metabolism occur in cancer cells resistant to chemotherapeutic medications. We compared expression/activity of sulfur amino acid metabolizing enzymes and cellular levels of sulfur amino acids and their metabolites between normal MCF-7 cells and doxorubicin-resistant MCF-7 (MCF-7/Adr) cells. The S-adenosylmethionine/S-adenosylhomocysteine ratio, an index of transmethylation potential, in MCF-7/Adr cells decreased to {approx} 10% relative to that in MCF-7 cells, which may have resulted from down-regulation of S-adenosylhomocysteine hydrolase. Expression of homocysteine-clearing enzymes, such as cystathionine beta-synthase, methionine synthase/methylene tetrahydrofolate reductase, and betaine homocysteine methyltransferase, was up-regulated in MCF-7/Adr cells, suggesting that acquiring doxorubicin resistance attenuated methionine-dependence and activated transsulfuration from methionine to cysteine. Homocysteine was similar, which is associated with a balance between the increased expressions of homocysteine-clearing enzymes and decreased extracellular homocysteine. Despite an elevation in cysteine, cellular GSH decreased in MCF-7/Adr cells, which was attributed to over-efflux of GSH into the medium and down-regulation of the GSH synthesis enzyme. Consequently, MCF-7/Adr cells were more sensitive to the oxidative stress induced by bleomycin and menadione than MCF-7 cells. In conclusion, our results suggest that regulating sulfur amino acid metabolism may be a possible therapeutic target for chemoresistant cancer cells. These results warrant further investigations to determine the role of sulfur amino acid metabolism in acquiring anticancer drug resistance in cancer cells using chemical and biological regulators involved in sulfur amino acid metabolism. - Research Highlights: > MCF-7/Adr cells showed decreases in cellular GSH

  9. THE EFFECT OF ANOLYTE PRODUCT ACID CONCENTRATION ON HYBRID SULFUR CYCLE PERFORMANCE

    SciTech Connect

    Gorensek, M.; Summers, W.

    2010-03-24

    The Hybrid Sulfur (HyS) cycle (Fig. 1) is one of the simplest, all-fluids thermochemical cycles that has been devised for splitting water with a high-temperature nuclear or solar heat source. It was originally patented by Brecher and Wu in 1975 and extensively developed by Westinghouse in the late 1970s and early 1980s. As its name suggests, the only element used besides hydrogen and oxygen is sulfur, which is cycled between the +4 and +6 oxidation states. HyS comprises two steps. One is the thermochemical (>800 C) decomposition of sulfuric acid (H{sub 2}SO{sub 4}) to sulfur dioxide (SO{sub 2}), oxygen (O{sub 2}), and water. H{sub 2}SO{sub 4} = SO{sub 2} + 1/2 O{sub 2} + H{sub 2}O. The other is the SO{sub 2}-depolarized electrolysis of water to H{sub 2}SO{sub 4} and hydrogen (H{sub 2}), SO{sub 2} + 2 H{sub 2}O = H{sub 2}SO{sub 4} + H{sub 2}, E{sup o} = -0.156 V, explaining the 'hybrid' designation. These two steps taken together split water into H{sub 2} and O{sub 2} using heat and electricity. Researchers at the Savannah River National Laboratory (SRNL) and at the University of South Carolina (USC) have successfully demonstrated the use of proton exchange membrane (PEM) electrolyzers (Fig. 2) for the SO{sub 2}-depolarized electrolysis (sulfur oxidation) step, while Sandia National Laboratories (SNL) successfully demonstrated the high-temperature sulfuric acid decomposition (sulfur reduction) step using a bayonet-type reactor (Fig. 3). This latter work was performed as part of the Sulfur-Iodine (SI) cycle Integrated Laboratory Scale demonstration at General Atomics (GA). The combination of these two operations results in a simple process that will be more efficient and cost-effective for the massive production of hydrogen than alkaline electrolysis. Recent developments suggest that the use of PEMs other than Nafion will allow sulfuric acid to be produced at higher concentrations (>60 wt%), offering the possibility of net thermal efficiencies around 50% (HHV basis

  10. Binary nucleation in acid-water systems. II. Sulfuric acid-water and a comparison with methanesulfonic acid-water

    NASA Astrophysics Data System (ADS)

    Wyslouzil, B. E.; Seinfeld, J. H.; Flagan, R. C.; Okuyama, K.

    1991-05-01

    This work presents a systematic investigation of binary nucleation rates for sulfuric acid and water and the effect of temperature on these rates at isothermal, subsaturated conditions. The results from nucleation rate measurements for the sulfuric acid (H2SO4) -water system are discussed and compared to those previously presented for methanesulfonic acid (MSA)-water [B. E. Wyslouzil, J. H. Seinfeld, R. C. Flagan, and K. Okuyama, J. Chem. Phys. (submitted)]. Experiments were conducted at relative humidities (Rh) ranging from 0.006acidities (Ra) in the range of 0.04acid molecules in the critical nucleus for both the H2SO4 -water and MSA-water systems.

  11. A method for calculating the acid-base equilibria in aqueous and nonaqueous electrolyte solutions

    NASA Astrophysics Data System (ADS)

    Tanganov, B. B.; Alekseeva, I. A.

    2017-06-01

    Concentrations of particles in acid-base equilibria in aqueous and nonaqueous solutions of electrolytes are calculated on the basis of logarithmic charts, activity coefficients, and equilibrium constants.

  12. Modeling Sucrose Hydrolysis in Dilute Sulfuric Acid Solutions at Pretreatment Conditions for Lignocellulosic Biomass

    SciTech Connect

    Bower, S.; Wickramasinghe, R.; Nagle, N. J.; Schell, D. J.

    2008-01-01

    Agricultural and herbaceous feedstocks may contain appreciable levels of sucrose. The goal of this study was to evaluate the survivability of sucrose and its hydrolysis products, fructose and glucose, during dilute sulfuric acid processing at conditions typically used to pretreat lignocellulose biomass. Solutions containing 25 g/l sucrose with 0.1-2.0% (w/w) sulfuric acid concentrations were treated at temperatures of 160-200 C for 3-12 min. Sucrose was observed to completely hydrolyze at all treatment conditions. However, appreciable concentrations of fructose and glucose were detected and glucose was found to be significantly more stable than fructose. Different mathematical approaches were used to fit the kinetic parameters for acid-catalyzed thermal degradation of these sugars. Since both sugars may survive dilute acid pretreatment, they could provide an additional carbon source for production of ethanol and other bio-based products.

  13. Comparing the performance of Miscanthus x giganteus and wheat straw biomass in sulfuric acid based pretreatment.

    PubMed

    Kärcher, M A; Iqbal, Y; Lewandowski, I; Senn, T

    2015-03-01

    The objective of this study was to assess and compare the suitability of Miscanthus x giganteus and wheat straw biomass in dilute acid catalyzed pretreatment. Miscanthus and wheat straw were treated in a dilute sulfuric acid/steam explosion pretreatment. As a result of combining dilute sulfuric acid- and steam explosion pretreatment the hemicellulose hydrolysis yields (96% in wheat straw and 90% in miscanthus) in both substrates were higher than reported in literature. The combined severity factor (=CSF) for optimal hemicellulose hydrolysis was 1.9 and 1.5 in for miscanthus and wheat straw respectively. Because of the higher CSF value more furfural, furfuryl alcohol, 5-hydroxymethylfurfural and acetic acid was formed in miscanthus than in wheat straw pretreatment. Copyright © 2015 Elsevier Ltd. All rights reserved.

  14. Study of insoluble crystals derived from solutions of Kevlar 49 in sulfuric acid

    SciTech Connect

    Butler, N.L.

    1984-05-21

    The object of the study was to isolate and obtain x-ray diffraction analysis of the insoluble crystals which have been observed in Kevlar 49/H/sub 2/SO/sub 4/ dope. These insoluble crystals had previously been reported to be Kevlar single crystals after analysis by optical microscopy. A more detailed analysis does not support this conclusion. Additional optical microscopy coupled with FTIR and elemental analysis for C, H and N, has shown that these insoluble crystals are in fact terephthalic acid which is a decomposition product of the acid hydrolysis of Kevlar. A model compound study of sulfuric-acid hydrolysis of aromatic amide was carried out in order to better understand the sulfuric-acid-hydrolysis of Kevlar.

  15. Extraction of uranium from tailings by sulfuric acid leaching with oxidants

    NASA Astrophysics Data System (ADS)

    Huang, Jing; Li, Mi; Zhang, Xiaowen; Huang, Chunmei; Wu, Xiaoyan

    2017-06-01

    Recovery of uranium have been performed by leaching uranium-containing tailings in sulfuric acid system with the assistance of HF, HClO4, H2O2 and MnO2. The effect of reagent dosage, sulfuric acid concentration, Liquid/solid ratio, reaction temperature and particle size on the leaching of uranium were investigated. The results show that addiction of HF, HClO4, H2O2 and MnO2 significantly increased the extraction of uranium under 1M sulphuric acid condition and under the optimum reaction conditions a dissolution fraction of 85% by HClO4, 90% by HF, 95% by H2O2 can be reached respectively. The variation of technological mineralogy properites of tailings during leaching process show that the assistants can break gangue effectively. These observations suggest that optimum oxidants could potentially influence the extraction of uranium from tailings even under dilute acid condition.

  16. The reaction of CIONO{sub 2} with submicrometer sulfuric acid aerosol

    SciTech Connect

    Hanson, D.R.; Lovejoy, E.R.

    1995-03-03

    The measured reaction probability, {gamma}, for the reaction of chlorine nitrate CIONO{sub 2} with 60 percent (by weight) sulfuric acid aerosol increases monotonically with particle size at 250 kelvin. The reactor-diffusive length (l, the effective liquid depth over which reaction occurs) derived from these experiments is 0.037{+-}0.007 micrometer (95 percent confidence level for precision). The reaction probability for the reaction of CIONO{sub 2} with 60 percent sulfuric acid aerosol doped with {approximately}7 x 10{sup -4} M hydrochloric acid at 250 kelvin is larger by about a factor of 4 than in the absence of hydrochloric acid and varies less with particle size (l = 0.009{+-}0.005 micrometer). These results provide a test of the theory for gas-particle reactions and further insight into the reactivity of atmospheric aerosol. 19 refs., 3 figs.

  17. [Health aspects of sodium salts of sulfurous and sulfuric acids as environmental pollutants].

    PubMed

    Denisov, Iu N; Tkachev, P G

    1990-09-01

    For the first time hygienic characteristics of long-term inhalation exposure effects of sodium salts of sulphurous and sulphuric acids in low concentrations on animals is given. The most sensitive organs and organism systems have been identified. MACs of the substances under study for the ambient air are proposed. The degree of contamination and the distance of spreading of sodium sulfate from the source have been determined in field studies. The size of the sanitary-protective zone has been substantiated.

  18. Effect of ions on the measurement of sulfuric acid in the CLOUD experiment at CERN

    NASA Astrophysics Data System (ADS)

    Rondo, L.; Kürten, A.; Ehrhart, S.; Schobesberger, S.; Franchin, A.; Junninen, H.; Petäjä, T.; Sipilä, M.; Worsnop, D. R.; Curtius, J.

    2014-11-01

    Ternary aerosol nucleation experiments were conducted in the CLOUD chamber at CERN in order to investigate the influence of ions on new particle formation. Neutral and ion-induced nucleation experiments, i.e. without and with the presence of ions, respectively, were carried out under precisely controlled conditions. The sulfuric acid concentration was measured with a chemical ionisation mass spectrometer (CIMS) during the new particle formation experiments. The added ternary trace gases were ammonia (NH3), dimethylamine (DMA, C2H7N) or oxidised products of pinanediol (PD, C10H18O2). When pinanediol was introduced into the chamber, an increase in the mass spectrometric signal used to determine the sulfuric acid concentration (m/z 97, i.e. HSO4-) was observed due to ions from the CLOUD chamber. The enhancement was only observed during ion-induced nucleation measurements by using either galactic cosmic rays (GCRs) or the proton synchrotron (PS) pion beam for the ion generation, respectively. The ion effect typically involved an increase in the apparent sulfuric acid concentration by a factor of ~ 2 to 3 and was qualitatively verified by the ion measurements with an atmospheric-pressure interface-time of flight (APi-TOF) mass spectrometer. By applying a high-voltage (HV) clearing field inside the CLOUD chamber, the ion effect on the CIMS measurement was completely eliminated since, under these conditions, small ions are swept from the chamber in about 1 s. In order to exclude the ion effect and to provide corrected sulfuric acid concentrations during the GCR and PS beam nucleation experiments, a parameterisation was derived that utilises the trace gas concentrations and the UV light intensity as input parameters. Atmospheric sulfuric acid measurements with a CIMS showed an insignificant ion effect.

  19. On the growth of nitric and sulfuric acid aerosol particles under stratospheric conditions

    NASA Technical Reports Server (NTRS)

    Hamill, Patrick; Turco, R. P.; Toon, O. B.

    1988-01-01

    A theory for the formation of frozen aerosol particles in the Antarctic stratosphere was developed and applied to the formation of polar stratospheric clouds. The theory suggests that the condensed ice particles are composed primarily of nitric acid and water, with small admixtures of sulfuric and hydrochloric acids in solid solution. The proposed particle formation mechanism is in agreement with the magnitude and seasonal behavior of the optical extinction observed in the winter polar stratosphere.

  20. Smectite Formation From Basaltic Glass in the Presence of Sulfuric Acid on Mars

    NASA Astrophysics Data System (ADS)

    Peretyazhko, T.; Niles, P. B.; Sutter, B.; Morris, R. V.; Ming, D. W.

    2016-12-01

    Phyllosilicates of the smectite group detected in Noachian and early Hesperian terrains on Mars were hypothesized to form under neutral to alkaline conditions. These pH conditions and the presence of a CO2-rich atmosphere during the Noachian and early Hesperian should have been favorable for the formation of large carbonate deposits. However, large-scale carbonate deposits have not been detected on Mars. Recent orbital and landed missions have detected phyllosilicates co-existing with minerals that usually form under acidic conditions including jarosite and alunite. The occurrence of sulfates co-existing with phyllosilicates minerals on Mars and absences of large-scale carbonate in Noachian terrains indicate that phyllosilicate formation under sulfuric acid conditions was at least locally important. The pH effect and the nature of phyllosilicate minerals forming during acid-sulfate weathering of basalt remain unknown. We investigated formation of smectite minerals in the presence of sulfuric acid from Mars-analogue, glass-rich, basalt simulant. Hydrothermal (200º C) 14 d experiments were performed with addition of sulfuric acid of variable concentration at a pH range from 1.8 to 8.4. Sulfuric acid did not suppress smectite formation and gradual acid neutralization during basalt weathering led to montmorillonite formation at pH 3 followed by saponite at pH 4 and higher. Smectite formed through glass phase alteration and was accompanied by precipitation of calcium sulfate (anhydrite). Similar smectite and sulfate formation under acid sulfate conditions may have occurred in near-surface hydrothermal areas near magma bodies on Mars.

  1. Parenteral sulfur amino acid requirements in septic infants

    USDA-ARS?s Scientific Manuscript database

    To investigate parenteral methionine requirements of critically ill, septic infants, we conducted an investigation involving 12 infants (age 2+/-1 years; weight 13+/-2kg) using the intravenous indicator amino acid oxidation and balance technique. They received a balanced parenteral amino acid formul...

  2. Interfacial Chemistry of Aqueous Sulfur/Iodide Aerosol Microdroplets in Gaseous Ozone

    NASA Astrophysics Data System (ADS)

    Enami, S.; Vecitis, C. D.; Cheng, J.; Colussi, A. J.; Hoffmann, M. R.

    2007-12-01

    The intermediates ISO3- (m/z = 207) and IS2O3- (m/z = 239) generated in aqueous (iodide - thiosulfate) microdroplets traversing dilute ozone gas plumes at atmospheric pressure are detected via online electrospray mass spectrometry within 1 ms, and their stabilities gauged by collision-induced dissociation. The simultaneous detection of anionic reactants and the S2O62-, HSO4-, IO3- and I3- products as a function of experimental conditions provides evidence of unique interfacial reaction kinetics. Although ozone reacts ~3-4 times faster with I- than S2O332- in bulk solution, only S2O32- is apparently oxidized in [I--]o/[S2O32- ]o = 10 microdroplets below [O3(g)] ~ 50 ppm. The sulfite to sulfate and iodide to triiodide and iodate oxidations in the interfacial layers of aqueous thiosulfate or mixed thiosulfate and iodide microdroplets briefly exposed to dilute O3(g) gas mixtures are also investigated. S(IV) oxidation kinetics in sodium thiosulfate solutions, where the rates are proportional to [S(IV)] [O3(g)] in the ranges investigated, correspond to a surface-specific reaction. I3-/IO3- yields based on interfacial I- losses exceed their stoichiometric limits in the presence of excess S(IV), revealing that interfacial I- is competitively replenished from the microdroplets inner layers. Present results provide unequivocal evidence of distinct interfacial chemistry in gas-aerosol reactions of atmospheric relevance.

  3. Decoupling the Impacts of Heterotrophy and Autotrophy on Sulfuric Acid Speleogenesis

    NASA Astrophysics Data System (ADS)

    Jones, A. A.; Bennett, P.

    2013-12-01

    Within caves such as Movile Caves (Romania), the Frasassi Caves (Italy), and Lower Kane Cave (LKC, Wyoming, USA) the combination of abiotic autoxidation and microbiological oxidation of H2S produces SO42- and H+ that promotes limestone dissolution through sulfuric-acid speleogenesis (SAS). Microbial sulfide oxidation by sulfur-oxidizing bacteria (SOB) has been shown recently to be the dominant process leading to speleogenesis in these caves. However, due to the inherently large diversity of microbial communities within these environments, there are a variety of metabolic pathways that can impact limestone dissolution and carbon cycling to varying degrees. In order to investigate these variations we outfitted a continuous flow bioreactor with a Picarro Wavelength-Scanned Cavity Ring Down Spectrometer (WS-CRDS) that continuously monitored and logged 12CO2 and 13CO2 at ppmv sensitivity and isotope ratios at <0.3‰ precision in simulated cave atmospheres. Bioreactors containing Madison Limestone were inoculated with either a monoculture of the mixotrophic sulfur-oxidizing Thiothrix unzii or a mixed environmental (LKC) sulfur-metabolizing community. Ca2+ and pH were also continuously logged in order to quantify the impact of microbial metabolism on limestone dissolution rate. We found an order of magnitude of variability in limestone dissolution rates that were closely tied to microbial metabolism. In monocultures, limestone dissolution was inhibited by excessive reduced sulfur as T. unzii prefers to store sulfur internally as So under these conditions, generating no acidity. The headspace was depleted in 13C when sulfur was being stored as So and enriched in 13C when sulfur was being converted to SO42-. This suggests a preference for a heterotrophy during periods of high sulfur input and autotrophy when sulfur input is low. This was corroborated by an increase in SO42- during low sulfide input and microscope images showed loss of internal sulfur within the filaments

  4. Quantitative assessment of the sulfuric acid contribution to new particle growth.

    PubMed

    Bzdek, Bryan R; Zordan, Christopher A; Pennington, M Ross; Luther, George W; Johnston, Murray V

    2012-04-17

    The Nano Aerosol Mass Spectrometer (NAMS) was deployed to rural/coastal and urban sites to measure the composition of 20-25 nm diameter nanoparticles during new particle formation (NPF). NAMS provides a quantitative measure of the elemental composition of individual, size-selected nanoparticles. In both environments, particles analyzed during NPF were found to be enhanced in elements associated with inorganic species (nitrogen, sulfur) relative to that associated with organic species (carbon). A molecular apportionment algorithm was applied to the elemental data in order to place the elemental composition into a molecular context. These measurements show that sulfate constitutes a substantial fraction of total particle mass in both environments. The contribution of sulfuric acid to new particle growth was quantitatively determined and the gas-phase sulfuric acid concentration required to incorporate the measured sulfate fraction was calculated. The calculated values were compared to those calculated by a sulfuric acid proxy that considers solar radiation and SO(2) levels. The two values agree within experimental uncertainty. Sulfate accounts for 29-46% of the total mass growth of particles. Other species contributing to growth include ammonium, nitrate, and organics. For each location, the relative amounts of these species do not change significantly with growth rate. However, for the coastal location, sulfate contribution increases with increasing temperature whereas nitrate contribution decreases with increasing temperature.

  5. Delayed production of sulfuric acid condensation nuclei in the polar stratosphere from El Chichon volcanic vapors

    NASA Technical Reports Server (NTRS)

    Hofmann, D. J.; Rosen, J. M.; Gringel, W.

    1985-01-01

    It is pointed out that measurements of the vertical profiles of atmospheric condensation nuclei (CN) have been conducted since 1973. Studies with a new instrument revealed that the CN concentration undergoes a remarkable annual variation in the 30-km region characterized by a large increase in the late winter/early spring period with a subsequent decay during the remainder of the year. The event particles are observed to be volatile at 150 C, suggesting a sulfuric acid-water composition similar to that found in the normal 20 km aerosol layer. The development of about 10 to the 7th metric tons of sulfuric acid aerosol following the injection of sulfurous gases by El Chichon in April 1982, prompted Hofmann and Rosen (1983) to predict a very large CN event for 1983. The present investigation is concerned with the actual observation of the predicted event. Attention is given to the observation of a very large increase of what appear to be small sulfuric acid droplets at 30-km altitude in January 1983 over Laramie, WY, in January 1983.

  6. Development of Sulfuric Acid Decomposer for Thermo-Chemical IS Process

    SciTech Connect

    Hiroki, Noguchi; Hiroyuki, Ota; Atsuhiko, Terada; Shinji, Kubo; Kaoru, Onuki; Ryutaro, Hino

    2006-07-01

    The Japan Atomic Energy Agency (JAEA) has been conducting R and D on thermo-chemical Iodine-Sulfur (IS) process, which is one of most attractive water-splitting hydrogen production methods using nuclear heat of a high-temperature gas-cooled reactor (HTGR). In the IS process, sulfuric acid is evaporated and decomposed into H{sub 2}O and SO{sub 3} in a sulfuric acid decomposer operated under high temperature condition up to 500 deg C. Necessary heat is supplied by high temperature helium gas from the HTGR. Since the sulfuric acid decomposer will be exposed to severe corrosion condition, we have proposed a new decomposer concept of a block type heat exchanger made of SiC ceramic which has excellent corrosion and mechanical strength performance. To verify the concept, integrity of new type gaskets applied for boundary seal of the decomposer was examined as a first step. Pure gold gaskets coupled with absorption mechanism against thermal expansion showed good seal performance under 500 deg C. Based on this result, a mock-up model for a IS pilot-plant with 30 m{sup 3}/h-hydrogen production rate was test-fabricated as the next step. Through the fabrication and gas-tight tests, fabricability and structural integrity were confirmed. Also, the decomposer showed good mechanical strength and seal performances against horizontal loading simulating earthquake motion. (authors)

  7. HPLC Determination of Bioactive Sulfur Compounds, Amino Acids and Biogenic Amines in Biological Specimens.

    PubMed

    Francioso, Antonio; Fanelli, Sergio; Vigli, Daniele; Ricceri, Laura; Cavallaro, Rosaria A; Conrado, Alessia Baseggio; Fontana, Mario; D'Erme, Maria; Mosca, Luciana

    2017-01-01

    There is an increasing interest for analytical methods aimed to detect biological sulfur-containing amines, because of their involvement in human diseases and metabolic disorders. This work describes an improved HPLC method for the determination of sulfur containing amino acids and amines from different biological matrices. We optimized a pre-column derivatization procedure using dabsyl chloride, in which dabsylated products can be monitored spectrophotometrically at 460 nm. This method allows the simultaneous analysis of biogenic amines, amino acids and sulfo-amino compounds including carnosine, dopamine, epinephrine, glutathione, cysteine, taurine, lanthionine, and cystathionine in brain specimens, urines, plasma, and cell lysates. Moreover, the method is suitable for the study of physiological and non-physiological derivatives of taurine and glutathione such as hypotaurine, homotaurine, homocysteic acid and S-acetylglutathione. The present method displays good efficiency of derivatization, having the advantage to give rise to stable products compared to other derivatizing agents such as o-phthalaldehyde and dansyl chloride.With this method, we provide a tool to study sulfur cycle from a metabolic point of view in relation to the pattern of biological amino-compounds, allowing researchers to get a complete scenario of organic sulfur and amino metabolism in tissues and cells.

  8. Chemolithotrophic Bacteria in Copper Ores Leached at High Sulfuric Acid Concentration

    PubMed Central

    Vasquez, M.; Espejo, R. T.

    1997-01-01

    Extensive bacterial growth was observed when copper sulfide ores were leached with 0.6 N sulfuric acid. The bacterial population developed in this condition was examined by characterization of the spacer regions between the 16S and 23S rRNA genetic loci obtained after PCR amplification of the DNA extracted from the leached ore. The spacers observed had the sizes found in strains of "Leptospirillum ferrooxidans" and Thiobacillus thiooxidans, except for a larger one, approximately 560 bp long, that was not observed in any of the strains examined, including those of Thiobacillus ferrooxidans. The bacteria with this last spacer were selected after culturing in mineral and elemental sulfur media containing 0.7 N sulfuric acid. The spacer and the 16S ribosomal DNA of this isolate were sequenced and compared with those in species commonly found in bioleaching processes. Though the nucleotide sequence of the spacer showed an extensive heterologous region with T. thiooxidans, the sequence of its 16S rDNA gene indicated a close relationship (99.85%) with this species. These results indicate that a population comprised of bacterial strains closely related to T. thiooxidans and of another strain, possibly related to "L. ferrooxidans," can develop during leaching at high sulfuric acid concentration. Iron oxidation in this condition is attributable to "L. ferrooxidans" and not T. ferrooxidans, based on the presence of spacers with the "L. ferrooxidans" size range and the absence of spacers characteristic of T. ferrooxidans. PMID:16535497

  9. Evidence for a Morin Type Intramolecular Cyclization of an Alkene with a Phenylsulfenic Acid Group in Neutral Aqueous Solution

    PubMed Central

    Keerthi, Kripa; Sivaramakrishnan, Santhosh; Gates, Kent S.

    2009-01-01

    Sulfenic acids (RSOH) are among the most common sulfur-centered reactive intermediates generated in biological systems. Given the biological occurrence of sulfenic acids, it is important to explore the reactivity of these intermediates under physiological conditions. The Morin rearrangement is a synthetic process developed for the conversion of penicillin derivatives into cephalosporins that proceeds via nucleophilic attack of an alkene on a sulfenic acid intermediate. In its classic form, the Morin reaction involves initial elimination of a sulfenic acid from a cyclic sulfoxide, followed by intramolecular cyclization of the resulting alkene and sulfenic acid groups to generate an episulfonium ion intermediate that undergoes further reaction to yield ring-expanded products. On the basis of the existing literature, it is difficult to assess whether the reaction between an alkene and a sulfenic group can occur under mild conditions because the conditions required to generate the sulfenic acid from the sulfoxide precursor in the Morin reaction typically involve high temperatures and strong acid. In the work described here, β-sulfinylketone precursors were used to generate a “Morin type” sulfenic acid intermediate under mild conditions. This approach made it possible to demonstrate that the intramolecular cyclization of an alkene with a phenylsulfenic acid to generate an episulfonium ion intermediate can occur in neutral aqueous solution at room temperature. PMID:18500784

  10. A Combined Proteomic and Transcriptomic Analysis on Sulfur Metabolism Pathways of Arabidopsis thaliana under Simulated Acid Rain

    PubMed Central

    Wang, Wenhua; Simon, Martin; Wu, Feihua; Hu, Wenjun; Chen, Juan B.; Zheng, Hailei

    2014-01-01

    With rapid economic development, most regions in southern China have suffered acid rain (AR) pollution. In our study, we analyzed the changes in sulfur metabolism in Arabidopsis under simulated AR stress which provide one of the first case studies, in which the systematic responses in sulfur metabolism were characterized by high-throughput methods at different levels including proteomic, genomic and physiological approaches. Generally, we found that all of the processes related to sulfur metabolism responded to AR stress, including sulfur uptake, activation and also synthesis of sulfur-containing amino acid and other secondary metabolites. Finally, we provided a catalogue of the detected sulfur metabolic changes and reconstructed the coordinating network of their mutual influences. This study can help us to understand the mechanisms of plants to adapt to AR stress. PMID:24595051

  11. A combined proteomic and transcriptomic analysis on sulfur metabolism pathways of Arabidopsis thaliana under simulated acid rain.

    PubMed

    Liu, Tingwu; Chen, Juan A; Wang, Wenhua; Simon, Martin; Wu, Feihua; Hu, Wenjun; Chen, Juan B; Zheng, Hailei

    2014-01-01

    With rapid economic development, most regions in southern China have suffered acid rain (AR) pollution. In our study, we analyzed the changes in sulfur metabolism in Arabidopsis under simulated AR stress which provide one of the first case studies, in which the systematic responses in sulfur metabolism were characterized by high-throughput methods at different levels including proteomic, genomic and physiological approaches. Generally, we found that all of the processes related to sulfur metabolism responded to AR stress, including sulfur uptake, activation and also synthesis of sulfur-containing amino acid and other secondary metabolites. Finally, we provided a catalogue of the detected sulfur metabolic changes and reconstructed the coordinating network of their mutual influences. This study can help us to understand the mechanisms of plants to adapt to AR stress.

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

    PubMed

    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%.

  13. Temperature Shifts for Extraction and Purification of Zygomycetes Chitosan with Dilute Sulfuric Acid

    PubMed Central

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

    2010-01-01

    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%. PMID:21152285

  14. Characterization and improvement of phenol-sulfuric acid microassay for glucose-based glycogen.

    PubMed

    Rasouli, M; Ostovar-Ravari, A; Shokri-Afra, H

    2014-01-01

    Phenol-sulfuric acid reagent is used to measure the concentration of glyco-polymers and -conjugates. There are several uncertainties on glycogen measurement in the tissues. We aimed to improve phenol-sulfuric reagent for microassay of glucose based-glycogen in small tube or microplate. The condition of the reaction was optimized and scaled down for both small tube and microplate application. The color intensity was found to be a function of all components of the assay mixture, that is, the amount of sugar and phenol together with the volume of total water and acid. The absorbance increased in the range of 4-10 mg of phenol and reached the plateau between 10-16 mg per 1 mL of acid. The color intensity was a linear function of total water volume (sugar-water- phenol). The sensitivity increased eight times as total water volume was changed from 50 up to 400 µL. The curve for acid volume peaked at about 1 mL. The optimal assay condition was determined to be 13 mg of phenol (200 µL 6.5%), 400-425 µL of total water volume (100 µL of sugar, 100 µL water) for 1 mL of acid. The initial spontaneous high temperature is essential the reaction to proceed and any handling gives inconsistent results and decreases the precision and sensitivity of the method. The values were scaled down by a factor of 0.5 for tube application and reading in cuvet or microplate and by 0.2 or 0.15 for microplate application. The results indicated that phenol-sulfuric acid reagent could be scaled down to 1.0, 0.5 and 0.20, 0.15 mL of sulfuric acid for microassay of glucose based-glycogen.

  15. Theoretical study of interactions between cysteine and perfluoropropanoic acid in gas and aqueous phase

    NASA Astrophysics Data System (ADS)

    Holmes, Tiffani M.; Doskocz, Jacek; Wright, Terrance; Hill, Glake A.

    The interaction of perfluoropropanoic acid (PFPA) with the amino acid cysteine was investigated using density functional theory. Previous studies suggest that the peroxisome proliferator chemical, perfluorooctanoic acid, is circulated throughout the body by way of sulfur-containing amino acids. We present conformational analysis of the interactions of PFPA, a small model of perfluorooctanoic acid, with the sulfur-containing amino acid which occur by the process of hydrogen bonding, in which the hydrogen of the sulfhydryl group interacts with the carboxyl oxygen, and the amino nitrogen forms a hydrogen bond with the hydrogen of the bond OH group of the fluorinated alkyl. We also show in our structures a recently characterized weak nonbonded interaction between divalent sulfur and a main chain carboxyl oxygen in proteins. B3LYP calculated free energies and interaction energies predict low-energy, high-interaction conformations for complex systems of perfluorinated fatty acid interactions with cysteine.

  16. Perfluoroalkyl acids in aqueous samples from Germany and Kenya.

    PubMed

    Shafique, Umer; Schulze, Stefanie; Slawik, Christian; Böhme, Alexander; Paschke, Albrecht; Schüürmann, Gerrit

    2017-04-01

    Continuous monitoring of chemicals in the environment is important to control their fate and to protect human health, flora, and fauna. Perfluoroalkyl acids (PFAAs) have been detected frequently in different environmental compartments during the last 15 years and have drawn much attention because of their environmental persistence, omnipresence, and bioaccumulation potential. Water is an important source of their transport. In the present study, distributions of PFAAs in river water, wastewater treatment plant (WWTP) effluent, and tap water from eastern part of Germany and western part of Kenya were investigated. Eleven perfluorocarboxylic acids (PFCAs) and five perfluorosulfonic acids (PFSAs) were analyzed using liquid chromatography/tandem mass spectrometry. Sum of mean concentrations of eight PFAAs detected in drinking tap water from Leipzig was 11.5 ng L(-1), dominated by perfluorooctanoic acid (PFOA, 6.2 ng L(-1)). Sums of mean riverine concentrations of PFAAs detected in Pleiße/White Elster, Saale, and Elbe (Germany) were 24.8, 54.3, and 26.8 ng L(-1), respectively. Annual flux of PFAAs from River Saale was estimated to be 164 ± 23 kg a(-1). The effluent of WWTP in Halle was found to contain four times higher levels of PFAAs than river water and was dominated by perfluorobutane sulfonate (PFBS) with 32 times higher concentration than the riverine level. It advocates that WWTPs are the point source of contaminating water bodies with PFAAs, and short-chain PFAAs are substituting long-chain homologues. Sums of mean riverine concentrations of PFAAs in Sosiani (Kenya) in samples from sparsely populated and densely populated areas were 58.8 and 109.4 ng L(-1), respectively, indicating that population directly affected the emissions of PFAAs to surface waters. The discussion includes thorough review and comparison of recently published literature reporting occurrence of PFAAs in aqueous matrices. Graphical abstract Perfluoroalkyl acids in aqueous

  17. Acid-base thermochemistry of gaseous oxygen and sulfur substituted amino acids (Ser, Thr, Cys, Met).

    PubMed

    Riffet, Vanessa; Frison, Gilles; Bouchoux, Guy

    2011-11-07

    Acid-base thermochemistry of isolated amino acids containing oxygen or sulfur in their side chain (serine, threonine, cysteine and methionine) have been examined by quantum chemical computations. Density functional theory (DFT) was used, with B3LYP, B97-D and M06-2X functionals using the 6-31+G(d,p) basis set for geometry optimizations and the larger 6-311++G(3df,2p) basis set for energy computations. Composite methods CBS-QB3, G3B3, G4MP2 and G4 were applied to large sets of neutral, protonated and deprotonated conformers. Conformational analysis of these species, based on chemical approach and AMOEBA force field calculations, has been used to identify the lowest energy conformers and to estimate the population of conformers expected to be present at thermal equilibrium at 298 K. It is observed that G4, G4MP2, G3B3, CBS-QB3 composite methods and M06-2X DFT lead to similar conformer energies. Thermochemical parameters have been computed using either the most stable conformers or equilibrium populations of conformers. Comparison of experimental and theoretical proton affinities and Δ(acid)H shows that the G4 method provides the better agreement with deviations of less than 1.5 kJ mol(-1). From this point of view, a set of evaluated thermochemical quantities for serine, threonine, cysteine and methionine may be proposed: PA = 912, 919, 903, 938; GB = 878, 886, 870, 899; Δ(acid)H = 1393, 1391, 1396, 1411; Δ(acid)G = 1363, 1362, 1367, 1382 kJ mol(-1). This study also confirms that a non-negligible ΔpS° is associated with protonation of methionine and that the most acidic hydrogen of cysteine in the gas phase is that of the SH group. In several instances new conformers were identified thus suggesting a re-examination of several IRMPD spectra. This journal is © the Owner Societies 2011

  18. Reversible absorption of SO2 by amino acid aqueous solutions.

    PubMed

    Deng, Renpan; Jia, Lishan; Song, Qianqian; Su, Shuai; Tian, Zhongbiao

    2012-08-30

    Six water-soluble amino acids (glycine, l-α-alanine, dl-alanine, β-alanine, proline and arginine) aqueous solutions were applied to remove SO(2) from SO(2)-N(2) system in this report. All the tested amino acids solutions were found to be excellent absorbents for SO(2) removal, and SO(2) saturation uptake of β-alanine solution was the highest under the same experimental conditions. The effects of amino acid concentration, SO(2) concentration, absorption temperature, desorption temperature and initial pH value of the absorbent on the removal of SO(2) were investigated with β-Ala solution. The experimental results showed that SO(2) saturation uptake increased with the increase in β-alanine solution and SO(2) concentration. Room temperature (20-30°C) was found to be optimal for SO(2) absorption. Additionally the SO(2) desorption capacity increased with increasing desorption temperature. The neutral environment pH value of 6.8 was found to be optimal for SO(2) removal. Ten continuous absorption-desorption cycles showed that the absorbent had an excellent regeneration performance. (13)C NMR and ultraviolet analyses offer ample evidence to speculate that the bonding between SO(2) and β-alanine was not covalent but some weak interactive forces, such as dispersion force, induction force, dipole-dipole force and hydrogen bond. Copyright © 2012 Elsevier B.V. All rights reserved.

  19. UV photolysis of perfluorooctanoic acid (PFOA) in dilute aqueous solution.

    PubMed

    Giri, R R; Ozaki, H; Morigaki, T; Taniguchi, S; Takanami, R

    2011-01-01

    Perfluorooctanoic acid (PFOA) is very persistent in the environment and widely detected in the water environment. Only some advanced methods with extreme reaction conditions are shown to be capable of degrading the compound efficiently, and almost all the earlier investigations used very high PFOA concentrations. The compound is detected normally at very low concentrations in the water environment, while mild reaction conditions for its degradation are preferable. This article aimed to elucidate photodegradation of PFOA in dilute aqueous solutions by combined UV wavelengths (185 nm+254 nm) and 254 nm using a newly designed UV jacket. PFOA degradation was greatly enhanced with the combined wavelengths with almost one hundred percent PFOA removals in four-hour reaction. The removals were well described by the first-order reaction kinetic. The removal efficiencies and rate values significantly decreased with smaller initial PFOA concentrations. But defluorination was greatly enhanced with smaller PFOA concentrations possibly due to accelerated decomposition of fluorinated intermediates of PFOA. Formic acid and acetic acid were two tentatively identified intermediates of PFOA photolysis while the former was a major intermediate predominantly controlling solution pH during the oxidation. The results demonstrated that PFOA photolysis by the combined wavelengths with mild reaction conditions can be greatly enhanced by proper design of UV jacket and reactor system.

  20. Influence of ions on aqueous acid-base reactions.

    PubMed

    Cox, M Jocelyn; Siwick, Bradley J; Bakker, Huib J

    2009-01-12

    We study the effects of bromide salts on the rate and mechanism of the aqueous proton/deuteron-transfer reaction between the photoacid 8-hydroxy-1,3,6-pyrenetrisulfonic acid (HPTS) and the base acetate. The proton/deuteron release is triggered by exciting HPTS with 400 nm femtosecond laser pulses. Probing the electronic and vibrational resonances of the photoacid, the conjugate photobase, the hydrated proton/deuteron and the accepting base with femtosecond visible and mid-infrared pulses monitors the proton transfer. Two reaction channels are identified: 1) direct long-range proton transfer over hydrogen-bonded water bridges that connect the acid and base and 2) acid dissociation to produce fully solvated protons followed by proton scavenging from solution by acetate. We observe that the addition of salt affects the long-range reaction pathway, and reduces both the rate at which protons are released to solution by HPTS and the rate at which solvated protons are scavenged from solution by acetate. We study the dependence of these effects on the nature and concentration of the dissolved salt.

  1. Conformation of poly(γ-glutamic acid) in aqueous solution.

    PubMed

    Muroga, Yoshio; Nakaya, Asami; Inoue, Atsuki; Itoh, Daiki; Abiru, Masaya; Wada, Kaori; Takada, Masako; Ikake, Hiroki; Shimizu, Shigeru

    2016-04-01

    Local conformation and overall conformation of poly(γ-DL-glutamic acid) (PγDLGA) and poly(γ-L-glutamic acid) (PγLGA) in aqueous solution was studied as a function of degree of ionization ε by (1) H-NMR, circular dichroism, and potentiometric titration. It was clarified that their local conformation is represented by random coil over an entire ε range and their overall conformation is represented by expanded random-coil in a range of ε > ε(*) , where ε(*) is about 0.3, 0.35, 0.45, and 0.5 for added-salt concentration of 0.02M, 0.05M, 0.1M, and 0.2M, respectively. In a range of ε < ε(*) , however, ε dependence of their overall conformation is significantly differentiated from each other. PγDLGA tends to aggregate intramolecularly and/or intermolecularly with decreasing ε, but PγLGA still behaves as expanded random-coil. It is speculated that spatial arrangement of adjacent carboxyl groups along the backbone chain essentially affects the overall conformation of PγGA in acidic media.

  2. Surface oxide growth on platinum electrode in aqueous trifluoromethanesulfonic acid

    NASA Astrophysics Data System (ADS)

    Furuya, Yoshihisa; Mashio, Tetsuya; Ohma, Atsushi; Dale, Nilesh; Oshihara, Kenzo; Jerkiewicz, Gregory

    2014-10-01

    Platinum in the form of nanoparticles is the key and most expensive component of polymer electrolyte membrane fuel cells, while trifluoromethanesulfonic acid (CF3SO3H) is the smallest fluorinated sulfonic acid. Nafion, which acts as both electrolyte and separator in fuel cells, contains -CF2SO3H groups. Consequently, research on the electrochemical behaviour of Pt in aqueous CF3SO3H solutions creates important background knowledge that can benefit fuel cell development. In this contribution, Pt electro-oxidation is studied in 0.1 M aqueous CF3SO3H as a function of the polarization potential (Ep, 1.10 ≤ Ep ≤ 1.50 V), polarization time (tp, 100 ≤ tp ≤ 104 s), and temperature (T, 278 ≤ T ≤ 333 K). The critical thicknesses (X1), which determines the applicability of oxide growth theories, is determined and related to the oxide thickness (dox). Because X1 > dox for the entire range of Ep, tp, and T values, the formation of Pt surface oxide follows the interfacial place-exchange or the metal cation escape mechanism. The mechanism of Pt electro-oxidation is revised and expanded by taking into account possible interactions of cations, anions, and water molecules with Pt. A modified kinetic equation for the interfacial place exchange is proposed. The application of the interfacial place-exchange and metal cation escape mechanisms leads to an estimation of the Ptδ+-Oδ- surface dipole (μPtO), and the potential drop (Vox) and electric field (Eox) within the oxide. The Pt-anion interactions affect the oxidation kinetics by indirectly influencing the electric field within the double layer and the surface oxide.

  3. Carbon monoxide poisoning and pulmonary injury from the mixture of formic and sulfuric acids.

    PubMed

    Schneir, Aaron; Rentmeester, Landen

    2016-06-01

    The inhalation of carbon monoxide produced by the incomplete combustion of carbon remains a popular method of suicide. A much less common method of producing carbon monoxide for suicide is by mixing formic and sulfuric acids. We describe a patient who attempted suicide by mixing formic and sulfuric acids. He presented with a depressed level of consciousness, chemical burns of his airway and skin, and respiratory distress. He was found to have a metabolic acidosis, a carboxyhemoglobin of 36.8%, hyperkalemia, and rhabdomyolysis. His hospital course was notable for copious pulmonary secretions and hypoxia, but he ultimately recovered with supportive care. The case highlights the potential toxicity, particularly from inhaled carbon monoxide and formic acid, with this method of suicide.

  4. Effect of dikes and sulfuric acid on cotton under effluent irrigation

    SciTech Connect

    Oron, G.; DeMalach, Y. )

    1989-06-01

    Extensive efforts are being undertaken to improve effluent use in arid zones with alkaline soils. In Israel, this type of soil (loess), with a relatively large amount of water loss due to runoff generation, is mainly found in the south. The possibility of decreasing runoff, soil erosion, improving water intake rate, and obtaining economic cotton yields was examined in a series of field experiments. Various combinations of dike construction between cotton rows and sulfuric acid applications were examined. Results showed that sulfuric acid significantly reduced runoff reduction and improved water infiltration, and that the acid treatments improves water intake and cotton yield more significantly than that of the dikes, under sprinkler and trickle irrigation systems.

  5. Effect of Mineral Admixtures on Resistance to Sulfuric Acid Solution of Mortars with Quaternary Binders

    NASA Astrophysics Data System (ADS)

    Makhloufi, Zoubir; Bederina, Madani; Bouhicha, Mohamed; Kadri, El-Hadj

    This research consists to study the synergistic action of three mineral additions simultaneously added to the cement. This synergistic effect has a positive effect on the sustainability of limestone mortars. Tests were performed on mortars based on crushed limestone sand and manufactured by five quaternary binders (ordinary Portland cement and CPO mixed simultaneously with filler limestone, blast-furnace and natural pozzolan). The purpose of this research was to identify the resistance of five different mortars to the solution of sulfuric acid. Changes in weight loss and compressive strength measured at 30, 60, 90, 120 and 180 days for each acid solution were studied. We followed up on the change in pH of the sulfuric acid solution at the end of each month up to 180 days.

  6. Iron dissolution of dust source materials during simulated acidic processing: the effect of sulfuric, acetic, and oxalic acids.

    PubMed

    Chen, Haihan; Grassian, Vicki H

    2013-09-17

    Atmospheric organic acids potentially display different capacities in iron (Fe) mobilization from atmospheric dust compared with inorganic acids, but few measurements have been made on this comparison. We report here a laboratory investigation of Fe mobilization of coal fly ash, a representative Fe-containing anthropogenic aerosol, and Arizona test dust, a reference source material for mineral dust, in pH 2 sulfuric acid, acetic acid, and oxalic acid, respectively. The effects of pH and solar radiation on Fe dissolution have also been explored. The relative capacities of these three acids in Fe dissolution are in the order of oxalic acid > sulfuric acid > acetic acid. Oxalate forms mononuclear bidentate ligand with surface Fe and promotes Fe dissolution to the greatest extent. Photolysis of Fe-oxalate complexes further enhances Fe dissolution with the concomitant degradation of oxalate. These results suggest that ligand-promoted dissolution of Fe may play a more significant role in mobilizing Fe from atmospheric dust compared with proton-assisted processing. The role of atmospheric organic acids should be taken into account in global-biogeochemical modeling to better access dissolved atmospheric Fe deposition flux at the ocean surface.

  7. Photoproduction of glyoxylic acid in model wine: Impact of sulfur dioxide, caffeic acid, pH and temperature.

    PubMed

    Grant-Preece, Paris; Schmidtke, Leigh M; Barril, Celia; Clark, Andrew C

    2017-01-15

    Glyoxylic acid is a tartaric acid degradation product formed in model wine solutions containing iron and its production is greatly increased by exposure to UV-visible light. In this study, the combined effect of sulfur dioxide, caffeic acid, pH and temperature on the light-induced (⩾300nm) production of glyoxylic acid in model wine containing tartaric acid and iron was investigated using a Box-Behnken experimental design and response surface methodology (RSM). Glyoxylic acid produced in the irradiated model wine was present in free and hydrogen sulfite adduct forms and the measured total, free and percentage free glyoxylic acid values were modeled using RSM. Sulfur dioxide significantly decreased the total amount of glyoxylic acid produced, but could not prevent its production, while caffeic acid showed no significant impact. The interaction between pH and temperature was significant, with low pH values and low temperatures giving rise to higher levels of total glyoxylic acid. Copyright © 2016 Elsevier Ltd. All rights reserved.

  8. Heterogeneous freezing of single sulfuric acid solution droplets: laboratory experiments utilizing an acoustic levitator

    NASA Astrophysics Data System (ADS)

    Ettner, M.; Mitra, S. K.; Borrmann, S.

    2004-09-01

    The heterogeneous freezing temperatures of single binary sulfuric acid solution droplets were measured in dependency of acid concentration down to temperatures as low as -50°C. In order to avoid influence of supporting substrates on the freezing characteristics, a new technique has been developed to suspend the droplet by means of an acoustic levitator. The droplets contained immersed particles of graphite, kaolin or montmorillonite in order to study the influence of the presence of such contamination on the freezing temperature. The radii of the suspended droplets spanned the range between 0.4 and 1.1mm and the concentration of the sulfuric acid solution varied between 5 and 14 weight percent. The presence of the particles in the solution raises the freezing temperature with respect to homogeneous freezing of these solution droplets. The pure solution droplets can be supercooled up to 40 degrees below the ice-acid solution thermodynamic equilibrium curve. Depending on the concentration of sulfuric acid and the nature of the impurity the polluted droplets froze between -11°C and -35°C. The new experimental set-up, combining a deep freezer with a movable ultrasonic levitator and suitable optics, proved to be a useful approach for such investigations on individual droplets.

  9. Heterogeneous chemistry of acetone in sulfuric acid solutions: Implications for the upper troposphere

    SciTech Connect

    Kane, S.M.; Timonen, R.S.; Leu, M.T.

    1999-11-18

    The uptake of acetone vapor by liquid sulfuric acid has been investigated over the range of 40--87 wt % H{sub 2}SO{sub 4} and between the temperatures 198 and 300 K. Studies were performed with a flow-tube reactor, using a quadrupole mass spectrometer for detection. At most concentrations studied (40--75 wt %), acetone was physically absorbed by sulfuric acid without undergoing irreversible reaction. However, at acid concentrations at or above 80 wt %, reactive uptake of acetone was observed, leading to products such as mesityl oxide and/or mesitylene. From time-dependent uptake data and liquid-phase diffusion coefficients calculated from molecular viscosity, the effective Henry's law solubility constant (H*) was determined. The solubility of acetone in liquid sulfuric acid was found to increase with increasing acid concentration and decreasing temperature. In the 75 wt % and 230 K range, the value for H* was found to be {approximately}2 x 10{sup 6} M/atm. This value suggests that acetone primarily remains in the gas phase rather than absorbing into sulfate aerosols under atmospheric conditions.

  10. Effect of sulfuric acid concentration of bentonite and calcination time of pillared bentonite

    NASA Astrophysics Data System (ADS)

    Mara, Ady; Wijaya, Karna; Trisunaryati, Wega; Mudasir

    2016-04-01

    An activation of natural clay has been developed. Activation was applied by refluxing the natural bentonite in variation of the sulfuric acid concentration and calcination time of pillared bentonite (PLC). Calcination was applied using oven in microwave 2,45 GHz. Determination of acidity was applied by measuring the amount of adsorbed ammonia and pyridine. Morphological, functional groups and chrystanility characterizations were analyzed using SEM, TEM, FTIR and XRD. Porosity was analyzed using SSA. The results showed that the greater of the concentration of sulfuric acid and calcination time was, the greater the acidity of bentonite as well as the pore diameter were. FTIR spectra showed no fundamental changes in the structure of the natural bentonite, SEM, and TEM images were showing an increase in space or field due to pillarization while the XRD patterns showed a shift to a lower peak. Optimization was obtained at a concentration of 2 M of sulfuric acid and calcination time of 20 minutes, keggin ion of 2.2 and suspension of 10 mmol, respectively each amounted to 11.7490 mmol/gram of ammonia and 2.4437 mmol/gram of pyridine with 154.6391 m2/gram for surface area, 0.130470 m3/gram of pore volume and 3.37484 nm of pore diameter.

  11. Preparation of manganese sulfate from low-grade manganese carbonate ores by sulfuric acid leaching

    NASA Astrophysics Data System (ADS)

    Lin, Qing-quan; Gu, Guo-hua; Wang, Hui; Zhu, Ren-feng; Liu, You-cai; Fu, Jian-gang

    2016-05-01

    In this study, a method for preparing pure manganese sulfate from low-grade ores with a granule mean size of 0.47 mm by direct acid leaching was developed. The effects of the types of leaching agents, sulfuric acid concentration, reaction temperature, and agitation rate on the leaching efficiency of manganese were investigated. We observed that sulfuric acid used as a leaching agent provides a similar leaching efficiency of manganese and superior selectivity against calcium compared to hydrochloric acid. The optimal leaching conditions in sulfuric acid media were determined; under the optimal conditions, the leaching efficiencies of Mn and Ca were 92.42% and 9.61%, respectively. Moreover, the kinetics of manganese leaching indicated that the leaching follows the diffusion-controlled model with an apparent activation energy of 12.28 kJ·mol-1. The purification conditions of the leaching solution were also discussed. The results show that manganese dioxide is a suitable oxidant of ferrous ions and sodium dimethyldithiocarbamate is an effective precipitant of heavy metals. Finally, through chemical analysis and X-ray diffraction analysis, the obtained product was determined to contain 98% of MnSO4·H2O.

  12. Separation of hafnium from zirconium in sulfuric acid solutions using pressurized ion exchange

    SciTech Connect

    Hurst, F.J.

    1981-01-01

    High-resolution pressurized ion exchange has been used successfully to study and separate hafnium and zirconium sulfate complexes by chromatographic elution from Dowex 50W-X8 (15 to 25 ..mu..m) resin with sulfuric acid solutions. Techniques were developed to continuously monitor the column effluents for zirconium and hafnium by reaction with fluorometric and colorimetric reagents. Since neither reagent was specific for either metal ion, peak patterns were initially identified by using the stable isotopes /sup 90/Zr and /sup 180/Hf as fingerprints of their elution position. Distribution ratios for both zirconium and hafnium decrease as the inverse fourth power of the sulfuric acid concentration below 2N and as the inverse second power at higher acid concentration. The hafnium-to-zirconium separation factor is approximately constant (approx. 8) over the 0.5 to 3N range. Under certain conditions, an unseparated fraction was observed that was not retained by the resin. The amount of this fraction which is thought to be a polymeric hydrolysis product appears to be a function of metal and sulfuric acid concentrations. Conditions are being sought to give the highest zirconium concentration and the lowest acid concentration that can be used as a feed material for commercial scale-up in the continuous annular chromatographic (CAC) unit without formation of the polymer.

  13. Effects of ageing on the content in sulfur-containing amino acids in rat brain.

    PubMed

    Benedetti, M S; Russo, A; Marrari, P; Dostert, P

    1991-01-01

    Concentrations of the sulfur-containing amino acids methionine, homocysteic acid, cysteic acid and taurine were measured in brain structures of young and old Wistar rats in an attempt to establish a possible link between the increase in oxidative stress with ageing and changes in tissue levels of these amino acids. Contrary to data reported by others, in all brain structures of young and old rats homocysteic acid levels could not be quantified. Compared with young rats, in old animals taurine and methionine concentrations significantly decreased in striatum and cortex; decreased taurine levels were also found in nucleus accumbens and cerebellum and lower concentrations of methionine were found in midbrain, hippocampus and pons-medulla. Cysteic acid levels either did not change or significantly increased in cortex and hippocampus. These results are discussed taking into account the biosynthesis of sulfur-containing amino acids in rat brain and the decrease in glutathione in relation to oxidative stress with ageing. Changes in aspartic acid, glutamic acid, serine, glutamine, glycine and GABA concentrations with ageing were also determined in the same brain structures and were in good agreement with those previously reported (Strolin Benedetti et al., 1990 a, b).

  14. Determination of aqueous acid-dissociation constants of aspartic acid using PCM/DFT method

    NASA Astrophysics Data System (ADS)

    Sang-Aroon, Wichien; Ruangpornvisuti, Vithaya

    Determination of acid-dissociation constants, pKa, of aspartic acid in aqueous solution, using density functional theory calculations combined with the conductor-like polarizable continuum model (CPCM) and with integral-equation-formalism polarizable continuum model (IEFPCM) based on the UAKS and UAHF radii, was carried out. The computed pKa values derived from the CPCM and IEFPCM with UAKS cavity model of bare structures of the B3LYP/6-31+G(d,p)-optimized tetrahydrated structures of aspartic acid species are mostly close to the experimental pKa values.0

  15. Corrosion abatement in sulfuric acid alkylation unit horizontal contactors

    SciTech Connect

    Schutt, H.U.

    1997-09-01

    The need to increase throughput in alkylation plants has resulted in higher operating temperatures and higher water levels in alkylation acids than projected by design. Combined with higher flow rates, the more severe process environment causes carbon steel to corrode at increased rates. Carbon steel is the main material of construction for horizontal contactors (Stratco reactors). A leak to the atmosphere in the hydraulic end cone of one contactor and the realization that basic corrosion data are not available for high throughput process conditions in alkylation units prompted a laboratory study to develop the lacking expertise. Corrosion in alkylation unit horizontal contactors is successfully mitigated by saturating fresh alkylation acid with ferrous sulfate.

  16. Influence of Sulfur on Acid-Mediated Enamide Formation.

    PubMed

    Lutz, Joshua A; Subasinghege Don, Visal; Kumar, Revati; Taylor, Carol M

    2017-09-11

    The acid-mediated condensation of acetamide with butanal dimethylacetal and EtSCH2CH(OMe)2, followed by dehydration, was investigated by electronic structure calculations that supported the prediction that the Z-geometry would be favored in the product. The reaction was investigated experimentally using suitably functionalized cysteine building blocks. Some side reactions and optimization of reaction conditions are reported, en route to identifying a mild, inexpensive Lewis acid that achieves a reasonable yield of (Z)-thioenamide 21 with high stereoselectivity.

  17. Exploration of Sulfur Assimilation of Aspergillus fumigatus Reveals Biosynthesis of Sulfur-Containing Amino Acids as a Virulence Determinant

    PubMed Central

    Dümig, Michaela; O'Keeffe, Gráinne; Binder, Jasmin; Doyle, Sean; Beilhack, Andreas

    2016-01-01

    Fungal infections are of major relevance due to the increased numbers of immunocompromised patients, frequently delayed diagnosis, and limited therapeutics. To date, the growth and nutritional requirements of fungi during infection, which are relevant for invasion of the host, are poorly understood. This is particularly true for invasive pulmonary aspergillosis, as so far, sources of (macro)elements that are exploited during infection have been identified to only a limited extent. Here, we have investigated sulfur (S) utilization by the human-pathogenic mold Aspergillus fumigatus during invasive growth. Our data reveal that inorganic S compounds or taurine is unlikely to serve as an S source during invasive pulmonary aspergillosis since a sulfate transporter mutant strain and a sulfite reductase mutant strain are fully virulent. In contrast, the S-containing amino acid cysteine is limiting for fungal growth, as proven by the reduced virulence of a cysteine auxotroph. Moreover, phenotypic characterization of this strain further revealed the robustness of the subordinate glutathione redox system. Interestingly, we demonstrate that methionine synthase is essential for A. fumigatus virulence, defining the biosynthetic route of this proteinogenic amino acid as a potential antifungal target. In conclusion, we provide novel insights into the nutritional requirements of A. fumigatus during pathogenesis, a prerequisite to understanding and fighting infection. PMID:26787716

  18. Exploration of Sulfur Assimilation of Aspergillus fumigatus Reveals Biosynthesis of Sulfur-Containing Amino Acids as a Virulence Determinant.

    PubMed

    Amich, Jorge; Dümig, Michaela; O'Keeffe, Gráinne; Binder, Jasmin; Doyle, Sean; Beilhack, Andreas; Krappmann, Sven

    2016-04-01

    Fungal infections are of major relevance due to the increased numbers of immunocompromised patients, frequently delayed diagnosis, and limited therapeutics. To date, the growth and nutritional requirements of fungi during infection, which are relevant for invasion of the host, are poorly understood. This is particularly true for invasive pulmonary aspergillosis, as so far, sources of (macro)elements that are exploited during infection have been identified to only a limited extent. Here, we have investigated sulfur (S) utilization by the human-pathogenic mold Aspergillus fumigatus during invasive growth. Our data reveal that inorganic S compounds or taurine is unlikely to serve as an S source during invasive pulmonary aspergillosis since a sulfate transporter mutant strain and a sulfite reductase mutant strain are fully virulent. In contrast, the S-containing amino acid cysteine is limiting for fungal growth, as proven by the reduced virulence of a cysteine auxotroph. Moreover, phenotypic characterization of this strain further revealed the robustness of the subordinate glutathione redox system. Interestingly, we demonstrate that methionine synthase is essential for A. fumigatus virulence, defining the biosynthetic route of this proteinogenic amino acid as a potential antifungal target. In conclusion, we provide novel insights into the nutritional requirements ofA. fumigatus during pathogenesis, a prerequisite to understanding and fighting infection. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

  19. Performance of a pilot-scale wet electrostatic precipitator for the control of sulfuric acid mist.

    PubMed

    Huang, Jiayu; Wang, Hongmei; Shi, Yingjie; Zhang, Fan; Dang, Xiaoqing; Zhang, Hui; Shu, Yun; Deng, Shuang; Liu, Yu

    2016-10-01

    The use of a wet electrostatic precipitator (WESP) is often regarded as a viable option to reduce sulfuric acid mist emitted from the wet flue gas desulfurization (WFGD) tower in coal-fired power plants. In this study, a pilot-scale wet electrostatic precipitator equipped with a wall-cooled collection electrode is investigated for the control of sulfuric acid mist from a simulated WFGD system. The results show that due to partial charging effect, the removal efficiency of sulfuric acid aerosol decreases when the aerosol size decreases to several tens of nanometers. Moreover, due to the plasma-induced effect, a large number of ultrafine sulfuric acid aerosols below 50 nm formed at a voltage higher than 24 kV inside the WESP. The percentages of submicron-sized aerosols significantly increase together with the voltage. To minimize the adverse plasma-induced effect, a WESP should be operated at a high gas velocity with an optimum high voltage. Even at a high flue gas velocity of 2.3 m s(-1), the mass concentration and the total number concentration of uncaptured sulfuric acid aerosols at the WESP outlet are as low as ca. 0.6 mg m(-3) and ca. 10(4) 1 cm(-3) at 28 kV, respectively. The corresponding removal efficiencies were respectively higher than 99.4 and 99.9 % and are very similar to that at 1.1 and 1.6 m s(-1). Moreover, the condensation-induced aerosol growth enhances the removal of sulfuric acid mist inside a WESP and enables a low emission concentration of ca. 0.65 mg m(-3) with a corresponding removal efficiency superior to 99.4 % even at a low voltage of 21 kV, and of ca. 0.35 mg m(-3) with a corresponding removal efficiency superior to 99.6 % at a higher voltage level of 26 kV.

  20. Role of sulfur-reducing bacteria in a wetland system treating acid mine drainage.

    PubMed

    Riefler, R Guy; Krohn, Jeremy; Stuart, Ben; Socotch, Cheryl

    2008-05-15

    This report describes a twenty month case study of a successive alkalinity producing system (SAPS) treating a strong acid mine drainage (AMD) source in Coshocton County, Ohio. Prior to the commencement of the project, a large volume of black amorphous sludge had accumulated in several of the constructed wetlands. The sludge was found to be 43% organic, with very high concentrations of sulfur, iron, aluminum, and acidity. Based on several biological, physical, and chemical analyses, the sludge was determined to be an anaerobic biofilm with a large population of sulfur-reducing bacteria and a high mineral content due to the formation of iron sulfide and aluminum precipitates. On average the system performed well, generating 26 kg CaCO3/d of alkalinity and capturing 5.0 kg/d of iron and 1.7 kg/d of aluminum. Several simple performance analysis tools were presented in this work. By comparing the pollutant influent and effluent loading, it was determined that the SAPS was performing at capacity and over the past year increased effluent concentrations were due to increased influent loadings and not system deterioration. Further, by performing a detailed cell-by-cell loading analysis of multiple chemical components, the alkalinity generated by limestone dissolution and by sulfate reduction was determined. Interestingly, 61% of the alkalinity generation in the vertical flow wetlands was due to sulfur-reducing bacteria activity, indicating that sulfur-reducing bacteria may play a more significant role in SAPS than expected.