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Sample records for acid h2so4 sulfuric

  1. Thermodynamics of the formation of sulfuric acid dimers in the binary (H2SO4-H2O) and ternary (H2SO4-H2O-NH3) system

    NASA Astrophysics Data System (ADS)

    Kürten, A.; Münch, S.; Rondo, L.; Bianchi, F.; Duplissy, J.; Jokinen, T.; Junninen, H.; Sarnela, N.; Schobesberger, S.; Simon, M.; Sipilä, M.; Almeida, J.; Amorim, A.; Dommen, J.; Donahue, N. M.; Dunne, E. M.; Flagan, R. C.; Franchin, A.; Kirkby, J.; Kupc, A.; Makhmutov, V.; Petäjä, T.; Praplan, A. P.; Riccobono, F.; Steiner, G.; Tomé, A.; Tsagkogeorgas, G.; Wagner, P. E.; Wimmer, D.; Baltensperger, U.; Kulmala, M.; Worsnop, D. R.; Curtius, J.

    2015-09-01

    Sulfuric acid is an important gas influencing atmospheric new particle formation (NPF). Both the binary (H2SO4-H2O) system and the ternary system involving ammonia (H2SO4-H2O-NH3) may be important in the free troposphere. An essential step in the nucleation of aerosol particles from gas-phase precursors is the formation of a dimer, so an understanding of the thermodynamics of dimer formation over a wide range of atmospheric conditions is essential to describe NPF. We have used the CLOUD chamber to conduct nucleation experiments for these systems at temperatures from 208 to 248 K. Neutral monomer and dimer concentrations of sulfuric acid were measured using a chemical ionization mass spectrometer (CIMS). From these measurements, dimer evaporation rates in the binary system were derived for temperatures of 208 and 223 K. We compare these results to literature data from a previous study that was conducted at higher temperatures but is in good agreement with the present study. For the ternary system the formation of H2SO4·NH3 is very likely an essential step in the formation of sulfuric acid dimers, which were measured at 210, 223, and 248 K. We estimate the thermodynamic properties (dH and dS) of the H2SO4·NH3 cluster using a simple heuristic model and the measured data. Furthermore, we report the first measurements of large neutral sulfuric acid clusters containing as many as 10 sulfuric acid molecules for the binary system using chemical ionization-atmospheric pressure interface time-of-flight (CI-APi-TOF) mass spectrometry.

  2. Laboratory measurement of the millimeter wave properties of liquid sulfuric acid (H2SO4). [study of microwave emission from Venus

    NASA Technical Reports Server (NTRS)

    Fahd, Antoine K.; Steffes, Paul G.

    1991-01-01

    The methodology and the results of laboratory measurements of the millimeter wave properties of liquid sulfuric acid are presented. Measurements conducted at 30-40 and 90-100 GHz are reported, using different concentrations of liquid H2SO4. The measured data are used to compute the expected opacity of H2SO4 condensates and their effects on the millimeter wave emission from Venus. The cloud condensate is found to have an effect on the emission from Venus. The calculated decrease in brightness temperature is well below the observed decrease in brightness temperature found by de Pater et al. (1991). It is suggested that other constituents such as gaseous H2SO4 also affect the observed variation in the brightness temperature.

  3. Influences of temperature, H2SO4 concentration and Sn content on corrosion behaviors of PbSn alloy in sulfuric acid solution

    NASA Astrophysics Data System (ADS)

    Li, D. G.; Chen, D. R.; Wang, J. D.; Chen, H. S.

    2011-10-01

    The influences of temperature, H2SO4 concentration and Sn content on corrosion behaviors of PbSn alloys in sulfuric acid solution were investigated by potentiodynamic curve, cyclic voltammetry (CV), linear sweeping voltage (LSV), electrochemical impedance spectra (EIS), a.c. voltammetry (ACV) and Mott-Schottky analysis. The microstructure of the corrosion layer on PbSn alloy was analyzed by scanning electron microscopy (SEM). The results showed that the corrosion resistance of PbSn alloy increased with ascending Sn content and H2SO4 concentration, the increment of temperature can decrease the corrosion resistance of PbSn alloy in H2SO4 solution. The conductivity of the anodic film on PbSn alloy was enhanced with increasing temperature, ascending Sn content and descending H2SO4 concentration. SEM result revealed that the corrosion film after cyclic voltammetry was consisted of tetragonal crystal, the porosity enlarged with decreasing temperature, Sn content and H2SO4 concentration.

  4. Vertical profiles of H2O, H2SO4, and sulfuric acid concentration at 45-75 km on Venus

    NASA Astrophysics Data System (ADS)

    Krasnopolsky, Vladimir A.

    2015-05-01

    A method developed by Krasnopolsky and Pollack (Krasnopolsky, V.A., Pollack, J.B. [1994]. Icarus 109, 58-78) to model vertical profiles of H2O and H2SO4 vapors and sulfuric acid concentration in the Venus cloud layer has been updated with improved thermodynamic parameters for H2O and H2SO4 and reduced photochemical production of sulfuric acid. The model is applied to the global-mean conditions and those at the low latitudes and at 60°. Variations in eddy diffusion near the lower cloud boundary are used to simulate variability in the cloud properties and abundances of H2O and H2SO4. The best version of the model for the global-mean condition results in a lower cloud boundary (LCB) at 47.5 km, H2SO4 peak abundance of 7.5 ppm at the LCB, and H2O mixing ratios of 7 ppm at 62 km and 3.5 ppm above 67 km. The model for low latitudes gives LCB at 48.5 km, the H2SO4 peak of 5 ppm, H2O of 8.5 ppm at 62 km and 3 ppm above 67 km. The model for 60° shows LCB at 46 km, the H2SO4 peak of 8.5 ppm, H2O of 9 ppm at 62 km and 4.5 ppm above 67 km. The calculated variability is induced by the proper changes in the production of sulfuric acid (by factors of 1.2 and 0.7 for the low latitudes and 60°, respectively) and reduction of eddy diffusion near 45 km relative to the value at 54 km by factors of 1.1, 3, and 4.5 for the low and middle (global-mean) latitudes and 60°, respectively. Concentration of sulfuric acid at the low and middle latitudes varies from ∼98% near 50 km to ∼80% at 60 km and then is almost constant at 79% at 70 km. Concentration at 60° is 98% at 50 km, 73% at 63 km, and 81% at 70 km. There is a reasonable agreement between the model results and observations except for the sulfuric acid concentration in the lower clouds. Variations of eddy diffusion in the lower cloud layer simulate variations in atmospheric dynamics and may induce strong variations in water vapor near the cloud tops. Variations in temperature may affect abundances of the H2O and H2SO4 vapors

  5. H-Bonding of Sulfuric Acid with Its Decomposition Products: An Infrared Matrix Isolation and Computational Study of the H2SO4·H2O·SO3 Complex.

    PubMed

    Rozenberg, Mark; Loewenschuss, Aharon; Nielsen, Claus J

    2016-05-26

    The FTIR matrix isolation spectra of H2SO4 vapors show a group of bands with synchronous growth of their relative intensities which is independent of the water species content of the matrix layer. Their frequency positions indicate that the species they represent is H-bonded and composed of all three components (H2SO4, H2O, and SO3) involved in the vapor decomposition equilibrium of the acid molecule. Structure, stabilization energies, and vibrational frequencies of several H-bonded complexes between these components were considered in B3LYP calculations employing Dunning's correlation-consistent aug-cc-pVTZ basis sets. Correlations between spectral shifts, bond lengths, and H-bond energies were also considered. The best fitting complex is a ring structured 1:1:1 H2SO4·H2O·SO3. The indications are that the complex is formed in the vapor phase and not after deposition. The atmospheric significance may be in its ability to serve as a H-bonding nucleation center even without the presence of additional contaminants. PMID:27135379

  6. H-Bonding of Sulfuric Acid with Its Decomposition Products: An Infrared Matrix Isolation and Computational Study of the H2SO4·H2O·SO3 Complex.

    PubMed

    Rozenberg, Mark; Loewenschuss, Aharon; Nielsen, Claus J

    2016-05-26

    The FTIR matrix isolation spectra of H2SO4 vapors show a group of bands with synchronous growth of their relative intensities which is independent of the water species content of the matrix layer. Their frequency positions indicate that the species they represent is H-bonded and composed of all three components (H2SO4, H2O, and SO3) involved in the vapor decomposition equilibrium of the acid molecule. Structure, stabilization energies, and vibrational frequencies of several H-bonded complexes between these components were considered in B3LYP calculations employing Dunning's correlation-consistent aug-cc-pVTZ basis sets. Correlations between spectral shifts, bond lengths, and H-bond energies were also considered. The best fitting complex is a ring structured 1:1:1 H2SO4·H2O·SO3. The indications are that the complex is formed in the vapor phase and not after deposition. The atmospheric significance may be in its ability to serve as a H-bonding nucleation center even without the presence of additional contaminants.

  7. Theoretical studies on the coupling interactions in H2SO4···HOO˙···(H2O)n (n = 0-2) clusters: toward understanding the role of water molecules in the uptake of HOO˙ radical by sulfuric acid aerosols.

    PubMed

    Li, Ping; Ma, Zhiying; Wang, Weihua; Zhai, Yazhou; Sun, Haitao; Bi, Siwei; Bu, Yuxiang

    2011-01-21

    A detailed knowledge of coupling interactions among sulfuric acid (H(2)SO(4)), the hydroperoxyl radical (HOO˙), and water molecules (H(2)O) is crucial for the better understanding of the uptake of HOO˙ radicals by sulfuric acid aerosols at different atmospheric humidities. In the present study, the equilibrium structures, binding energies, equilibrium distributions, and the nature of the coupling interactions in H(2)SO(4)···HOO˙···(H(2)O)(n) (n = 0-2) clusters have been systematically investigated at the B3LYP/6-311++G(3df,3pd) level of theory in combination with the atoms in molecules (AIM) theory, natural bond orbital (NBO) method, energy decomposition analyses, and ab initio molecular dynamics. Two binary, five ternary, and twelve tetramer clusters possessing multiple intermolecular H-bonds have been located on their potential energy surfaces. Two different modes for water molecules have been observed to influence the coupling interactions between H(2)SO(4) and HOO˙ through the formations of intermolecular H-bonds with or without breaking the original intermolecular H-bonds in the binary H(2)SO(4)···HOO˙ cluster. It was found that the introduction of one or two water molecules can efficiently enhance the interactions between H(2)SO(4) and HOO˙, implying the positive role of water molecules in the uptake of the HOO˙ radical by sulfuric acid aerosols. Additionally, the coupling interaction modes of the most stable clusters under study have been verified by the ab initio molecular dynamics. PMID:21052607

  8. Interactions of methylamine and ammonia with atmospheric nucleation precursor H2SO4 and common organic acids: Thermodynamics and atmospheric implications

    NASA Astrophysics Data System (ADS)

    Xu, Y.; Nadykto, A. B.; Jiang, L.; Bai, Z.

    2016-06-01

    Interactions of the two common atmospheric bases, ammonia (NH3) and methylamine MA (CH3NH2), which are considered to be important stabilizers of binary clusters in the Earth's atmosphere, with H2SO4, the key atmospheric precursor, and 14 common atmospheric organic acids (COA) (formic (CH2O2), acetic (C2H4O2), oxalic (C2H2O4), malonic (C3H4O4), succinic (C4H6O4), glutaric acid (C5H8O4), adipic (C6H10O4), benzoic (C6H5COOH), phenylacetic (C6H5CH2COOH), pyruvic (C3H4O3), maleic acid (C4H4O4), malic (C4H6O5), tartaric (C4H6O6) and pinonic acid (C10H16O3)) have been studied using the composite high-accuracy G3MP2 method. The thermodynamic stability of mixed (COA) (H2SO4), (COA)(B1) and (COA)(B2) dimers and (COA) (H2SO4) (B1) and (COA) (H2SO4) (B1) trimers, where B1 and B2 represent methylamine (CH3NH2) and ammonia (NH3), respectively, have been investigated and their impacts on the thermodynamic stability of clusters containing H2SO4 have been analyzed. It has been shown that in many cases the interactions of H2SO4 with COA, ammonia and methylamine lead to the formation of heteromolecular dimers and trimers, which are certainly more stable than (H2SO4)2 and (H2SO4)3. It has also been found that free energies of (COA) (H2SO4)+ CH3NH2⇔(COA) (H2SO4)(CH3NH2) reactions exceed 10-15 kcal mol-1. This is a clear indication that mixed trimers composed of COA, H2SO4 and methylamine are very stable and can thus serve as possible nucleation sites. The present study leads us to conclude that the interactions of COA coexisting with H2SO4 and common atmospheric bases in the Earth's atmosphere may be an important factor affecting the stability of nucleating sulfuric acid clusters and that the impacts of COA on atmospheric nucleation should be studied in further details.

  9. Removal of arsenic in coal fly ash by acid washing process using dilute H2SO4 solvent.

    PubMed

    Kashiwakura, Shunsuke; Ohno, Hajime; Matsubae-Yokoyama, Kazuyo; Kumagai, Yuichi; Kubo, Hiroshi; Nagasaka, Tetsuya

    2010-09-15

    Coal fly ash emitted from coal thermal power plants generally contains tens ppm of arsenic, one of the hazardous elements in coal, during combustion and their elution to soil or water has become a public concern. In this study, the acid washing process developed by the authors was applied to the removal of arsenic from coal fly ash. Laboratory- and bench-scale investigations on the dissolution behavior of arsenic from various coal fly ash samples into dilute H(2)SO(4) were conducted. Arsenic in the coal fly ash samples were dissolved into H(2)SO(4) solutions rapidly. However, its concentrations decreased with an increase in the pH of H(2)SO(4) solution in some cases. The species of arsenic in the dilute H(2)SO(4) was estimated as H(3)AsO(4), and its anionic species was considered to adsorb with the elevation of pH under the presence of ash particle. Such adsorption behavior was enhanced under the presence of Fe ion in the solution. The sufficient removal of arsenic was achieved by controlling pH and avoiding the adsorption of arsenic on the surface of coal fly ash particles, and the elution of arsenic from coal fly ash sample was successfully below the regulation limit.

  10. Reductive atmospheric acid leaching of spent alkaline batteries in H2SO4/Na2SO3 solutions

    NASA Astrophysics Data System (ADS)

    Morcali, Mehmet Hakan

    2015-07-01

    This work studies the optimum reductive leaching process for manganese and zinc recovery from spent alkaline battery paste. The effects of reducing agents, acid concentration, pulp density, reaction temperature, and leaching time on the dissolution of manganese and zinc were investigated in detail. Manganese dissolution by reductive acidic media is an intermediate-controlled process with an activation energy of 12.28 kJ·mol-1. After being leached, manganese and zinc were selectively precipitated with sodium hydroxide. The zinc was entirely converted into zincate (Zn(OH){4/2-}) ions and thus did not co-precipitate with manganese hydroxide during this treatment (2.0 M NaOH, 90 min, 200 r/min, pH > 13). After the manganese was removed from the solution, the Zn(OH){4/2-} was precipitated as zinc sulfate in the presence of sulfuric acid. The results indicated that this process could be effective in recovering manganese and zinc from alkaline batteries.

  11. The corrosion inhibition and gas evolution studies of some surfactants and citric acid on lead alloy in 12.5 M H2SO4 solution

    NASA Astrophysics Data System (ADS)

    Tizpar, A.; Ghasemi, Z.

    2006-10-01

    The inhibition action of the citric acid and three surfactants: sodium dodecyl sulfate (SDS), t-octyl phenoxy polyethoxyethanol (Triton X-100), sodium dodecyl benzene sulphonate (SDBS) on the corrosion behavior and gas evolution of Pb Sb As Se was investigated in 12.5 M H2SO4 solution with linear sweep polarization, cyclic voltammetry and weight loss measurements methods. The results drawn from different techniques are comparable. It was found that these surfactants and citric acid act as good inhibitors for the corrosion of lead alloy in H2SO4 solution. SDS inhibited most effectively the lead alloy corrosion among the three surfactants and citric acid. The inhibition efficiency for the inhibitors decreases in the order: SDS > SDBS > Triton X-100 > citric acid > blank. The inhibition efficiency increases with rising of the inhibitor concentration. In this work, the effect of the inhibitors on hydrogen and oxygen evolution was studied. In addition, it was found that the adsorption of used inhibitors on lead alloy surface follows Langmuir isotherm.

  12. Study on nonlinear kinetic and thermodynamics of oscillating reaction of amino Acid-BrO{3/-}-Mn2+-H2SO4-acetone system

    NASA Astrophysics Data System (ADS)

    Li, Zongxiao; Yuan, Chunlan

    2011-08-01

    With the help of the kinetic parameters (the rate constant ( k in k p) and the apparent activation energy ( E in E p) of the oscillatory induction period and oscillation period) of the oscillating reaction using thirteen amino acids, leucine (Leu), threonine (Thr), arginine (Arg), lysine (Lys), histidine (His), alanine (Ala), glutamine (Glu), glycine (Gly), methionine (Met), cystine (Cys), tryptophan (Trp), serine (Ser) and tyrosine (Tyr), as organic substrates in amino acid-BrO{3/-}-Mn2+-H2SO4-acetone system, then based on the Oregonator model and the thermodynamics theory on irreversible process, the thermodynamic function (Δ H in, Δ G in, Δ S in and Δ H p, Δ G p, Δ S p) of these oscillating system are studied. The results indicate the entropy Δ S of these oscillating reaction are negative, thereby it is proved that the oscillating reaction is a noequilibrium system with dissipation structure in agreement with the character of the oscillating reaction from disorder to order in irreversible thermodynamics. These are satisfactorily to explain the experimental phenomena.

  13. Generation of acids from mine waste: Oxidative leaching of pyrrhotite in dilute H 2SO 4 solutions at pH 3.0

    NASA Astrophysics Data System (ADS)

    Pratt, A. R.; Nesbitt, H. W.; muir, I. J.

    1994-12-01

    Pyrrhotite (Fe 7S 8) grains 3 × 3 × 6 mm were reacted in solutions of H 2SO 4 (pH 3.0) for eight hours and analyzed using secondary electron microscopy (SEM), Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). SEM images of reacted surfaces display an array of reaction textures, which are interpreted to represent a five-stage (T1-T5) paragenetic alteration sequence. Leached pyrrhotite surfaces are initially featureless (T1 texture). Surfaces leached more extensively develop a mottled felty texture (T2). Subsequent drying of reacted surfaces causes dehydration, producing cracked, tiled surfaces (T3 textures). Prolonged drying intensifies the effects of desiccation, producing rubbly (T4) textures. The rubble is readily spalled, exposing smooth underlayers (T5 textures). AES and XPS data collected from T1 through T4 textured surfaces indicate primarily Fe-oxyhydroxide reaction products. AES depth profiles show that S varies antipathetically with oxygen. AES analysis of T5 textured surfaces (underlayer exposed by spalling) detect only Fe and S, with S significantly enriched over Fe. XPS and modelled AES data show T5 textured regions are mainly ferric iron bonded to disulphide and/or polysulphide species. The accumulation of S in the underlayer is accomplished by preferential migration of Fe to the overlying oxyhydroxide layer to the pyrrhotite surface, thus, promoting spallation. Spalling of Fe(III)-oxyhydroxides is promoted in waste rock dumps and tailings situated above the water table by periodic wetting, drying and desiccation of the oxyhydroxide layer. These circumstances may, in turn, lead to high concentrations of suspended Fe-oxyhydroxide in tailings ponds during flooding and in ponds where there are dramatic seasonal overturns of lake or pond water. Exposure by spalling of S-rich sublayers to aqueous solutions is an effective means for producing sulphuric acid-rich mine waste runoff and of producing periodic flushes of sulphuric

  14. H2O-H2SO4 system in Venus' clouds and OCS, CO, and H2SO4 profiles in Venus' troposphere.

    PubMed

    Krasnopolsky, V A; Pollack, J B

    1994-05-01

    A coupled problem of diffusion and condensation is solved for the H2SO4-H2O system in Venus' cloud layer. The position of the lower cloud boundary and profiles of the H2O and H2SO4 vapor mixing ratios and of the H2O/H2SO4 ratio of sulfuric acid aerosol and its flux are calculated as functions of the column photochemical production rate of sulfuric acid, phi H2SO4. Variations of the lower cloud boundary are considered. Our basic model, which is constrained to yield fH2O (30 km) = 30 ppm (Pollack et al. 1993), predicts the position of the lower cloud boundary at 48.4 km coinciding with the mean Pioneer Venus value, the peak H2SO4 mixing ratio of 5.4 ppm, and the H2SO4 production rate phi H2SO4 = 2.2 x 10(12) cm-2 sec-1. The sulfur to sulfuric acid mass flux ratio in the clouds is 1 : 27 in this model, and the mass loading ratio may be larger than this value if sulfur particles are smaller than those of sulfuric acid. The model suggests that the extinction coefficient of sulfuric acid particles with radius 3.7 micrometers (mode 3) is equal to 0.3 km-1 in the middle cloud layer. The downward flux of CO is equal to 1.7 x 10(12) cm-2 sec-1 in this model. Our second model, which is constrained to yield fH2SO4 = 10 ppm at the lower cloud boundary, close to the value measured by the Magellan radiooccultations, predicts the position of this boundary to be at 46.5 km, which agrees with the Magellan data; fH2O(30 km) = 90 ppm, close to the data of Moroz et al. (1983) at this altitude; phi H2SO4 = 6.4 x 10(12) cm-2 sec-1; and phi co = 4.2 x 10(12) cm-2 sec-1. The S/H2SO4 flux mass ratio is 1 : 18, and the extinction coefficient of the mode 3 sulfuric acid particles is equal to 0.9 km-1 in the middle cloud layer. A strong gradient of the H2SO4 vapor mixing ratio near the bottom of the cloud layer drives a large upward flux of H2SO4, which condenses and forms the excessive downward flux of liquid sulfuric acid, which is larger by a factor of 4-7 than the flux in the middle cloud

  15. H2O-H2SO4 system in Venus' clouds and OCS, CO, and H2SO4 profiles in Venus' troposphere.

    PubMed

    Krasnopolsky, V A; Pollack, J B

    1994-05-01

    A coupled problem of diffusion and condensation is solved for the H2SO4-H2O system in Venus' cloud layer. The position of the lower cloud boundary and profiles of the H2O and H2SO4 vapor mixing ratios and of the H2O/H2SO4 ratio of sulfuric acid aerosol and its flux are calculated as functions of the column photochemical production rate of sulfuric acid, phi H2SO4. Variations of the lower cloud boundary are considered. Our basic model, which is constrained to yield fH2O (30 km) = 30 ppm (Pollack et al. 1993), predicts the position of the lower cloud boundary at 48.4 km coinciding with the mean Pioneer Venus value, the peak H2SO4 mixing ratio of 5.4 ppm, and the H2SO4 production rate phi H2SO4 = 2.2 x 10(12) cm-2 sec-1. The sulfur to sulfuric acid mass flux ratio in the clouds is 1 : 27 in this model, and the mass loading ratio may be larger than this value if sulfur particles are smaller than those of sulfuric acid. The model suggests that the extinction coefficient of sulfuric acid particles with radius 3.7 micrometers (mode 3) is equal to 0.3 km-1 in the middle cloud layer. The downward flux of CO is equal to 1.7 x 10(12) cm-2 sec-1 in this model. Our second model, which is constrained to yield fH2SO4 = 10 ppm at the lower cloud boundary, close to the value measured by the Magellan radiooccultations, predicts the position of this boundary to be at 46.5 km, which agrees with the Magellan data; fH2O(30 km) = 90 ppm, close to the data of Moroz et al. (1983) at this altitude; phi H2SO4 = 6.4 x 10(12) cm-2 sec-1; and phi co = 4.2 x 10(12) cm-2 sec-1. The S/H2SO4 flux mass ratio is 1 : 18, and the extinction coefficient of the mode 3 sulfuric acid particles is equal to 0.9 km-1 in the middle cloud layer. A strong gradient of the H2SO4 vapor mixing ratio near the bottom of the cloud layer drives a large upward flux of H2SO4, which condenses and forms the excessive downward flux of liquid sulfuric acid, which is larger by a factor of 4-7 than the flux in the middle cloud

  16. H2O-H2SO4 system in Venus' clouds and OCS, CO, and H2SO4 profiles in Venus' troposphere

    NASA Astrophysics Data System (ADS)

    Krasnopolsky, V. A.; Pollack, J. B.

    1994-05-01

    A coupled problem of diffusion and condensation is solved for the H2SO4-H2O system in Venus' cloud layer. The position of the lower cloud boundary and profiles of the H2O and H2SO4 vapor mixing ratios and of the H2O/H2SO4 ratio of sulfuric acid aerosol and its flux are calculated as functions of the column photochemical production rate of sulfuric acid, PhiH2SO4. Variations of the lower cloud boundary are considered. Our basic model, which is constrained to yield fH2O (30 km) = 30 ppm (Pollack et al. 1993), predicts the position of the lower cloud boundary at 48.4 km coinciding with the mean Pioneer Venus value, the peak H2SO4 mixing ratio of 5.4 ppm, and the H2SO4 production rate PhiH2SO4 = 2.2 x 1012/sq cm/s. The sulfur to sulfuric acid mass flux ratio in the clouds is 1:27 in this model, and the mass loading ratio may be larger than this value if sulfur particles are smaller than those of sulfuric acid. The model suggests that the extinction coefficient of sulfuric acid particles with radius 3.7 micrometers (mode 3) is equal to 0.3/km in the middle cloud layer. The downward flux of CO is equal to 1.7 x 1012/sq cm/s in this model. Our second model, which is constrained to yield fH2O = 10 ppm at the lower cloud boundary, close to the value measured by the Magellan radio occultations, predicts the position of this boundary to be at 46.5 km, which agrees with the Magellan data; fH2O (30 km) = 90 ppm, close to the data of Moroz et al. (1983) at this altitude; PhiH2SO4 = 6.4 x 1012/sq cm/s; and Phico = 4.2 x 1012/sq cm/s. The S/H2SO4 flux mass ratio is 1:18, and the extinction coefficient of the mode 3 sulfuric acid particles is equal to 0.9 km in the middle cloud layer. A strong gradient of the H2SO4 vapor mixing ratio near the bottom of the cloud layer drives a large upward flux of H2SO4, which condenses and forms the excessive downward flux of liquid sulfuric acid, which is larger by a factor of 4-7 than the flux in the middle cloud layer. This is the mechanism of

  17. H2O-H2SO4 system in Venus' clouds and OCS, CO, and H2SO4 profiles in Venus' troposphere

    NASA Technical Reports Server (NTRS)

    Krasnopolsky, V. A.; Pollack, J. B.

    1994-01-01

    A coupled problem of diffusion and condensation is solved for the H2SO4-H2O system in Venus' cloud layer. The position of the lower cloud boundary and profiles of the H2O and H2SO4 vapor mixing ratios and of the H2O/H2SO4 ratio of sulfuric acid aerosol and its flux are calculated as functions of the column photochemical production rate of sulfuric acid, Phi(sub H2SO4). Variations of the lower cloud boundary are considered. Our basic model, which is constrained to yield f(sub H2O) (30 km) = 30 ppm (Pollack et al. 1993), predicts the position of the lower cloud boundary at 48.4 km coinciding with the mean Pioneer Venus value, the peak H2SO4 mixing ratio of 5.4 ppm, and the H2SO4 production rate Phi(sub H2SO4) = 2.2 x 10(exp 12)/sq cm/s. The sulfur to sulfuric acid mass flux ratio in the clouds is 1:27 in this model, and the mass loading ratio may be larger than this value if sulfur particles are smaller than those of sulfuric acid. The model suggests that the extinction coefficient of sulfuric acid particles with radius 3.7 micrometers (mode 3) is equal to 0.3/km in the middle cloud layer. The downward flux of CO is equal to 1.7 x 10(exp 12)/sq cm/s in this model. Our second model, which is constrained to yield f(sub H2O) = 10 ppm at the lower cloud boundary, close to the value measured by the Magellan radiooccultations, predicts the position of this boundary to be at 46.5 km, which agrees with the Magellan data; f(sub H2O) (30 km) = 90 ppm, close to the data of Moroz et al. (1983) at this altitude; Phi(sub H2SO4) = 6.4 x 10(exp 12)/sq cm/s; and Phi(sub co) = 4.2 x 10(exp 12)/sq cm/s. The S/H2SO4 flux mass ratio is 1:18, and the extinction coefficient of the mode 3 sulfuric acid particles is equal to 0.9 km in the middle cloud layer. A strong gradient of the H2SO4 vapor mixing ratio near the bottom of the cloud layer drives a large upward flux of H2SO4, which condenses and forms the excessive downward flux of liquid sulfuric acid, which is larger by a factor of 4

  18. The influence of treatment temperature on the acidity of MWCNT oxidized by HNO 3 or a mixture of HNO 3/H 2SO 4

    NASA Astrophysics Data System (ADS)

    Saleh, Tawfik A.

    2011-06-01

    The nature of multi-walled carbon nanotubes (MWCNTs) varies with the change in oxidation conditions. In this work, the effect of treatment temperatures on the acidity of MWCNTs was studied. Oxidation was performed by refluxing the MWCNTs in nitric acid or mixtures of sulfuric acid and nitric acid at different temperatures. After oxidative treatment, a quantitative characterization of o-MWCNTs has been performed using acid-base titrations which show that the number of surface acidic functional groups increased by increasing the treatment temperatures. Energy dispersive X-ray (EDX) measurements show that the oxygen content increased with increasing treatment temperatures. Fourier transform infrared absorption spectroscopy (FTIR) was used for qualitative characterization. It has been demonstrated that the acidity is a function of the type of oxidizing agent used and the treatment temperatures. Due to the importance in attachment strategies and functionalization, this study adds to the global discussion of the possibility of controlling the MWCNTs' surface chemistry which plays a crucial role in determining its reactivity.

  19. A Study on the Passivation Behavior and Semiconducting Properties of Gamma Titanium Aluminide in 0.1 N H2SO4, HNO3, and HClO4 Acidic Solutions

    NASA Astrophysics Data System (ADS)

    Memarbashi, S.; Saebnoori, E.; Shahrabi, T.

    2014-03-01

    The study focuses on the passivation behavior of single-gamma-phase titanium aluminide in acidic solutions with a particular emphasis on the role of oxidizing strength in characteristics of passive layer. The report includes potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) studies along with Mott-Schottky analysis in order to determine the corrosion behavior of the alloy and the semiconducting properties of the scale formed during exposure to acidic environment. Passive current density measured from potentiodynamic polarization curve, polarization resistance ( R p) estimated by EIS, defect density, and flatband potential drawn from Mott-Schottky analysis are mainly used in estimating the ability of passive film formed on alloy in protecting it against high corrosion rates in Sulfuric acid (a non-oxidizing acid), perchloric acid, and nitric acid (oxidizing acid with different oxidizing strength). The results show that passive current density ( i pass) in Sulfuric acid is 2.67 × 10-5 A cm-2, which is 2.5 and 3 times greater than the values obtained in perchloric acid ( i pass = 9.91 × 10-6) and nitric acid ( i pass = 7.98 × 10-6), respectively. EIS data reveal that the value of R p in sulfuric acid (20 kΩ cm2) is about three and five times smaller than that its value in perchloric acid and Nitric acid, respectively. Mott-Schottky analysis shows that the passive layer exhibits an n-type semiconducting characteristics irrespective of acidic environment. The greatest and the smallest values of donor density ( N D) are obtained for the passive scale formed in sulfuric acid ( N D, H2SO4 = 18.36 × 1019) and nitric acid ( N D, HNO3 = 13.13 × 1019), respectively. The report concludes that characteristics of the passive scale are directly affected by reduction potential of the acid, which is the criterion of its oxidizing strength. An increase in the oxidizing strength of the acidic solution results in formation of more protective and less

  20. Behavior of OH, H2SO4, and MSA during PASE

    NASA Astrophysics Data System (ADS)

    Mauldin, L.; Kosciuch, E.; Cantrell, C.; Anderson, R.

    2008-12-01

    The role of aerosols in climatic feedback and oxidation chemistry has gained appreciation with the recognition of climate change. Key in the formation and growth of aerosols are hydroxyl radical (OH) and sulfuric acid (H2SO4). To a lesser extent methane sulfonic acid (MSA) is known to participate in particle growth. The Pacific Atmospheric Sulfur Experiment (PASE) was conducted out of Christmas Island, Kiribati during Aug-Sept 2006, with an overall goal of studying DMS oxidation. Here airborne results of OH, H2SO4, and MSA are presented. Typical midday OH concentrations were on the order of 2-3 x 106 molecule cm-3. Both H2SO4 and MSA concentrations showed a strong dependence upon relative humidity. These species will be discussed in terms of partitioning between the gas and particle phases, and in terms of particle neutralization.

  1. Three-phase extraction study of cyanex 923-n-heptane/H(2)SO(4) system.

    PubMed

    Liao, Wuping; Shang, Qingkun; Yu, Guihong; Li, Deqian

    2002-07-19

    Phase behavior of the extraction system, Cyanex 923-heptane/H(2)SO(4)-H(2)O has been studied. The third phase appeared at different aqueous H(2)SO(4) concentration with varying initial Cyanex 923 concentration and temperature affects its appearance. Almost all of H(2)SO(4) and H(2)O are extracted into the middle phase. The H(2)SO(4) concentration in the third phase increases with the increasing aqueous acid concentration (C(H(2)SO(4),b)) while the water content first increases and then reaches a constant value at C(H(2)SO(4),b)=11.3 mol l(-1). In the region of C(H(2)SO(4),b) higher than 5.2 mol l(-1), the composition of the middle phase is only related to the equilibrium concentration of H(2)SO(4) in the bottom phase. H(2)SO(4) and H(2)O are transferred into the middle phase mainly by their coordination with Cyanex 923 when C(H(2)SO(4),b) is less than 11.3 mol l(-1). When C(H(2)SO(4),b) is higher than 11.3 mol l(-1), excess H(2)SO(4) is solubilized into the polar layer of the aggregates. In the region considered, the extracted complex changes from C923 . H(2)SO(4) to C923 . H(2)SO(4) . H(2)O and then to C923 . (H(2)SO(4))(2) . H(2)O.

  2. Characterization of degradation products of ivabradine by LC-HR-MS/MS: a typical case of exhibition of different degradation behaviour in HCl and H2SO4 acid hydrolysis.

    PubMed

    Patel, Prinesh N; Borkar, Roshan M; Kalariya, Pradipbhai D; Gangwal, Rahul P; Sangamwar, Abhay T; Samanthula, Gananadhamu; Ragampeta, Srinivas

    2015-02-01

    A validated stability-indicating HPLC method was established, and comprehensive stress testing of ivabradine, a cardiotonic drug, was carried out as per ICH guidelines. Ivabradine was subjected to acidic, basic and neutral hydrolysis, oxidation, photolysis and thermal stress conditions, and the resulting degradation products were investigated by LC-PDA and LC-HR-MS/MS. The drug was found to degrade in acid and base hydrolysis. An efficient and selective stability assay method was developed on Phenomenex Luna C18 (250 × 4.6 mm, 5.0 µm) column using ammonium formate (10 mM, pH 3.0) and acetonitrile as mobile phase at 30 °C in gradient elution mode. The flow rate was 0.7 ml/min and detection wavelength was 286 nm. A total of five degradation products (I-1 to I-5) were identified and characterized by LC-HR-MS/MS in combination with accurate mass measurements. The drug exhibited different degradation behaviour in HCl and H2SO4 hydrolysis conditions. It is a unique example where two of the five degradation products in HCl hydrolysis were absent in H2SO4 acid hydrolysis. The present study provides guidance to revise the stress test for the determination of inherent stability of drugs containing lactam moiety under hydrolytic conditions. Most probable mechanisms for the formation of degradation products have been proposed on the basis of a comparison of the fragmentation pattern of the drug and its degradation products. In silico toxicity revealed that the degradation products (I-2 to I-5) were found to be severe irritants in case of ocular irritancy. The analytical assay method was validated with respect to specificity, linearity, range, precision, accuracy and robustness.

  3. Measurement and model results for gas phase OH and H2SO4 during PROPHET 2001.

    NASA Astrophysics Data System (ADS)

    Tanner, D.; Sjostedt, S.; Huey, G.; Slusher, D.; Chen, G.; Lefer, B.; Shetter, R.; Carroll, M.; Hengel, S.; Fortner, E.; Young, V.

    2002-12-01

    During the summer of 2001 a Chemical Ionization Mass Spectrometer (CIMS) was installed on top of the PROPHET tower to measure OH and H2SO4. Both OH and H2SO4 have a strong diurnal variation and correlate well with the measured ozone photolysis rate. Typical OH nighttime values are below the detection limit of 3e5 molecules cm-3. The maximum daytime value varied from 1-5 e6 molecules cm-3 with the highest OH levels corresponding to the lowest isoprene mixing ratios. The nighttime results are inconsistent with previous LIF measurements of high nighttime OH levels at this site and may indicate a systematic difference between the two techniques. However, the midday measured OH data is approximately 50% higher than the preliminary midday model values and is in accord with the previous LIF observations. A more detailed comparison of constrained photochemical models predictions to the observed OH levels will be presented. The daytime H2SO4 concentrations were highly variable and exceeded 5e7 molecules cm-3 on two days under "clean" northerly flow conditions. Evidence will be presented that suggest the source of the relatively high sulfuric acid concentrations is a large nickel smelting operation in Sudbury, Ontario. The nighttime levels of sulfuric acid were typically below the detection limit of the instrument of approximately 1e5 molecules cm-3. This data is consistent with the measured OH and suggests that large nighttime sources of radicals are not present in this environment.

  4. Vertical profile of H 2SO 4 vapor at 70-110 km on Venus and some related problems

    NASA Astrophysics Data System (ADS)

    Krasnopolsky, Vladimir A.

    2011-09-01

    The vertical profile of H 2SO 4 vapor is calculated using current atmospheric and thermodynamic data. The atmospheric data include the H 2O profiles observed at 70-112 km by the SOIR solar occultations, the SPICAV-UV profiles of the haze extinction at 220 nm, the VeRa temperature profiles, and a typical profile of eddy diffusion. The thermodynamic data are the saturated vapor pressures of H 2O and H 2SO 4 and chemical potentials of these species in sulfuric acid solutions. The calculated concentration of sulfuric acid in the cloud droplets varies from 85% at 70 km to a minimum of 70% at 90 km and then gradually increasing to 90-100% at 110 km. The H 2SO 4 vapor mixing ratio is ˜10 -12 at 70 and 110 km with a deep minimum of 3 × 10 -18 at 88 km. The H 2O-H 2SO 4 system matches the local thermodynamic equilibrium conditions up to 87 km. The column photolysis rate of H 2SO 4 is 1.6 × 10 5 cm -2 s -1 at 70 km and 23 cm -2 s -1 at 90 km. The calculated abundance of H 2SO 4 vapor at 90-110 km and its photolysis rate are smaller than those presented in the recent model by Zhang et al. (Zhang, X., Liang, M.C., Montmessin, F., Bertaux, J.L., Parkinson, C., Yung, Y.L. [2010]. Nat. Geosci. 3, 834-837) by factors of 10 6 and 10 9, respectively. Assumptions of 100% sulfuric acid, local thermodynamic equilibrium, too warm atmosphere, supersaturation of H 2SO 4 (impossible for a source of SO X), and cross sections for H 2SO 4·H 2O (impossible above the pure H 2SO 4) are the main reasons of this huge difference. Significant differences and contradictions between the SPICAV-UV, SOIR, and ground-based submillimeter observations of SO X at 70-110 km are briefly discussed and some weaknesses are outlined. The possible source of high altitude SO X on Venus remains unclear and probably does not exist.

  5. Berberine as a natural source inhibitor for mild steel in 1 M H 2SO 4

    NASA Astrophysics Data System (ADS)

    Li, Yan; Zhao, Peng; Liang, Qiang; Hou, Baorong

    2005-12-01

    Berberine was abstracted from coptis chinensis and its inhibition efficiency on corrosion of mild steel in 1 M H 2SO 4 was investigated through weight loss experiment, electrochemical techniques and scanning electronic microscope (SEM) with energy disperse spectrometer (EDS). The weight loss results showed that berberine is an excellent corrosion inhibitor for mild steel immersed in 1 M H 2SO 4. Potentiodynamic curves suggested that berberine suppressed both cathodic and anodic processes for its concentrations higher than 1.0 × 10 -4 M and mainly cathodic reaction was suppressed for lower concentrations. The Nyquist diagrams of impedance for mild steel in 1 M H 2SO 4 containing berberine with different concentrations showed one capacitive loop, and the polarization resistance increased with the inhibitor concentration rising. A good fit to Flory-Huggins isotherm was obtained between surface coverage degree and inhibitor concentration. The surface morphology and EDS analysis for mild steel specimens in sulfuric acid in the absence and presence of the inhibitor also proved the results obtained by the weight loss and electrochemical experiments. The correlation of inhibition effect and molecular structure of berberine was then discussed by quantum chemistry study.

  6. Modeling impacts of NH3 on uptake of H2SO4 by charged nucleating nanoparticles in the Earth's atmosphere

    NASA Astrophysics Data System (ADS)

    Nadykto, A. B.; Nazarenko, K. M.; Markov, P. N.; Yu, F.

    2016-06-01

    The understanding of the role of ammonia, a well-known stabilizer of binary sulfuric acid-water clusters, in the gas-to-nanoparticle conversion in the Earth atmosphere is critically important for the assessment of aerosol radiative forcing associated with the climate changes. The sulfuric acid H2SO4 is present in the atmosphere in the form of the gas-phase hydrates (H2SO4)(H2O)n, whose interaction with NH3 leads to the formation of more stable bisulfate clusters (NH3)(H2SO4)(H2O)n. Although the impact of NH3 on the thermochemical stability of binary clusters nucleating homogeneously has been studied in some detail in the past, the effect of ammonia on other microphysical properties relevant to nucleation remains insufficiently well understood. In the present study, the effect of ammonia on the electrical dipole moment controlling the nucleation of airborne ions via the dipole-charge interaction has been investigated using the Density Functional Theory (DFT), ab initio MP2 and model chemistry G3 methods. The presence of ammonia in (H2SO4)(H2O)n is found to lead to very large enhancement in the dipole moment, which exceeds 2.0-2.5 Debyes (˜60-80%), 3.7-5.0 Debyes (˜90-180%), 1.4-4.5 Debyes (˜50-150%) and 2.1-5.5 Debyes (˜60-700%) for n = 0, n = 1, n = 2 and n = 3, respectively. The implications of this include the significantly increased uptake of the sulfuric acid, the key atmospheric nucleation precursor, by airborne ions and neutrals (due to dipole-dipole interaction), enhanced nucleation rates and the elevated production of ultrafine particles, which cause adverse health impacts.

  7. Melting of H2SO4·4H2O Particles upon Cooling: Implications for Polar Stratospheric Clouds

    PubMed

    Koop; Carslaw

    1996-06-14

    Polar stratospheric clouds (PSCs) are important for the chemical activation of chlorine compounds and subsequent ozone depletion. Solid PSCs can form on sulfuric acid tetrahydrate (SAT) (H2SO4·4H2O) nuclei, but recent laboratory experiments have shown that PSC nucleation on SAT is strongly hindered. A PSC formation mechanism is proposed in which SAT particles melt upon cooling in the presence of HNO3 to form liquid HNO3-H2SO4-H2O droplets 2 to 3 kelvin above the ice frost point. This mechanism offers a PSC formation temperature that is defined by the ambient conditions and sets a temperature limit below which PSCs should form.

  8. Knowledge of the systems H2O-SO3-N2O3. Report 1: The system H2SO4-H2O-N2O3

    NASA Technical Reports Server (NTRS)

    Stopperka, K.; Kilz, F.

    1977-01-01

    The amount of N2O3 being absorbed in 50-100% H2SO4 at 19, 60, and 95 C is directly proportional to the acid concentration and inversely proportional to the temperature. NO+ formation according to the above-formulated equation occurs only at H2SO4 concentrations greater than 52%. Absorption in highly concentrated sulfuric acid results in the formation of crystalline NOHSO4.

  9. Dissolution of Olivine, Siderite, and Basalt at 80 Deg C in 0.1 M H2SO4 in a Flow Through Process: Insights into Acidic Weathering on Mars

    NASA Technical Reports Server (NTRS)

    Golden, D. C.; Ming, D. W.; Hausrath, E. M.; Morris, R. V.; Niles, P. B.; Achilles, C. N.; Ross, D. K.; Cooper, B. L.; Gonzalex, C. P.; Mertzman, S. A.

    2012-01-01

    The occurrence of jarosite, other sulfates (e.g., Mg-and Ca-sulfates), and hematite along with silicic-lastic materials in outcrops of sedimentary materials at Meridiani Planum (MP) and detection of silica rich deposits in Gusev crater, Mars, are strong indicators of local acidic aqueous processes [1,2,3,4,5]. The formation of sediments at Meridiani Planum may have involved the evaporation of fluids derived from acid weathering of Martian basalts and subsequent diagenesis [6,7]. Also, our previous work on acid weathering of basaltic materials in a closed hydro-thermal system was focused on the mineralogy of the acid weathering products including the formation of jarosite and gray hematite spherules [8,9,10]. The object of this re-search is to extend our earlier qualitative work on acidic weathering of rocks to determine acidic dissolution rates of Mars analog basaltic materials at 80 C using a flow-thru reactor. We also characterized residual phases, including poorly crystalline or amorphous phases and precipitates, that remained after the treatments of olivine, siderite, and basalt which represent likely MP source rocks. This study is a stepping stone for a future simulation of the formation of MP rocks under a range of T and P.

  10. 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.

  11. Enhancement of bio-oil production via pyrolysis of wood biomass by pretreatment with H2SO4.

    PubMed

    Kumagai, Shogo; Matsuno, Ryo; Grause, Guido; Kameda, Tomohito; Yoshioka, Toshiaki

    2015-02-01

    In this work, a Japanese cedar wood sample was treated during the first step at ambient temperature and atmospheric pressure using several concentrations of sulfuric acid (H2SO4) in a stirred flask. During this pretreatment C-O bonds of cellulose, hemicellulose, and lignin were cleaved. The second step involved the pyrolysis of the pretreated wood sample at 550 °C in a quartz glass tube reactor. A maximum oil yield of 46.8 wt% with the minimum char yield of 10.1 wt% was obtained by the treatment with 3 M H2SO4, whereas untreated wood samples resulted in a 30.1 wt% yield of oil. The main components in the oils were levoglucosan and tar. These results suggest that moderate acid pretreatment produced shorter chain units of cellulose, hemicellulose, and lignin, thereby facilitating the conversion into oil by pyrolysis. The results of thermogravimetry-mass spectroscopy supported the presence of shorter chain units in the pretreated wood samples.

  12. Enhancement of bio-oil production via pyrolysis of wood biomass by pretreatment with H2SO4.

    PubMed

    Kumagai, Shogo; Matsuno, Ryo; Grause, Guido; Kameda, Tomohito; Yoshioka, Toshiaki

    2015-02-01

    In this work, a Japanese cedar wood sample was treated during the first step at ambient temperature and atmospheric pressure using several concentrations of sulfuric acid (H2SO4) in a stirred flask. During this pretreatment C-O bonds of cellulose, hemicellulose, and lignin were cleaved. The second step involved the pyrolysis of the pretreated wood sample at 550 °C in a quartz glass tube reactor. A maximum oil yield of 46.8 wt% with the minimum char yield of 10.1 wt% was obtained by the treatment with 3 M H2SO4, whereas untreated wood samples resulted in a 30.1 wt% yield of oil. The main components in the oils were levoglucosan and tar. These results suggest that moderate acid pretreatment produced shorter chain units of cellulose, hemicellulose, and lignin, thereby facilitating the conversion into oil by pyrolysis. The results of thermogravimetry-mass spectroscopy supported the presence of shorter chain units in the pretreated wood samples. PMID:25451777

  13. Morphological modification of MWCNT functionalized with HNO3/H2SO4 mixtures.

    PubMed

    Pistone, A; Ferlazzo, A; Lanza, M; Milone, C; Iannazzo, D; Piperno, A; Piperopoulos, E; Galvagno, S

    2012-06-01

    The acidic oxidation with HNO3/H2SO4 mixtures is widely reported as an effective method to functionalize multi-walled carbon nanotubes (MWCNT). Although effective, a bad control of the oxidation conditions frequently cause serious modifications of carbon nanotube network, limiting further potential applications. Investigations about the effect of functionalization operating conditions on the morphological, chemical and chemical-physical properties of MWCNT can be useful for a proper setting of oxidation reactions of MWCNT according to their specific applications. In this work the effect of HNO3/H2SO4 ratio on the morphological and chemical-physical properties and on the degree of functionalization of MWCNT was investigated. Electron microscopy, thermogravimetric, X-ray diffraction, titration and water dispersion analyses clearly revealed that the increase of the amount of concentrated sulphuric acid in the HNO3/H2SO4 mixture lead to an increase of the amount of functional groups on the MWCNT surface but also to an increase of structural damage in terms of tube cutting and generation of additional defects in the graphitic network of pristine PMID:22905576

  14. Measurement of OH, H2SO4, MSA, and HNO3 Aboard the P-3B Aircraft

    NASA Technical Reports Server (NTRS)

    Eisele, F. L.

    2003-01-01

    This paper addresses the measurement of OH, H2SO4, MSA, and HNO3 aboard the P-3B aircraft under the following headings: 1) Performance Report; 2) Highlights of OH, H2SO4, and MSA Measurements Made Aboard the NASA P-3B During TRACE-P; 3) Development and characteristics of an airborne-based instrument used to measure nitric acid during the NASA TRACE-P field experiment.

  15. Competition Between H2SO4(-)(CH3)3N and H2SO4-H2O Interactions: Theoretical Studies on the Clusters [(CH3)3N]·(H2SO4)·(H2O)(3-7).

    PubMed

    Xu, Zhen-Zhen; Fan, Hong-Jun

    2015-08-27

    The role of the nucleation of sulfuric acid with amines in aerosol formation and its implications for environment is one of the fundamental unsettled questions in atmospheric chemistry. We have investigated the cluster of [(CH3)3N]·(H2SO4)·(H2O)n (n = 3–7) by molecular dynamics to obtain configurational sampling combination with CAM-B3LYP/6-311G(d,p) level to locate the global and many local minima for each cluster size. According to the binding energies at the method of MP2/6-311++G(d,p), the total binding energies decrease with the increasing of the water molecules. For each global minimum, the average binding energies decrease from n = 3 to 4, then increase slowly. The protons of H2SO4 are preferred to transfer to the (CH3)3N to form ion-pair HSO4(–) and (CH3)3NH(+), and the (CH3)3NH(+) ions are coordinated at the first hydrated shell of HSO4(–) when n is between 3 and 5 and coordinated at the second or third hydrated shell when n is larger than 5.

  16. An Experimental Study of Atmospheric Homogeneous Nucleation: Cluster Growth and Gas-Particle Reactions of H2SO4

    NASA Technical Reports Server (NTRS)

    Eisele, F. L.

    1996-01-01

    The work proposed on this project included both field and laboratory studies. The laboratory studies were to consist of measurements of H2SO4 uptake and evaporation from aerosols of varying chemical composition, while the field component would include measurements of H2SO4 and other compounds which would be conducted as part of a large field campaign. By chance, the opportunity to conduct such an H2SO4/aerosol/ultrafine particle study in conjunction with an OH intercomparison/photochemistry study became available very early in this project (September 1993). This study was conducted at Caribou, Colorado in conjunction with several other groups from NCAR, NOAA and a number of universities. Our group measured OH, H2SO4, SO2, and H20, while Dr. McMurfy's group measured ultrafine particles, and total particle number and size distribution. In addition measurements of HO2/RO2, O3, NO, NO2, NO(y) CO, hydrocarbons, CH2O, and other chemical compounds and meteorological parameters were performed by the other participants and a new laser oblation/mass spectrometry technique was also employed by the NOAA Aeronomy Laboratory to study aerosol composition. The study of aerosol production and growth in conjunction with photochemical measurements is highly advantageous because particle growth precursors such as H2SO4.or MSA are formed by OH initiated sulfur oxidation. The large number of hydrocarbon measurements included in this study were also important in understanding particle growth.

  17. Heterogeneous Uptake and Conversion of HOBr on H2SO4 at Upper Tropospheric and Stratospheric Temperatures (255 - 210 K)

    NASA Technical Reports Server (NTRS)

    Iraci, Laura T.; Ashbourn, Samantha F. M.; Rammer, Thomas A.; Golden, David M.; Hipskind, R. Stephen (Technical Monitor)

    2001-01-01

    Halogen species are known to catalytically destroy ozone in several different regions of the atmosphere. In addition to directly destroying ozone, bromine compounds can indirectly enhance ozone loss through coupling to other radical families. Hypobromous acid (HOBr), a key species in the linkage of BrOx to ClOx and HOx, is produced by the hydrolysis of BrONO2 on sulfate aerosols, and thus the heterogeneous behavior of HOBr must be understood. We have measured the solubility of HOBr in 45 to 70 percent by weight sulfuric acid solutions. Over the temperature range 208 to 255 K, HOBr is very soluble in sulfuric acid, H(*) = 10(exp 4) to 10(exp 8) M/atm. The solubility is temperature dependent, and our results agree well with those of Waschewsky and Abbott for 60 percent by weight H2SO4. HOBr is nearly as soluble as HBr, indicating that equilibrium concentrations of HOBr could approach those of HBr in sulfuric acid aerosols. Despite the high solubility of HOBr, stratospheric aerosol volumes are not large enough to sequester a significant fraction of inorganic bromine from the gas phase. Uptake of HOBr was nearly always accompanied by reaction, producing Br2O and possibly Br2. The effect of this bromine conversion pathway on the HOx and ClOx families, particularly at temperatures as warm as 255 K, will be considered.

  18. 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),...

  19. 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),...

  20. 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),...

  1. 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),...

  2. 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,...

  3. Oxidation of electrodeposited lead-tin alloys in 5 M H 2SO 4

    NASA Astrophysics Data System (ADS)

    Petersson, I.; Ahlberg, E.

    By electroplating lead-tin alloys on a lightweight substrate material, such as glassy carbon, it is possible to obtain less dense electrodes with good contact between the active material and the substrate. The former is especially important for the lead-acid battery since it has relatively low energy density compared to many other battery systems. In order to obtain higher power densities for applications in, for example, electric or hybrid vehicles, the weight of the battery needs to be minimised. In the present investigation, the oxidation of electrodeposited lead-tin alloys in 5 M H 2SO 4 was studied as a function of tin concentration. The alloys were prepared by electrodeposition and the oxidation behaviour was studied by the means of cyclic voltammetry. Microstructural information on the deposited layer was obtained by scanning electron microscopy (SEM). The experimental results show that electrodeposited lead-tin alloys contain a supersaturated solid solution phase with up to 12 at.% Sn. Oxidation of this phase in 5 M H 2SO 4 leads to the formation of a PbO phase with increased conductivity compared to pure PbO. In addition, the amounts of PbO and PbO 2 decrease with increasing amounts of tin in the alloy and for high tin alloys, where a bulk tin phase is present, no PbO phase is observed.

  4. Calculation of composition distribution of ultrafine ion-H2O-H2SO4 clusters using a modified binary ion nucleation theory

    NASA Technical Reports Server (NTRS)

    Singh, J. J.; Smith, A. S.; Chan, L. Y.; Yue, G. K.

    1982-01-01

    Thomson's ion nucleation theory was modified to include the effects of curvature dependence of the microscopic surface tension of field dependent, nonlinear, dielectric properties of the liquid; and of sulfuric acid hydrate formation in binary mixtures of water and sulfuric acid vapors. The modified theory leads to a broadening of the ion cluster spectrum, and shifts it towards larger numbers of H2O and H2SO4 molecules. Whether there is more shifting towards larger numbers of H2O or H2SO4 molecules depends on the relative humidity and relative acidity of the mixture. Usually, a broadening of the spectrum is accompanied by a lowering of the mean cluster intensity. For fixed values of relative humidity and relative acidity, a similar broadening pattern is observed when the temperature is lowered. These features of the modified theory illustrate that a trace of sulfuric acid can facilitate the formation of ultrafine, stable, prenucleation ion clusters as well as the growth of the prenucleation ion clusters towards the critical saddle point conditions, even with low values of relative humidity and relative acidity.

  5. 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.

  6. Enhancement of atmospheric H2SO4 / H2O nucleation: organic oxidation products versus amines

    NASA Astrophysics Data System (ADS)

    Berndt, T.; Sipilä, M.; Stratmann, F.; Petäjä, T.; Vanhanen, J.; Mikkilä, J.; Patokoski, J.; Taipale, R.; Mauldin, R. L., III; Kulmala, M.

    2014-01-01

    Atmospheric H2SO4 / H2O nucleation influencing effects have been studied in the flow tube IfT-LFT (Institute for Tropospheric Research - Laminar Flow Tube) at 293 ± 0.5 K and a pressure of 1 bar using synthetic air as the carrier gas. The presence of a possible background amine concentration in the order of 107-108 molecule cm-3 throughout the experiments has to be taken into account. In a first set of investigations, ozonolysis of olefins (tetramethylethylene, 1-methyl-cyclohexene, α-pinene and limonene) for close to atmospheric concentrations, served as the source of OH radicals and possibly other oxidants initiating H2SO4 formation starting from SO2. The oxidant generation is inevitably associated with the formation of organic oxidation products arising from the parent olefins. These products (first generation mainly) showed no clear effect on the number of nucleated particles within a wide range of experimental conditions for H2SO4 concentrations higher than ~107 molecule cm-3. Also the early growth process of the nucleated particles was not significantly influenced by the organic oxidation products in line with the expected growth by organic products using literature data. An additional, H2SO4-independent process of particle (nano-CN) formation was observed in the case of α-pinene and limonene ozonolysis for H2SO4 concentrations smaller than ~107 molecule cm-3. Furthermore, the findings confirm the appearance of an additional oxidant for SO2 beside OH radicals, very likely stabilized Criegee Intermediates (sCI). A second set of experiments has been performed in the presence of added amines in the concentrations range of a few 107-1010 molecule cm-3 applying photolytic OH radical generation for H2SO4 production without addition of other organics. All amines showed significant nucleation enhancement with increasing efficiency in the order pyridine < aniline < dimethylamine < trimethylamine. This result supports the idea of H2SO4 cluster stabilization by

  7. 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.

  8. SiO2/H2SO4: An Efficient Catalytic System for Solvent-free 1, 5-benzodiazepines Synthesis

    PubMed Central

    Shushizadeh, Mohammad Reza; Dalband, Narges

    2012-01-01

    Background 1, 5-Benzodiazepines have been investigated extensively by organic chemists due to their medicinal and pharmacological properties. These compounds are synthesized by condensation of o-phenylenediamines with carbonyl compounds in the presence of acid catalysts. Objectives During our studies on the application of silica resin with acid functional moieties, we found that SiO2/H2SO4 mixture is a simple and efficient catalyst for this method under microwave irradiation. Materials and Methods The reaction was carried out simply by grinding SiO2/H2SO4 mixture with o-phenylenediamine, and ketone in the mortar; then the mixture was poured out into a sealed flask. Subsequently, it was irradiated in a microwave oven. Results In this method a series of cyclic and acyclic ketones underwent above conversion to form corresponding 1, 5-benzodiazepines. Conclusions In conclusion, this method is a simple, rapid, and high yielding reaction (78–95%). PMID:24624156

  9. Enhancement of atmospheric H2SO4/H2O nucleation: organic oxidation products versus amines

    NASA Astrophysics Data System (ADS)

    Berndt, T.; Sipilä, M.; Stratmann, F.; Petäjä, T.; Vanhanen, J.; Mikkilä, J.; Patokoski, J.; Taipale, R.; Mauldin, R. Lee, III; Kulmala, M.

    2013-06-01

    Atmospheric H2SO4/H2O nucleation influencing effects have been studied in the flow tube IfT-LFT (Institute for Tropospheric Research - Laminar Flow Tube) at 293 ± 0.5 K and a pressure of 1 bar using synthetic air as the carrier gas. The presence of a~possible background amine concentration in the order of 107-108 molecule cm-3 throughout the experiments has to be taken into account. In a first set of investigations, ozonolysis of olefins (tetramethylethylene, 1-methyl-cyclohexene, α-pinene and limonene) for close to atmospheric concentrations, served as the source of OH radicals and possibly other oxidants initiating H2SO4 formation starting from SO2. The oxidant generation is inevitably associated with the formation of a series of organic oxidation products arising from the parent olefins. These products (first generation mainly) showed no clear effect on the number of nucleated particles within a wide range of experimental conditions for H2SO4 concentrations higher than ~107 molecule cm-3. A comparison of the results of two different particle counters (50% cut-off size: about 1.5 nm or 2.5-3 nm) suggested that the early growth process of the nucleated particles was not significantly influenced by the organic oxidation products. An additional, H2SO4-independent process of particle (nano-CN) formation was observed in the case of α-pinene and limonene ozonolysis for H2SO4 concentrations smaller than ~10 7 molecule cm-3. Furthermore, the findings confirm the existence of an additional oxidant for SO2 beside OH radicals, very likely stabilized Criegee Intermediate (sCI). In the case of the ozonolysis of tetramethylethylene, the H2SO4 measurements in the absence and presence of an OH radical scavenger were well described by modelling using recently obtained kinetic data for the sCI reactivity in this system. A second set of experiments has been performed in the presence of added amines (trimethylamine, dimethylamine, aniline and pyridine) in the concentration range

  10. Optimization of H2SO4-catalyzed hydrothermal pretreatment of rapeseed straw for bioconversion to ethanol: focusing on pretreatment at high solids content.

    PubMed

    Lu, Xuebin; Zhang, Yimin; Angelidaki, Irini

    2009-06-01

    A central composite design of response surface method was used to optimize H(2)SO(4)-catalyzed hydrothermal pretreatment of rapeseed straw, in respect to acid concentration (0.5-2%), treatment time (5-20 min) and solid content (10-20%) at 180 degrees C. Enzymatic hydrolysis and fermentation were also measured to evaluate the optimal pretreatment conditions for maximizing ethanol production. The results showed that acid concentration and treatment time were more significant than solid content for optimization of xylose release and cellulose recovery. Pretreatment with 1% sulfuric acid and 20% solid content for 10 min at 180 degrees C was found to be the most optimal condition for pretreatment of rapeseed straw for ethanol production. After pretreatment at the optimal condition and enzymatic hydrolysis, 75.12% total xylan and 63.17% total glucan were converted to xylose and glucose, respectively. Finally, 66.79% of theoretical ethanol yielded after fermentation.

  11. Physical Chemistry of the H2SO4/HNO3/H2O System: Implications for Polar Stratospheric Clouds.

    PubMed

    Molina, M J; Zhang, R; Wooldridge, P J; McMahon, J R; Kim, J E; Chang, H Y; Beyer, K D

    1993-09-10

    Polar stratospheric clouds (PSCs) play a key role in stratospheric ozone depletion. Surface-catalyzed reactions on PSC particles generate chlorine compounds that photolyze readily to yield chlorine radicals, which in turn destroy ozone very efficiently. The most prevalent PSCs form at temperatures several degrees above the ice frost point and are believed to consist of HNO(3) hydrates; however, their formation mechanism is unclear. Results of laboratory experiments are presented which indicate that the background stratospheric H(2)SO(4)/H(2)O aerosols provide an essential link in this mechanism: These liquid aerosols absorb significant amounts of HNO(3) vapor, leading most likely to the crystallization of nitric acid trihydrate (NAT). The frozen particles then grow to form PSCs by condensation of additional amounts of HNO(3) and H(2)O vapor. Furthermore, reaction probability measurements reveal that the chlorine radical precursors are formed readily at polar stratospheric temperatures not just on NAT and ice crystals, but also on liquid H(2)SO(4) solutions and on solid H(2)SO(4) hydrates. These results imply that the chlorine activation efficiency of the aerosol particles increases rapidly as the temperature approaches the ice frost point regardless of the phase or composition of the particles. PMID:17745351

  12. Physical Chemistry of the H2SO4/HNO3/H2O System: Implications for Polar Stratospheric Clouds.

    PubMed

    Molina, M J; Zhang, R; Wooldridge, P J; McMahon, J R; Kim, J E; Chang, H Y; Beyer, K D

    1993-09-10

    Polar stratospheric clouds (PSCs) play a key role in stratospheric ozone depletion. Surface-catalyzed reactions on PSC particles generate chlorine compounds that photolyze readily to yield chlorine radicals, which in turn destroy ozone very efficiently. The most prevalent PSCs form at temperatures several degrees above the ice frost point and are believed to consist of HNO(3) hydrates; however, their formation mechanism is unclear. Results of laboratory experiments are presented which indicate that the background stratospheric H(2)SO(4)/H(2)O aerosols provide an essential link in this mechanism: These liquid aerosols absorb significant amounts of HNO(3) vapor, leading most likely to the crystallization of nitric acid trihydrate (NAT). The frozen particles then grow to form PSCs by condensation of additional amounts of HNO(3) and H(2)O vapor. Furthermore, reaction probability measurements reveal that the chlorine radical precursors are formed readily at polar stratospheric temperatures not just on NAT and ice crystals, but also on liquid H(2)SO(4) solutions and on solid H(2)SO(4) hydrates. These results imply that the chlorine activation efficiency of the aerosol particles increases rapidly as the temperature approaches the ice frost point regardless of the phase or composition of the particles.

  13. Physical chemistry of the H2SO4/HNO3/H2O system - Implications for polar stratospheric clouds

    NASA Technical Reports Server (NTRS)

    Molina, M. J.; Zhang, R.; Wooldridge, P. J.; Mcmahon, J. R.; Kim, J. E.; Chang, H. Y.; Beyer, K. D.

    1993-01-01

    Polar stratospheric clouds (PSCs) play a key role in stratospheric ozone depletion. Surface-catalyzed reactions on PSC particles generate chlorine compounds that photolyze readily to yield chlorine radicals, which in turn destroy ozone very efficiently. The most prevalent PSCs form at temperatures several degrees above the ice frost point and are believed to consist of HNO3 hydrates; however, their formation mechanism is unclear. Results of laboratory experiments are presented which indicate that the background stratospheric H2SO4/H2O aerosols provide an essential link in this mechanism: These liquid aerosols absorb significant amounts of HNO3 vapor, leading most likely to the crystallization of nitric acid trihydrate (NAT). The frozen particles then grow to form PSCs by condensation of additional amounts of HNO3 and H2O vapor. Furthermore, reaction probability measurements reveal that the chlorine radical precursors are formed readily at polar stratospheric temperatures not just on NAT and ice crystals, but also on liquid H2SO4 solutions and on solid H2SO4 hydrates. These results imply that the chlorine activation efficiency of the aerosol particles increases rapidly as the temperature approaches the ice frost point regardless of the phase or composition of the particles.

  14. Freezing temperatures of H2SO4/HNO3/H2O mixtures: Implications for polar stratospheric clouds

    NASA Technical Reports Server (NTRS)

    Song, Naihui

    1994-01-01

    The freezing temperatures of H2SO4/HNO3/H2O mixtures were systematically documented. Nitric acid was found to affect freezing significantly. Measurements show that nitric acid can cause substantial supercooling over a broad composition range. However, some ternary compositions, like to those in polar stratospheric clouds (PSCs), have high freezing temperatures. The freezing of PSC particles could be controlled by the temperature and vapor pressure of both nitric acid and water in a non-linear way. Formation of polar stratospheric clouds may be forecasted on the basic of conditions of temperature and vapor contents of water and nitric acid.

  15. Formation of low-temperature cirrus from H2SO4/H2O aerosol droplets.

    PubMed

    Bogdan, A; Molina, M J; Sassen, K; Kulmala, M

    2006-11-23

    We present experimental results obtained with a differential scanning calorimeter (DSC) that indicate the small ice particles in low-temperature cirrus clouds are not completely solid but rather coated with an unfrozen H2SO4/H2O overlayer. Our results provide a new look on the formation, development, and microphysical properties of low-temperature cirrus clouds.

  16. 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.

  17. 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.

  18. Quantum chemical study of atmospheric aggregates: HCl•HNO3•H2SO4.

    PubMed

    Verdes, Marian; Paniagua, Miguel

    2014-06-01

    HCl, HNO3 and H2SO4 are implicated in atmospheric processes in areas such as polar stratospheric clouds in the stratosphere. Ternary complexes of HCl, HNO3 and H2SO4 were investigated by ab initio calculations at B3LYP level of theory with aug-cc-pVTZ and aug-cc-pVQZ basis sets, taking into account basis set superposition error (BSSE). The results were assessed in terms of structures (five hexagonal cyclic structures and two quasi-pentagonal cyclic structures), inter-monomeric parameters (all ternary complexes built three hydrogen bonds), energetics (seven minima obtained), infrared harmonic vibrational frequencies (red shifting of complexes from monomers), and relative stability of complexes, which were favorable when the temperature decreases under stratospheric conditions, from 298 K to 188 K, and in concrete, at 210 K, 195 K and 188 K. PMID:24844391

  19. Quantum chemical study of atmospheric aggregates: HCl•HNO3•H2SO4.

    PubMed

    Verdes, Marian; Paniagua, Miguel

    2014-06-01

    HCl, HNO3 and H2SO4 are implicated in atmospheric processes in areas such as polar stratospheric clouds in the stratosphere. Ternary complexes of HCl, HNO3 and H2SO4 were investigated by ab initio calculations at B3LYP level of theory with aug-cc-pVTZ and aug-cc-pVQZ basis sets, taking into account basis set superposition error (BSSE). The results were assessed in terms of structures (five hexagonal cyclic structures and two quasi-pentagonal cyclic structures), inter-monomeric parameters (all ternary complexes built three hydrogen bonds), energetics (seven minima obtained), infrared harmonic vibrational frequencies (red shifting of complexes from monomers), and relative stability of complexes, which were favorable when the temperature decreases under stratospheric conditions, from 298 K to 188 K, and in concrete, at 210 K, 195 K and 188 K.

  20. Electron Impact Ionization of SOx, NOx and H2 SO4 - The Aerosol Relevance

    NASA Astrophysics Data System (ADS)

    Vaishnav, B. G.; Patel, U. R.; Joshipura, K. N.; Pandya, S. H.

    2016-05-01

    This paper reports our theoretical studies on electron impact ionization of reactive molecules SOx, NOx (x = 1-3) and H2 SO4, at incident energies from threshold to 2000 eV. Motivation for this work derives from the relevance of these molecules in connection with atmospheric aerosols analysis through mass spectrometric studies and quantification of mass concentrations amongst the aerosol species. The ionization efficiency of a molecule is directly proportional to ionization cross section, which represents the efficiency on a per-molecule basis. Study of electron impact ionization cross sections of molecules, like H2 SO4, versus number of electrons in the molecule can lead to information about mass concentrations of aerosol species. We have employed in this work, the well-known spherical complex potential formalism (SCOP), which provides total elastic as well as inelastic cross sections, wherein the latter includes ionization cross sections. We have developed a method to extract ionization cross section from calculated inelastic cross section by introducing a ratio function, in a semi-empirical formalism known as CSP-ic method. For SOx and NOx targets single-centre scattering calculations are performed, while for H2 SO4, the additivity rule augmented with overlap or screening corrections, has been employed. The calculated cross sections are examined as functions of incident electron energy along with comparisons (theoretical or experimental) as available.

  1. Determination of traces of chloride and fluoride in H2SO4, H3PO4 and H3BO3 by in situ analyte distillation-ion chromatography.

    PubMed

    Thangavel, S; Dash, K; Dhavile, S M; Chaurasia, S C; Mukherjee, T

    2005-05-13

    A simple dual vessel in situ analyte distillation (IAD) system has been developed for suppressed ion chromatographic determination of chloride and fluoride ions in complex matrices. In IAD system, water vapours generated from the outer vessel reacts with sulfuric acid generating heat, thus favouring the quantitative distillation of chloride and fluoride within 30 min on water bath temperature (approximately 80 degrees C). The distilled analytes, as their respective acids in water, were directly injected into an ion-chromatograph. This newly developed method has been applied for analysis of trace impurities in H2SO4, H3PO4 and H3BO3. The detection limits for chloride is 8, 80 and 70ppb (w/w) for H2SO4, H3PO4 and H3BO3, respectively. For fluoride the detection limits are 6 and 60 ppb (w/w) for H2SO4 and H3PO4, respectively. The recovery of spikes for both the analytes ranged between 87 and 100%.

  2. Influence of H2SO4 and ferric iron on Cd bioleaching from spent Ni-Cd batteries.

    PubMed

    Velgosová, Oksana; Kaduková, Jana; Marcinčáková, Renáta; Palfy, Pavol; Trpčevská, Jarmila

    2013-02-01

    The paper is concerned with biohydrometallurgical methods of cadmium recovery from spent Ni-Cd batteries. Cd leaching efficiency from electrode material in different media (H(2)SO(4) and Fe(2)(SO(4))(3) solutions), at different Fe(III) concentrations and using the bacteria Acidithiobacillus ferrooxidans were investigated. The main aim of this study was to understand which from the bioleaching products (sulphuric acid or ferric sulphate) play a main role in the bioleaching process of Cd recovery. The influence of Fe ions on Cd leachability was confirmed. The best leaching efficiency of Cd (100%) was reached by bioleaching and also by leaching in Fe(2)(SO(4))(3) solution. The results of X-ray diffraction confirmed that no cadmium was present in solid residuum obtained after the Cd bioleaching as well as Cd leaching using solely ferric iron. The use of H(2)SO(4) solution resulted in the lowest efficiency of Cd leachability, the presence of hydroxides in electrode materials caused neutralization of the leaching solution and inhibition of Cd leaching. PMID:23131752

  3. 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.

  4. Influence of Metal Oxides on Platinum Activity towards Methanol Oxidation in H2SO4 solution.

    PubMed

    Hameed, R M Abdel; Amin, R S; El-Khatib, K M; Fetohi, Amani E

    2016-04-01

    Pt-CeO2 /C, Pt-TiO2 /C, and Pt-ZrO2 /C electrocatalysts were prepared by using a modified microwave-assisted polyol process. Physical characterization was performed by using XRD, TEM, and EDX analyses. The incorporation of different metal oxides increased the dispersion degree of Pt nanoparticles and reduced their diameter to 2.50 and 2.33 nm when TiO2 and ZrO2 were introduced to Pt/C, respectively. The electrocatalytic activity of various electrocatalysts was examined towards methanol oxidation in H2 SO4 solution by using cyclic voltammetry, chronoamperometry, and electrochemical impedance spectroscopy. Among the studied composites, Pt-ZrO2 /C was selected to be a candidate electrocatalyst for better electrochemical performance in direct methanol fuel cells.

  5. On the composition of ammonia-sulfuric-acid ion clusters during aerosol particle formation

    NASA Astrophysics Data System (ADS)

    Schobesberger, S.; Franchin, A.; Bianchi, F.; Rondo, L.; Duplissy, J.; Kürten, A.; Ortega, I. K.; Metzger, A.; Schnitzhofer, R.; Almeida, J.; Amorim, A.; Dommen, J.; Dunne, E. M.; Ehn, M.; Gagné, S.; Ickes, L.; Junninen, H.; Hansel, A.; Kerminen, V.-M.; Kirkby, J.; Kupc, A.; Laaksonen, A.; Lehtipalo, K.; Mathot, S.; Onnela, A.; Petäjä, T.; Riccobono, F.; Santos, F. D.; Sipilä, M.; Tomé, A.; Tsagkogeorgas, G.; Viisanen, Y.; Wagner, P. E.; Wimmer, D.; Curtius, J.; Donahue, N. M.; Baltensperger, U.; Kulmala, M.; Worsnop, D. R.

    2015-01-01

    The formation of particles from precursor vapors is an important source of atmospheric aerosol. Research at the Cosmics Leaving OUtdoor Droplets (CLOUD) facility at CERN tries to elucidate which vapors are responsible for this new-particle formation, and how in detail it proceeds. Initial measurement campaigns at the CLOUD stainless-steel aerosol chamber focused on investigating particle formation from ammonia (NH3) and sulfuric acid (H2SO4). Experiments were conducted in the presence of water, ozone and sulfur dioxide. Contaminant trace gases were suppressed at the technological limit. For this study, we mapped out the compositions of small NH3-H2SO4 clusters over a wide range of atmospherically relevant environmental conditions. We covered [NH3] in the range from < 2 to 1400 pptv, [H2SO4] from 3.3 × 106 to 1.4 × 109 cm-3 (0.1 to 56 pptv), and a temperature range from -25 to +20 °C. Negatively and positively charged clusters were directly measured by an atmospheric pressure interface time-of-flight (APi-TOF) mass spectrometer, as they initially formed from gas-phase NH3 and H2SO4, and then grew to larger clusters containing more than 50 molecules of NH3 and H2SO4, corresponding to mobility-equivalent diameters greater than 2 nm. Water molecules evaporate from these clusters during sampling and are not observed. We found that the composition of the NH3-H2SO4 clusters is primarily determined by the ratio of gas-phase concentrations [NH3] / [H2SO4], as well as by temperature. Pure binary H2O-H2SO4 clusters (observed as clusters of only H2SO4) only form at [NH3] / [H2SO4] < 0.1 to 1. For larger values of [NH3] / [H2SO4], the composition of NH3-H2SO4 clusters was characterized by the number of NH3 molecules m added for each added H2SO4 molecule n (Δm/Δ n), where n is in the range 4-18 (negatively charged clusters) or 1-17 (positively charged clusters). For negatively charged clusters, Δ m/Δn saturated between 1 and 1.4 for [NH3] / [H2SO4] > 10. Positively

  6. On the composition of ammonia-sulfuric acid clusters during aerosol particle formation

    NASA Astrophysics Data System (ADS)

    Schobesberger, S.; Franchin, A.; Bianchi, F.; Rondo, L.; Duplissy, J.; Kürten, A.; Ortega, I. K.; Metzger, A.; Schnitzhofer, R.; Almeida, J.; Amorim, A.; Dommen, J.; Dunne, E. M.; Ehn, M.; Gagné, S.; Ickes, L.; Junninen, H.; Hansel, A.; Kerminen, V.-M.; Kirkby, J.; Kupc, A.; Laaksonen, A.; Lehtipalo, K.; Mathot, S.; Onnela, A.; Petäjä, T.; Riccobono, F.; Santos, F. D.; Sipilä, M.; Tomé, A.; Tsagkogeorgas, G.; Viisanen, Y.; Wagner, P. E.; Wimmer, D.; Curtius, J.; Donahue, N. M.; Baltensperger, U.; Kulmala, M.; Worsnop, D. R.

    2014-05-01

    The formation of particles from precursor vapors is an important source of atmospheric aerosol. Research at the Cosmics Leaving OUtdoor Droplets (CLOUD) facility at CERN tries to elucidate which vapors are responsible for this new particle formation, and how in detail it proceeds. Initial measurement campaigns at the CLOUD stainless-steel aerosol chamber focused on investigating particle formation from ammonia (NH3) and sulfuric acid (H2SO4). Experiments were conducted in the presence of water, ozone and sulfur dioxide. Contaminant trace gases were suppressed at the technological limit. For this study, we mapped out the compositions of small NH3-H2SO4 clusters over a wide range of atmospherically relevant environmental conditions. We covered [NH3] in the range from <2 to 1400 pptv, [H2SO4] from 3.3 × 106 to 1.4 × 109 cm-3, and a temperature range from -25 to +20 °C. Negatively and positively charged clusters were directly measured by an atmospheric pressure interface time-of-flight (APi-TOF) mass spectrometer, as they initially formed from gas-phase NH3 and H2SO4, and then grew to larger clusters containing more than 50 molecules of NH3 and H2SO4, corresponding to mobility-equivalent diameters greater than 2 nm. Water molecules evaporate from these clusters during sampling and are not observed. We found that the composition of the NH3-H2SO4 clusters is primarily determined by the ratio of gas-phase concentrations [NH3] / [H2SO4], as well as by temperature. Pure binary H2O-H2SO4 clusters (observed as clusters of only H2SO4) only form at [NH3] / [H2SO4]<0.1 to 1. For larger values of [NH3] / [H2SO4], the composition of NH3-H2SO4 clusters was characterized by the number of NH3 molecules m added for each added H2SO4 molecule n (Δm / Δn), where n is in the range 4-18 (negatively charged clusters) or 1-17 (positively charged clusters). For negatively charged clusters, Δm / Δn saturated between 1 and 1.4 for [NH3] / [H2SO4]>10. Positively charged clusters grew on

  7. H2O-mediated trimerization of H2SO4: A computational study and comparison with experimental data

    NASA Astrophysics Data System (ADS)

    Nadykto, A. B.; Nazarenko, K. M.; Jakovleva, M. V.; Uvarova, L. A.; Yu, F.

    2016-06-01

    In the present paper, the formation of stable hydrated (H2SO4)3(H2O)n clusters has been studied using the Density Functional Theory (DFT) at PW91PW91/6-311++(3df,3pd) level. We have found that the hydration of H2SO4 trimers is stronger than that of H2SO4 dimers and tends to decrease at large hydration numbers. We have shown that the affinity of H2SO4 to (H2SO4)2(H2O)n is much higher than that H2SO4 to (H2SO4) (H2O)n. We have compared the equilibrium constants of H2O-mediated trimerization of H2SO4 obtained using PW91PW91/6-311++(3df,3pd) method with experimental data and found that theory and experimentation are in good agreement. The new thermochemical data can be used in a wide range of nucleation studies and can be utilized for the development of quantum-based models of nucleation rates.

  8. Status of initial testing of the H2SO4 section of the ILS experiment.

    SciTech Connect

    Moore, Robert Charles; Parma, Edward J., Jr.; Gelbard, Fred

    2007-12-01

    A sulfuric acid catalytic decomposer section was assembled and tested for the Integrated Laboratory Scale experiments of the Sulfur-Iodine Thermochemical Cycle. This cycle is being studied as part of the U. S. Department of Energy Nuclear Hydrogen Initiative. Tests confirmed that the 54-inch long silicon carbide bayonet could produce in excess of the design objective of 100 liters/hr of SO{sub 2} at 2 bar. Furthermore, at 3 bar the system produced 135 liters/hr of SO{sub 2} with only 31 mol% acid. The gas production rate was close to the theoretical maximum determined by equilibrium, which indicates that the design provides adequate catalyst contact and heat transfer. Several design improvements were also implemented to greatly minimize leakage of SO{sub 2} out of the apparatus. The primary modifications were a separate additional enclosure within the skid enclosure, and replacement of Teflon tubing with glass-lined steel pipes.

  9. Relative stabilities of HCl•H2SO4•HNO3 aggregates in polar stratospheric clouds.

    PubMed

    Verdes, Marian; Paniagua, M

    2015-04-01

    Strong acids such as HCl (C), HNO3 (N) and H2SO4 (S) acquire relevance in Polar Stratospheric Clouds (PSCs) and aerosols in which nucleation processes occur. Ab initio quantum chemical studies of aggregates were performed for these strong acids. Structures were calculated using DFT methods with the B3LYP hybrid functional and aug-cc-pVTZ basis set. As an initial constraint, an H2SO4 moiety was placed in all candidate structures. A total of 11 optimized structures was found: a global minimum (CSN-a) plus ten local minima on the Potential Energy Surface (PES). The global minimum aggregate gave four hydrogen bonds, yielding a hexagonal ring in its structure. HNO3 acts as proton donor in all clusters; nevertheless, using trans-H2SO4 as the proton donor yielded the most stable structures, whereas HCl acts mainly as a proton donor/acceptor. Real harmonic frequencies, IR spectra, and inter-monomeric parameters were obtained. CSN-a symmetric stretching modes were shifted to 2805.56 cm(-1) and 3520.00 cm(-1) for H-Cl modes, while O-H modes shifted to 3256.87 cm(-1) and 3362.47 cm(-1). On the other hand, relative stabilities improved for 5 of the 11 aggregates when the temperature decreased from 298 K to 210 K, 195 K and 188 K. The aggregate CSN-f remained unstable only at 210 K. Moreover, the relative Gibbs free energy, ΔG(0-298K) was -9.26 kcalmol(-1) with respect to CSN-a; relative reaction Gibbs free energy [Δ(ΔG)] values ranged from 0.0 at 298 K, to -6.9 kcalmol(-1) at 188 K. It seems that CSN aggregates remain slightly more stable than CNS aggregates with a HNO3 moiety when the temperature decreases from 298 to 188 K. Five structures remained relatively stable under both study conditions.

  10. A Comprehensive Evaluation of H2SO4 formation from OH and sCI pathways in high BVOC environments

    NASA Astrophysics Data System (ADS)

    Kim, S.; Seco, R.; Park, J. H.; Guenther, A. B.; Smith, J. N.; Kuang, C.; Bustillos, J. O. V.; Tota, J.; Souza, R. A. F. D.

    2014-12-01

    The recently highlighted importance of stabilized Criegee intermediates (sCI) as an oxidant for atmospheric SO2 triggered a number of studies to assess the atmospheric implications of H2SO4 formation from the sCI reaction pathway. In addition, it has not been clear why new particle formation events are not observed in the Amazon rain forest. The mostly widely speculated reason has been a very low H2SO4 level. We will present quantitative assessments of SO2 oxidation by sCI leading to the H2SO4 production using a comprehensive observational dataset from a tropical rainforest study during the GOAmazon field campaign at the T3 site in Manacapuru, Amazonas, Brazil. To our best knowledge, this is the first observation of H2SO4 and OH in Amazon and is unique for all tropical sites due to the accompanying comprehensive gas and aerosol observations such as CO, NOX, SO2, VOCs, and physical and chemical characteristics of aerosols. We will discuss observed H2SO4 levels during the GOAmazon field campaigns to demonstrate 1) H2SO4 formation potential from OH and sCI oxidation pathways by contrasting extremely clean and relatively polluted air masses and 2) the Implications of the observed H2SO4 levels in new particle formation and particle growth events.

  11. Kinetics of Cerium(IV) Extraction from H(2)SO(4)-HF Medium with Cyanex 923.

    PubMed

    Liao, Wuping; Yu, Guihong; Yue, Shantang; Li, Deqian

    2002-03-11

    Studies of the extraction kinetics of cerium(IV) from H(2)SO(4)-HF solutions with Cyanex 923 in n-heptane have been carried out using a constant interfacial area cell with laminar flow. The experimental hydrodynamic conditions were chosen so that the contribution of diffusion to the measured rate of reaction was minimized. The data were analyzed in terms of pseudo-first order constants. The results were compared with those of the system without HF. It was concluded that the addition of HF reduces the activation energy for the forward rate from 46.2 to 36.5 kJ mol(-1) while it has an opposite effect on the activation energy for the reverse process(the activation energy increased from 23.3 to 90.8 kJ mol(-1)). Thus, HF can accelerate the rate of cerium(IV) extraction. At the same time, the extraction rate is controlled by a mixed chemical reaction-diffusion rather than by a chemical reaction alone. A rate equation has also been obtained.

  12. Surface modification with alumina blasting and H2SO4-HCl etching for bonding two resin-composite veneers to titanium.

    PubMed

    Taira, Yohsuke; Egoshi, Takafumi; Kamada, Kohji; Sawase, Takashi

    2014-02-01

    The purpose of this study was to investigate the effect of an experimental surface treatment with alumina blasting and acid etching on the bond strengths between each of two resin composites and commercially pure titanium. The titanium surface was blasted with alumina and then etched with 45wt% H2SO4 and 15wt% HCl (H2SO4-HCl). A light- and heat-curing resin composite (Estenia) and a light-curing resin composite (Ceramage) were used with adjunctive metal primers. Veneered specimens were subjected to thermal cycling between 4 and 60°C for 50,000 cycles, and the shear bond strengths were determined. The highest bond strengths were obtained for Blasting/H2SO4-HCl/Estenia (30.2 ± 4.5 MPa) and Blasting/Etching/Ceramage (26.0 ± 4.5 MPa), the values of which were not statistically different, followed by Blasting/No etching/Estenia (20.4 ± 2.4 MPa) and Blasting/No etching/Ceramage (0.8 ± 0.3 MPa). Scanning electron microscopy observations revealed that alumina blasting and H2SO4-HCl etching creates a number of micro- and nanoscale cavities on the titanium surface, which contribute to adhesive bonding. PMID:24372961

  13. Surface modification with alumina blasting and H2SO4-HCl etching for bonding two resin-composite veneers to titanium.

    PubMed

    Taira, Yohsuke; Egoshi, Takafumi; Kamada, Kohji; Sawase, Takashi

    2014-02-01

    The purpose of this study was to investigate the effect of an experimental surface treatment with alumina blasting and acid etching on the bond strengths between each of two resin composites and commercially pure titanium. The titanium surface was blasted with alumina and then etched with 45wt% H2SO4 and 15wt% HCl (H2SO4-HCl). A light- and heat-curing resin composite (Estenia) and a light-curing resin composite (Ceramage) were used with adjunctive metal primers. Veneered specimens were subjected to thermal cycling between 4 and 60°C for 50,000 cycles, and the shear bond strengths were determined. The highest bond strengths were obtained for Blasting/H2SO4-HCl/Estenia (30.2 ± 4.5 MPa) and Blasting/Etching/Ceramage (26.0 ± 4.5 MPa), the values of which were not statistically different, followed by Blasting/No etching/Estenia (20.4 ± 2.4 MPa) and Blasting/No etching/Ceramage (0.8 ± 0.3 MPa). Scanning electron microscopy observations revealed that alumina blasting and H2SO4-HCl etching creates a number of micro- and nanoscale cavities on the titanium surface, which contribute to adhesive bonding.

  14. Competitive reaction pathways in vibrationally induced photodissociation of H2SO4.

    PubMed

    Yosa Reyes, Juvenal; Nagy, Tibor; Meuwly, Markus

    2014-09-14

    Vibrationally induced photodissociation of sulfuric acid into H2O + SO3 is investigated based on reactive molecular dynamics (MD) simulations. Multisurface adiabatic reactive MD simulations allow us to follow both, H-transfer and water elimination after excitation of the ν9 OH-stretching mode. Analysis of several thousand trajectories finds that the H2O and SO3 fragments have distinct final state distributions with respect to translational, rotational, and vibrational degrees of freedom. Rotational distributions peak at quantum numbers j ≤ 5 for water and j ≈ 60 for SO3. The final state distributions should be useful in identifying products in forthcoming experiments. Based on the MD trajectories, a kinetic scheme has been developed which is able to explain most of the trajectory data and suggests that IVR is very rapid. Typical lifetimes of the excited complex range from several 10 picoseconds to hundreds of nanoseconds, depending on the excitation level. Including temperature and pressure profiles characteristic for the stratosphere in the kinetic model shows that excitations higher than ν9 = 4 can significantly contribute to the photolysis rate. This extends and specifies earlier work in that multi-level modeling is required to understand the significance of vibrationally induced decomposition pathways of sulfuric acid in the middle atmosphere. PMID:25072517

  15. Composition and freezing of aqueous H2SO4/HNO3 solutions under polar stratospheric conditions

    NASA Technical Reports Server (NTRS)

    Beyer, K. D.; Seago, S. W.; Chang, H. Y.; Molina, M. J.

    1994-01-01

    The results of laboratory investigations of the freezing behavior of aqueous acid solutions indicate that in the stratosphere H2SO/H2O aerosol droplets would not freeze at temperatures above the ice frost point in the absence of HNO3; however, in the presence of typical levels of HNO3 liquid sulfuric acid aerosols take up significant amounts of HNO3 and H2O vapors and freeze much more readily. This is a consequence of the very rapid change in composition of the liquid droplets as the temperature drops to within two to three degrees of the equilibrium temperature at which HNO3 and H2O vapors would co-condense to form a liquid solution. In the high latitude stratosphere this HNO3/H2O 'dew point' is typically around 192-194 K at 100 mbar.

  16. Characterization of direct methanol fuel cell (DMFC) applications with H 2SO 4 modified chitosan membrane

    NASA Astrophysics Data System (ADS)

    Osifo, Peter O.; Masala, Aluwani

    Chitosan (Chs) flakes were prepared from chitin materials that were extracted from the exoskeleton of Cape rock lobsters in South Africa. The Chs flakes were prepared into membranes and the Chs membranes were modified by cross-linking with H 2SO 4. The cross-linked Chs membranes were characterized for the application in direct methanol fuel cells. The Chs membrane characteristics such as water uptake, thermal stability, proton resistance and methanol permeability were compared to that of high performance conventional Nafion 117 membranes. Under the temperature range studied 20-60 °C, the membrane water uptake for Chs was found to be higher than that of Nafion. Thermal analysis revealed that Chs membranes could withstand temperature as high as 230 °C whereas Nafion 117 membranes were stable to 320 °C under nitrogen. Nafion 117 membranes were found to exhibit high proton resistance of 284 s cm -1 than Chs membranes of 204 s cm -1. The proton fluxes across the membranes were 2.73 mol cm -2 s -1 for Chs- and 1.12 mol cm -2 s -1 Nafion membranes. Methanol (MeOH) permeability through Chs membrane was less, 1.4 × 10 -6 cm 2 s -1 for Chs membranes and 3.9 × 10 -6 cm 2 s -1 for Nafion 117 membranes at 20 °C. Chs and Nafion membranes were fabricated into membrane electrode assemblies (MAE) and their performances measure in a free-breathing commercial single cell DMFC. The Nafion membranes showed a better performance as the power density determined for Nafion membranes of 0.0075 W cm -2 was 2.7 times higher than in the case of Chs MEA.

  17. Evaluation and Characterization of Membranes for H2SO4/Water and I2/HI/H2O Water Separation and Hydrogen Permeation for the S-I Cycle

    SciTech Connect

    Frederick R. Stewart

    2006-10-01

    In this report are the findings into three membrane separation studies for potential application to the Sulfur-Iodine (S-I) thermochemical cycle. The first is the removal of water from hydriodic acid/iodine mixtures. In the S-I cycle, iodine is added to the product of the Bunsen reaction to facilitate the separation of sulfuric acid (H2SO4) from hydriodic acid (HI). The amount of iodine can be as high as 83% of the overall mass load of the Bunsen product stream, which potentially introduces a large burden on the cycle’s efficiency. Removal of water from the HI and iodine mixture would substantially reduce the amount of required additional iodine. In this work, performance data for Nafion® and sulfonated poly (ether ether ketone) (SPEEK) membranes is shown.

  18. Macroscopic assembled, ultrastrong and H2SO4-resistant fibres of polymer-grafted graphene oxide

    PubMed Central

    Zhao, Xiaoli; Xu, Zhen; Zheng, Bingna; Gao, Chao

    2013-01-01

    Nacre realizes strength and toughness through hierarchical designs with primary “brick and mortar” structures of alternative arrangement of nanoplatelets and biomacromolecules, and these have inspired the fabrication of nanocomposites for decades. However, to simultaneously solve the three critical problems of phase separation, low interfacial strength and random orientation of nanofillers for nanocomposites is a great challenge yet. Here we demonstrate that polymer-grafted graphene oxide sheets are exceptional building blocks for nanocomposites. Their liquid crystalline dispersions can be wet-spun into continuous fibres. Because of well-ordering and efficient load transfer, the composites show remarkable tensile strength (500 MPa), three to four times higher than nacre. The uniform layered microstructures and strong interlayer interactions also endow the fibres good resistance to chemicals including 98% sulfuric acid. We studied the enhancing effect of nanofillers with fraction in a whole range (0–100%), and proposed an equation to depict the relationship. PMID:24196491

  19. Macroscopic assembled, ultrastrong and H2SO4-resistant fibres of polymer-grafted graphene oxide

    NASA Astrophysics Data System (ADS)

    Zhao, Xiaoli; Xu, Zhen; Zheng, Bingna; Gao, Chao

    2013-11-01

    Nacre realizes strength and toughness through hierarchical designs with primary ``brick and mortar'' structures of alternative arrangement of nanoplatelets and biomacromolecules, and these have inspired the fabrication of nanocomposites for decades. However, to simultaneously solve the three critical problems of phase separation, low interfacial strength and random orientation of nanofillers for nanocomposites is a great challenge yet. Here we demonstrate that polymer-grafted graphene oxide sheets are exceptional building blocks for nanocomposites. Their liquid crystalline dispersions can be wet-spun into continuous fibres. Because of well-ordering and efficient load transfer, the composites show remarkable tensile strength (500 MPa), three to four times higher than nacre. The uniform layered microstructures and strong interlayer interactions also endow the fibres good resistance to chemicals including 98% sulfuric acid. We studied the enhancing effect of nanofillers with fraction in a whole range (0-100%), and proposed an equation to depict the relationship.

  20. Ammonia removal from air stream and biogas by a H2SO4 impregnated adsorbent originating from waste wood-shavings and biosolids.

    PubMed

    Guo, Xuejun Jack; Tak, Jin Kwon; Johnson, Richard L

    2009-07-15

    A new and cost-effective adsorbent N-TRAP, made from waste wood-shavings and anaerobically digestion biosolids and impregnated with H(2)SO(4), was applied for the ammonia removal from air stream and biogas with high efficiency and effectiveness. Bearing a 75-80 and 65 wt.% sulfuric acid, the N-TRAPs mediated with wood shavings and biosolids showed the maximum ammonia adsorption capacity of 260-280 and 230 mg g(-1), respectively. Gas temperatures (20 and 60 degrees C) and moisture content (100% relative humidity) had no significantly negative effect on ammonia capture performance when temperature in the fixed-bed column was kept equalled to or slightly above the feed gas temperature. The pressure drop increased significantly when NH(3) began to break through the N-TRAP stripper due to the formation of ammonium sulfate blocking the vacuum space of packed adsorbent. At last, an alternative N-TRAP filter bed design was proposed to resolve the problem of pressure drop evolution.

  1. Aerosol chamber study of optical constants and N2O5 uptake on supercooled H2SO4/H2O/HNO3 solution droplets at polar stratospheric cloud temperatures.

    PubMed

    Wagner, Robert; Naumann, Karl-Heinz; Mangold, Alexander; Möhler, Ottmar; Saathoff, Harald; Schurath, Ulrich

    2005-09-15

    The mechanism of the formation of supercooled ternary H(2)SO(4)/H(2)O/HNO(3) solution (STS) droplets in the polar winter stratosphere, i.e., the uptake of nitric acid and water onto background sulfate aerosols at T < 195 K, was successfully mimicked during a simulation experiment at the large coolable aerosol chamber AIDA of Forschungszentrum Karlsruhe. Supercooled sulfuric acid droplets, acting as background aerosol, were added to the cooled AIDA vessel at T = 193.6 K, followed by the addition of ozone and nitrogen dioxide. N(2)O(5), the product of the gas phase reaction between O(3) and NO(2), was then hydrolyzed in the liquid phase with an uptake coefficient gamma(N(2)O(5)). From this experiment, a series of FTIR extinction spectra of STS droplets was obtained, covering a broad range of different STS compositions. This infrared spectra sequence was used for a quantitative test of the accuracy of published infrared optical constants for STS aerosols, needed, for example, as input in remote sensing applications. The present findings indicate that the implementation of a mixing rule approach, i.e., calculating the refractive indices of ternary H(2)SO(4)/H(2)O/HNO(3) solution droplets based on accurate reference data sets for the two binary H(2)SO(4)/H(2)O and HNO(3)/H(2)O systems, is justified. Additional model calculations revealed that the uptake coefficient gamma(N(2)O(5)) on STS aerosols strongly decreases with increasing nitrate concentration in the particles, demonstrating that this so-called nitrate effect, already well-established from uptake experiments conducted at room temperature, is also dominant at stratospheric temperatures.

  2. Aerosol chamber study of optical constants and N2O5 uptake on supercooled H2SO4/H2O/HNO3 solution droplets at polar stratospheric cloud temperatures.

    PubMed

    Wagner, Robert; Naumann, Karl-Heinz; Mangold, Alexander; Möhler, Ottmar; Saathoff, Harald; Schurath, Ulrich

    2005-09-15

    The mechanism of the formation of supercooled ternary H(2)SO(4)/H(2)O/HNO(3) solution (STS) droplets in the polar winter stratosphere, i.e., the uptake of nitric acid and water onto background sulfate aerosols at T < 195 K, was successfully mimicked during a simulation experiment at the large coolable aerosol chamber AIDA of Forschungszentrum Karlsruhe. Supercooled sulfuric acid droplets, acting as background aerosol, were added to the cooled AIDA vessel at T = 193.6 K, followed by the addition of ozone and nitrogen dioxide. N(2)O(5), the product of the gas phase reaction between O(3) and NO(2), was then hydrolyzed in the liquid phase with an uptake coefficient gamma(N(2)O(5)). From this experiment, a series of FTIR extinction spectra of STS droplets was obtained, covering a broad range of different STS compositions. This infrared spectra sequence was used for a quantitative test of the accuracy of published infrared optical constants for STS aerosols, needed, for example, as input in remote sensing applications. The present findings indicate that the implementation of a mixing rule approach, i.e., calculating the refractive indices of ternary H(2)SO(4)/H(2)O/HNO(3) solution droplets based on accurate reference data sets for the two binary H(2)SO(4)/H(2)O and HNO(3)/H(2)O systems, is justified. Additional model calculations revealed that the uptake coefficient gamma(N(2)O(5)) on STS aerosols strongly decreases with increasing nitrate concentration in the particles, demonstrating that this so-called nitrate effect, already well-established from uptake experiments conducted at room temperature, is also dominant at stratospheric temperatures. PMID:16834200

  3. A global three-dimensional model of the stratospheric sulfuric acid layer

    NASA Technical Reports Server (NTRS)

    Golombek, Amram; Prinn, Ronald G.

    1993-01-01

    A 3D model which encompasses SO2 production from OCS, followed by its oxidation to gaseous H2SO4, the condensation-evaporation equilibrium of gaseous and particulate H2SO4, and finally particle condensation and rainout, is presently used to study processes maintaining the nonvolcanically-perturbed stratosphere's sulfuric acid layer. A comparison of the results thus obtained with remotely sensed stratospheric aerosol extinction data shows the model to simulate the general behavior of stratospheric aerosol extinction.

  4. Opacity of monodisperse sulfuric acid aerosols

    NASA Astrophysics Data System (ADS)

    Pilat, Michael J.; Wilder, James M.

    The plume opacity and droplet diameters of a monodisperse sulfuric acid aerosol were calculated as a function of the initial H 2SO 4 concentration, initial H 2O concentration and final gas temperature after cooling from an original stack gas temperature of 300°C. Calculation assumptions include heterogeneous heteromolecular condensation of H 2SO 4 and H 2O onto monodisperse nuclei of 0.05 μm dia., three aerosol particle nuclei concentrations of 10 6, 10 7 and 10 8 cm -3 (at 300°C and 760 mm Hg); and a stack or plume diameter of 6 m. The calculated results show that for the conditions considered and with the stack temperatures in excess of 125°C, initial H 2SO 4 stack gas concentrations of 10ppm or less will result in calculated opacities of less than 20 % for a plume diameter of 6 m. The results show that the calculated opacity is significantly affected by the initial H 2SO 4 and initial H 2O concentrations and the final gas temperature. The increases in the calculated opacities upon cooling of the stack gases are similar in general to the increases in the measured opacities between instack and outstack reported by Nader and Conner (1978) for an oil-fired boiler.

  5. The reactions of SO3 with HO2 radical and H2O...HO2 radical complex. Theoretical study on the atmospheric formation of HSO5 and H2SO4.

    PubMed

    Gonzalez, Javier; Torrent-Sucarrat, Miquel; Anglada, Josep M

    2010-03-01

    The influence of a single water molecule on the gas-phase reactivity of the HO(2) radical has been investigated by studying the reactions of SO(3) with the HO(2) radical and with the H(2)O...HO(2) radical complex. The naked reaction leads to the formation of the HSO(5) radical, with a computed binding energy of 13.81 kcal mol(-1). The reaction with the H(2)O...HO(2) radical complex can give two different products, namely (a) HSO(5) + H(2)O, which has a binding energy that is computed to be 4.76 kcal mol(-1) more stable than the SO(3) + H(2)O...HO(2) reactants (Delta(E + ZPE) at 0K) and an estimated branching ratio of about 34% at 298K and (b) sulfuric acid and the hydroperoxyl radical, which is computed to be 10.51 kcal mol(-1) below the energy of the reactants (Delta(E + ZPE) at 0K), with an estimated branching ratio of about 66% at 298K. The fact that one of the products is H(2)SO(4) may have relevance in the chemistry of the atmosphere. Interestingly, the water molecule acts as a catalyst, [as it occurs in (a)] or as a reactant [as it occurs in (b)]. For a sake of completeness we have also calculated the anharmonic vibrational frequencies for HO(2), HSO(5), the HSO(5)...H(2)O hydrogen bonded complex, H(2)SO(4), and two H(2)SO(4)...H(2)O complexes, in order to help with the possible experimental identification of some of these species. PMID:20165760

  6. Sulfuric acid aerosol exposure in humans assessed by bronchoalveolar lavage

    SciTech Connect

    Frampton, M.W.; Voter, K.Z.; Morrow, P.E.; Roberts, N.J. Jr.; Culp, D.J.; Cox, C.; Utell, M.J. )

    1992-09-01

    Epidemiologic and experimental evidence suggests that exposure to acidic aerosols may affect human health. Brief exposures to acidic aerosols alter mucociliary clearance and increase airway responsiveness, but effects on host defense mechanisms at the alveolar level have not been studied in humans. Twelve healthy, nonsmoking volunteers between 20 and 39 yr of age were exposed for 2 h to aerosols of approximately 1,000 micrograms/m3 sulfuric acid (H2SO4) or sodium chloride (NaCl (control)), with intermittent exercise, in a randomized, double-blind fashion. Each subject received both exposures, separated by at least 2 wk. Bronchoalveolar lavage (BAL) was performed 18 h after exposure in order to detect evidence of an inflammatory response, changes in alveolar cell subpopulations, or changes in alveolar macrophage (AM) function, which is important in host defense. When compared with NaCl, exposure to H2SO4 did not increase polymorphonuclear leukocytes in BAL fluid. The percentage of T lymphocytes decreased in association with H2SO4 exposure, but the difference was not statistically significant (14.9% after NaCl, 11.5% after H2SO4; p = 0.14). Antibody-mediated cytotoxicity of AM increased in association with H2SO4 exposure (percent lysis 19.1 after NaCl, 23.6 after H2SO4; p = 0.16). No significant change was seen in release of superoxide anion or inactivation of influenza virus in vitro. Brief exposures to H2SO4 aerosol at 1,000 micrograms/m3 do not cause an influx of inflammatory cells into the alveolar space, and no evidence was found for alteration in antimicrobial defense 18 h after exposure.

  7. Experimental study of cluster formation in binary mixture of H2O and H2SO4 vapors in the presence of an ionizing radiation source

    NASA Technical Reports Server (NTRS)

    Singh, J. J.; Smith, A. C.; Yue, G. K.

    1980-01-01

    Molecular clusters formed in pure nitrogen containing H2O and H2SO4 vapors and exposed to a 3 mCi Ni63 beta source were studied in the mass range 50 to 780 amu using a quadrupole mass spectrometer. Measurements were made under several combinations of relative humidity and relative acidity ranging from 0.7 to 7.5 percent and 0.00047 to 0.06333 percent, respectively. The number of H2SO4 molecules in the clusters observed ranged from 1 to 7 whereas the number of H2O molecules ranged from 1 to 16. The experimental cluster spectra differ considerably from those calculated using the classical nucleation theory. First order calculations using modified surface tension values and including the effects of multipole moments of the nucleating molecules indicate that these effects may be enough to explain the difference between the measured and the calculated spectra.

  8. CORROSION OF AMORPHOUS AND NANOCRYSTALLINE Fe-BASED ALLOYS IN NaCl AND H2SO4 SOLUTIONS

    NASA Astrophysics Data System (ADS)

    Li, Xiang; Lu, Wei; Wang, Yuxin; Yan, Biao; Pan, Deng

    2013-07-01

    Corrosion resistance of nanocrystalline Fe73.5Si13.5B9Nb3Cu1 alloy was investigated and compared to its amorphous counterpart. Low-temperature crystallization occurred during the annealing of amorphous tapes was used to obtain a nanocrystalline structure. The influence of annealing condition on the structure and corrosion resistance of the alloy in NaCl and H2SO4 solutions was investigated. Based on the testing results, it was found that nanocrystalline tapes have higher corrosion resistance than amorphous counterpart and H2SO4 can promote the occurrence of corrosion compared with NaCl.

  9. 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.

  10. Microwave investigation of sulfuric acid monohydrate.

    PubMed

    Fiacco, Denise L; Hunt, Sherri W; Leopold, Kenneth R

    2002-04-24

    The complex H2SO4-H2O has been observed by rotational spectroscopy in a supersonic jet. A-type spectra for 18 isotopic forms have been analyzed, and the vibrationally averaged structure of the system has been determined. The complex forms a distorted, six-membered ring with the water unit acting as both a hydrogen bond donor and a hydrogen bond acceptor toward the sulfuric acid. One of the H2SO4 protons forms a short, direct hydrogen bond to the water oxygen, with an H...O distance of 1.645(5) A and an O-H...O angle of 165.2(4) degrees. Additionally, the orientation of the water suggests a weaker, secondary hydrogen bond between one of the H2O hydrogens and a nearby S=O oxygen on the sulfuric acid, with an O...H distance of 2.05(1) A and an O-H...O angle of 130.3(5) degrees. The experimentally determined structure is in excellent agreement with previously published DFT studies. Experiments with HOD in the jet reveal the formation of only isotopomers involving deuterium in the secondary hydrogen bond, providing direct experimental evidence for the secondary H...O interaction. Extensive isotopic substitution has also permitted a re-determination of the structure of the H2SO4 unit within the complex. The hydrogen-bonding OH bond of the sulfuric acid elongates by 0.07(2) A relative to that in free H2SO4, and the S=O bond involved in the secondary interaction stretches by 0.04(1) A. These changes reflect substantial distortion of the H2SO4 moiety in response to only a single water molecule, and prior to the proton transfer event. Spectral data indicate that the complex undergoes at least one, and probably more than one type of internal motion. Although the sulfuric acid in this work was produced from direct reaction of SO3 and water in the jet, experiments with H2(18)O indicate that about 2-3% of the acid is formed via processes not normally associated with the gas-phase hydration of SO3.

  11. Synthesis and electrocatalytic properties of H2SO4 -induced (100) Pt nanoparticles prepared in water-in-oil microemulsion.

    PubMed

    Martínez-Rodríguez, Roberto A; Vidal-Iglesias, Francisco J; Solla-Gullón, José; Cabrera, Carlos R; Feliu, Juan M

    2014-07-21

    The increasing number of applications for shape-controlled metal nanoparticles (NPs) has led to the need for easy, cheap, and scalable methodologies. We report the synthesis of (100) preferentially oriented Pt NPs, with a particle size of 9 nm, by using a water-in-oil microemulsion method. The specific surface structure of the NPs is induced by the presence of H(2)SO(4) in the water phase of the microemulsion. Interestingly, the results reported herein show how increasing amounts of H(2)SO(4) lead to the formation of Pt NPs containing a larger amount of (100) sites on their surface. This preferential surface orientation is confirmed electrochemically by using the so-called hydrogen adsorption/desorption process. In addition, transmission electron microscopy measurements confirm the presence of cubic-like Pt NPs. Finally, the electrocatalytic properties of the Pt NPs are evaluated towards ammonia and CO electro-oxidations, which are (100) structure-sensitive reactions. PMID:24648299

  12. 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.

  13. 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.

  14. 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.

  15. 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

  16. Phase and extraction equilibria in H2O-sulfonol-HCl (H2SO4) and H2O-sodium dodecyl sulfate-HCl (H2SO4) systems

    NASA Astrophysics Data System (ADS)

    Zabolotnykh, S. A.; Lesnov, A. E.; Denisova, S. A.

    2016-10-01

    Solubility isotherms of water-sulfonol-hydrochloric (or sulfuric) acid and water-sodium dodecyl sulfate-hydrochloric acid systems at 75°C and a water-sodium dodecyl sulfate-sulfuric acid system at 50°C are constructed. Regions of two-phase liquid equilibrium suitable for use in extraction are found. Concentration parameters for extraction are determined. The interfacial distribution of a series of metal ions with and without such additional complexing reagents as diantipyrylmethane and diantipyrylheptane is studied.

  17. Mechanism of protodesorption-exchange of heavy metal cations for protons in a heterophase system of H2O-H2SO4-MSO4-cellulose sorbent.

    PubMed

    Kozlov, V A; Nikiforova, T E; Loginova, V A; Koifman, O I

    2015-12-15

    The influence of pH on the distribution of metal cations [Cd(II), Cu(II), Fe(II), Ni(II), Zn(II)] in a four-component heterophase system (H2O-H2SO4-MSO4-cellulose sorbent) was studied. Protodesorption of metal cations was studied with indicator and constant quantities of [MSO4] salts and constant solvent-sorbent ratio. Linear dependence lgКDМ2+=f(рН) with tgα=1/2 of the КDМ2+ metal ions distribution coefficients from the acidity of the aqueous phase is observed in logarithmic coordinates. Depression of the exponent corresponding to proton involvement in protodesorption from 2 (theory) to 0.5 (experiment) indicates that anions of the aqueous phase are involved in the process of exchange of metal cation for proton on the anionic centers of the sorbent, which corresponds to participation of the salt and acid components of the system in molecular non-dissociated form in an equivalent proportion H2SO4/MSO4=1/1. Different behavior of the salt and acid components in ion exchange of cations for cations and cations for protons is due to the differences in the constraint coefficients of their molecular and ionic forms which must be taken into consideration in equations describing thermodynamics of the interphase exchange.

  18. Binderless Composite Electrode Monolith from Carbon Nanotube and Biomass Carbon Activated by H2 SO4 and CO2 Gas for Supercapacitor

    NASA Astrophysics Data System (ADS)

    Deraman, M.; Ishak, M. M.; Farma, R.; Awitdrus, Taer, E.; Talib, I. A.; Omar, R.

    2011-12-01

    Binderless composite electrodes in the monolithic form prepared from carbon nanotubes (CNTs) and self-adhesive carbon grains (SACG) from fibers of oil palm empty fruit bunch were studied as an electrode in a supercapacitor. The green monoliths (GMs) were prepared from three different types of precursors, SACG, SACG treated with 0.4 Molar H2 SO4 and mixture of SACG and 5% CNTs (by weight) treated with 0.4 Molar H2 SO4 , respectively. These GMs were carbonized at 600 ° C in N2 gas environment and activated by CO2 gas at 800 ° C for 1 hour to produce activated carbon monoliths (ACMs). The properties of the ACMs (density, porosity, microstructure, structure and electrical conductivity) were found affected by CNTs addition and acid treatment. The acid treatment did not improve the electrochemical behavior of the ACMs used as electrodes (specific capacitance, specific energy and specific power of the supercapacitor) in the supercapacitor cells but CNTs addition improves the equivalent series resistance of the cell.

  19. 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.

  20. Potential role of stabilized Criegee radicals in sulfuric acid production in a high biogenic VOC environment.

    PubMed

    Kim, Saewung; Guenther, Alex; Lefer, Barry; Flynn, James; Griffin, Robert; Rutter, Andrew P; Gong, Longwen; Cevik, Basak Karakurt

    2015-03-17

    We present field observations made in June 2011 downwind of Dallas-Fort Worth, TX, and evaluate the role of stabilized Criegee radicals (sCIs) in gaseous sulfuric acid (H2SO4) production. Zero-dimensional model calculations show that sCI from biogenic volatile organic compounds composed the majority of the sCIs. The main uncertainty associated with an evaluation of H2SO4 production from the sCI reaction channel is the lack of experimentally determined reaction rates for sCIs formed from isoprene ozonolysis with SO2 along with systematic discrepancies in experimentally derived reaction rates between other sCIs and SO2 and water vapor. In general, the maximum of H2SO4 production from the sCI channel is found in the late afternoon as ozone increases toward the late afternoon. The sCI channel, however, contributes minor H2SO4 production compared with the conventional OH channel in the mid-day. Finally, the production and the loss rates of H2SO4 are compared. The application of the recommended mass accommodation coefficient causes significant overestimation of H2SO4 loss rates compared with H2SO4 production rates. However, the application of a lower experimental value for the mass accommodation coefficient provides good agreement between the loss and production rates of H2SO4. The results suggest that the recommended coefficient for the H2O surface may not be suitable for this relatively dry environment. PMID:25700170

  1. Heterogeneous interactions of chlorine nitrate, hydrogen chloride, and nitric acid with sulfuric acid surfaces at stratospheric temperatures

    NASA Technical Reports Server (NTRS)

    Tolbert, Margaret A.; Rossi, Michel J.; Golden, David M.

    1988-01-01

    The heterogeneous interactions of ClONO2, HCl, and HNO3 with sulfuric acid surfaces were studied using a Knudsen cell flow reactor. The surfaces studied, chosen to simulate global stratospheric particulate, were composed of 65-75 percent H2SO4 solutions at temperatures in the range -63 to -43 C. Heterogeneous loss, but not reaction, of HNO3 and HCl occurred on these surfaces; the measured sticking coefficients are reported. Chlorine nitrate reacted on the cold sulfuric acid surfaces, producing gas-phase HOCl and condensed HNO3. CLONO2 also reacted with HCl dissolved in the 65-percent H2SO4 solution at -63 C, forming gaseous Cl2. In all cases studied, the sticking and/or reaction coefficients were much larger for the 65-percent H2SO4 solution at -63 C than for the 75-percent solution at -43 C.

  2. Thermal regeneration of sulfuric acid hydrates after irradiation

    NASA Astrophysics Data System (ADS)

    Loeffler, Mark J.; Hudson, Reggie L.

    2012-06-01

    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.

  3. 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.

  4. 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.

  5. Development of a new corona discharge based ion source for high resolution time-of-flight chemical ionization mass spectrometer to measure gaseous H2SO4 and aerosol sulfate

    NASA Astrophysics Data System (ADS)

    Zheng, Jun; Yang, Dongsen; Ma, Yan; Chen, Mindong; Cheng, Jin; Li, Shizheng; Wang, Ming

    2015-10-01

    A new corona discharge (CD) based ion source was developed for a commercial high-resolution time-of-flight chemical ionization mass spectrometer (HRToF-CIMS) (Aerodyne Research Inc.) to measure both gaseous sulfuric acid (H2SO4) and aerosol sulfate after thermal desorption. Nitrate core ions (NO3-) were used as reagent ions and were generated by a negative discharge in zero air followed by addition of excess nitrogen dioxide (NO2) to convert primary ions and hydroxyl radicals (OH) into NO3- ions and nitric acid (HNO3). The CD-HRToF-CIMS showed no detectable interference from hundreds parts per billion by volume (ppbv) of sulfur dioxide (SO2). Unlike the atmospheric pressure ionization (API) ToF-CIMS, the CD ion source was integrated onto the ion-molecule reaction (IMR) chamber and which made it possible to measure aerosol sulfate by coupling to a filter inlet for gases and aerosols (FIGAERO). Moreover, compared with a quadrupole-based mass spectrometer, the desired HSO4- signal was detected by its exact mass of m/z 96.960, which was well resolved from the potential interferences of HCO3-ṡ(H2O)2 (m/z 97.014) and O-ṡH2OṡHNO3 (m/z 97.002). In this work, using laboratory-generated standards the CD-HRToF-CIMS was demonstrated to be able to detect as low as 3.1 × 105 molecules cm-3 gaseous H2SO4 and 0.5 μg m-3 ammonium sulfate based on 10-s integration time and two times of the baseline noise. The CD ion source had the advantages of low cost and a simple but robust structure. Since the system was non-radioactive and did not require corrosive HNO3 gas, it can be readily field deployed. The CD-HRToF-CIMS can be a powerful tool for both field and laboratory studies of aerosol formation mechanism and the chemical processes that were critical to understand the evolution of aerosols in the atmosphere.

  6. Measurement of OH, H2SO4, MSA, DMSO, DMSO2 on the NASA P-3B Aircraft

    NASA Technical Reports Server (NTRS)

    Eisele, F. L.

    1998-01-01

    This project involves the deployment of a variety of unique aircraft measurements for the PEM-Tropics program. These measurements were all to be accomplished on a near simultaneous basis using a two channel selected ion chemical ionization mass spectrometer instrument. The first year of this project consisted of four components; improve and perform additional testing of the OH, H2SO4, and MSA instrument which had only flown on one previous mission (ACE-I); develop and test the vacuum and electronic hardware and software which would allow two independent mass spectrometer systems to be operated from a single instrument (one vacuum/pumping system); construct an aircraft compatible DMSO/DMS02 ion source and calibration system; and operate the above system on the NASA P-3B during PEM-Tropics. The first two of the components were to be accomplished at NCAR. The third component was to be completed at Georgia Tech and the fourth was to be conducted by researchers from both institutions on the NASA P-3B.

  7. Numerical simulation of flow, H2SO4 cycle and new particle formation in the CERN CLOUD chamber

    NASA Astrophysics Data System (ADS)

    Voigtländer, J.; Duplissy, J.; Stratmann, F.

    2011-07-01

    To study the effect of galactic cosmic rays on aerosols and clouds, the Cosmic Leaving OUtdoor Droplets (CLOUD) project was established. Experiments are carried out at a 26 m3 tank at CERN (Switzerland). In the experiments, the effect of ionising particle radiation on H2SO4 particle formation and growth is investigated. To evaluate the experimental configuration, the experiment was simulated using a coupled multidimensional CFD - particle model (CLOUD-FPM). In the model the coupled fields of gas/vapour species, temperature, flow velocity and particle properties were computed to investigate the tank's mixing state and mixing times. Simulation results show that the mixing state of the tank's contents largely depends on the characteristics of the mixing fans and a 1-fan configuration, as used in first experiments, may not be sufficient to ensure a homogeneously mixed chamber. To mix the tank properly, 2 fans are necessary. The 1/e response times for instantaneous changes of wall temperature and saturation ratio inside the chamber were found to be in the order of few minutes. Particle nucleation and growth was also simulated and particle number size distribution properties of the freshly nucleated particles (particle number, mean size, standard deviation of the assumed log-normal distribution) were found to be mixed over the tank's volume similar to the gas species.

  8. Alpha-amylase production is induced by sulfuric acid in rice aleurone cells.

    PubMed

    Mitsunaga, Shin-ichiro; Kobayashi, Midori; Fukui, Satoe; Fukuoka, Kayoko; Kawakami, Osamu; Yamaguchi, Junji; Ohshima, Masahiro; Mitsui, Toshiaki

    2007-12-01

    The hydrolytic enzyme alpha-amylase (EC 3.2.1.1) is produced mainly in aleurone cells of germinating cereals, and the phytohormone gibberellin (GA) is essential for its induction. However, in rice (Oryza sativa L.), sulfuric acid (H(2)SO(4)) induces alpha-amylase production in aleurone tissue even in the absence of GA. Here, the pre-treatment of rice aleurone cells with H(2)SO(4) and incubation in water induced alpha-amylase activity, as if the cells had been incubated in GA solution. PMID:17988885

  9. Surface Chemical Compositions and Dispersity of Starch Nanocrystals Formed by Sulfuric and Hydrochloric Acid Hydrolysis

    PubMed Central

    Wei, Benxi; Xu, Xueming; Jin, Zhengyu; Tian, Yaoqi

    2014-01-01

    Surface chemical compositions of starch nanocrystals (SNC) prepared using sulfuric acid (H2SO4) and hydrochloric acid (HCl) hydrolysis were analyzed by X-ray photoelectron spectroscopy (XPS) and FT-IR. The results showed that carboxyl groups and sulfate esters were presented in SNC after hydrolysis with H2SO4, while no sulfate esters were detected in SNC during HCl-hydrolysis. TEM results showed that, compared to H2SO4-hydrolyzed sample, a wider size distribution of SNC prepared by HCl-hydrolysis were observed. Zeta-potentials were −23.1 and −5.02 mV for H2SO4- and HCl-hydrolyzed SNC suspensions at pH 6.5, respectively. Nevertheless, the zeta-potential values decreased to −32.3 and −10.2 mV as the dispersion pH was adjusted to 10.6. After placed 48 h at pH 10.6, zeta-potential increased to −24.1 mV for H2SO4-hydrolyzed SNC, while no change was detected for HCl-hydrolyzed one. The higher zeta-potential and relative small particle distribution of SNC caused more stable suspensions compared to HCl-hydrolyzed sample. PMID:24586246

  10. Surface chemical compositions and dispersity of starch nanocrystals formed by sulfuric and hydrochloric acid hydrolysis.

    PubMed

    Wei, Benxi; Xu, Xueming; Jin, Zhengyu; Tian, Yaoqi

    2014-01-01

    Surface chemical compositions of starch nanocrystals (SNC) prepared using sulfuric acid (H2SO4) and hydrochloric acid (HCl) hydrolysis were analyzed by X-ray photoelectron spectroscopy (XPS) and FT-IR. The results showed that carboxyl groups and sulfate esters were presented in SNC after hydrolysis with H2SO4, while no sulfate esters were detected in SNC during HCl-hydrolysis. TEM results showed that, compared to H2SO4-hydrolyzed sample, a wider size distribution of SNC prepared by HCl-hydrolysis were observed. Zeta-potentials were -23.1 and -5.02 mV for H2SO4- and HCl-hydrolyzed SNC suspensions at pH 6.5, respectively. Nevertheless, the zeta-potential values decreased to -32.3 and -10.2 mV as the dispersion pH was adjusted to 10.6. After placed 48 h at pH 10.6, zeta-potential increased to -24.1 mV for H2SO4-hydrolyzed SNC, while no change was detected for HCl-hydrolyzed one. The higher zeta-potential and relative small particle distribution of SNC caused more stable suspensions compared to HCl-hydrolyzed sample.

  11. 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.

  12. H 2SO 4/HNO 3/HCl—Functionalization and its effect on dispersion of carbon nanotubes in aqueous media

    NASA Astrophysics Data System (ADS)

    Osorio, A. G.; Silveira, I. C. L.; Bueno, V. L.; Bergmann, C. P.

    2008-12-01

    Chemical functionalization is a procedure used in materials science to oxidize the surface of materials. Several researchers use this technique to improve carbon nanotubes (CNTs) interaction and dispersion. The present article evaluates the effect of different functionalization methodologies on dispersion of CNTs in aqueous media. Sulfuric, nitric and chloridric acids were used on the first functionalization. For the second procedure tested the addition of chloridric acid was eliminated; and the third functionalization was done using only nitric acid. Experimental results obtained by Raman spectroscopy indicated the maintenance of the structure of CNTs after all oxidations. The presence of other structures was proved by thermogravimetry decomposition and the addition of functional groups was confirmed by transform Fourier infrared spectroscopy. From these experimental results, we conclude that all methodologies used showed a percentage of adsorption of functional groups on the CNTs. However, based on dispersion analysis in aqueous media, it is observed that this adsorption showed more efficiency on the first functionalization method, followed by the second method.

  13. Synergism between rare earth cerium(IV) ion and vanillin on the corrosion of steel in H 2SO 4 solution: Weight loss, electrochemical, UV-vis, FTIR, XPS, and AFM approaches

    NASA Astrophysics Data System (ADS)

    Li, Xianghong; Deng, Shuduan; Fu, Hui; Mu, Guannan; Zhao, Ning

    2008-06-01

    The synergism between rare earth cerium(IV) ion and vanillin (4-hydroxy-3-methoxy-benzaldehyde) on the corrosion of cold rolled steel (CRS) in 1.0 M H 2SO 4 solution at five temperatures ranging from 20 to 60 °C was first studied by weight loss and potentiodynamic polarization methods. The inhibited solutions were analyzed by ultraviolet and visible spectrophotometer (UV-vis). The adsorbed film of CRS surface containing optimum doses of the blends Ce 4+-vanillin was investigated by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and atomic force microscope (AFM). The results revealed that vanillin had a moderate inhibitive effect, and the inhibition efficiency (IE) increased with the vanillin concentration. The adsorption of vanillin obeyed Temkin adsorption isotherm. Polarization curves showed that vanillin was a mixed-type inhibitor in sulfuric acid, while prominently inhibited the cathodic reaction. For the cerium(IV) ion, it had a negligible effect, and the maximum IE was only about 20%. However, incorporation of Ce 4+ with vanillin improved significantly the inhibition performance. The IE for Ce 4+ in combination with vanillin was higher than the summation of IE for single Ce 4+ and single vanillin, which was synergism in nature. A high inhibition efficiency, 98% was obtained by a mixture of 25-200 mg l -1 vanillin and 300-475 mg l -1 Ce 4+. UV-vis showed that the new complex of Ce 4+-vanillin was formed in 1.0 M H 2SO 4 for Ce 4+ combination with vanillin. Polarization studies showed that the complex of Ce 4+-vanillin acted as a mixed-type inhibitor, which drastically inhibits both anodic and cathodic reactions. FTIR and XPS revealed that a protective film formed in the presence of both vanillin and Ce 4+ was composed of cerium oxide and the complex of Ce 4+-vanillin. The synergism between Ce 4+ and vanillin could also be evidenced by AFM images. Depending on the results, the synergism mechanism was discussed from the

  14. Inhibitory action of quaternary ammonium bromide on mild steel and synergistic effect with other halide ions in 0.5 M H2SO4

    PubMed Central

    Khamis, A.; Saleh, Mahmoud M.; Awad, Mohamed I.; El-Anadouli, B.E.

    2013-01-01

    The corrosion inhibition of mild steel in 0.5 M H2SO4 solution has been investigated using electrochemical methods, X-ray diffraction (XRD) and scanning electron microscope (SEM). The adsorption and inhibition action of acid corrosion of mild steel using cetyltrimethylammonium bromide (CTABr) and different halides (NaCl, NaBr and NaI) has shown synergetic effect. The results showed that the protection efficiency (P%) has high values at considerable high concentration of CTABr. However, in the presence of the different halides, the P increases dramatically at low concentration of CTABr. Physisorption was proposed from the the values of ΔGads0. The synergism parameter (Sθ) is found to be greater than unity indicating that the enhanced P% caused by the addition of the halides to the CTABr is due to a co-operative adsorption of both species. Corrosion products phases and surface morphology were studied using X-ray diffraction (XRD) and scanning electron microscopy (SEM), respectively. PMID:25685532

  15. A Density Functional Theory Study of Temperature Dependence of Cluster Formation from Sulfuric Acid and Ammonia

    NASA Astrophysics Data System (ADS)

    lin, H.; Chon, N. L.; Lee, S.

    2013-12-01

    Recent atmospheric nucleation studies have shown that acid-base reactions are essential at the initial step of aerosol nucleation. Ammonia is the most abundant base compound present in the atmosphere. Ammonia can directly interact with sulfuric acid clusters to reduce Gibbs free energy of cluster formation and growth, but the role that ammonia plays in atmospheric nucleation is still not well understood, especially at the molecular cluster level. We have performed density functional theory (BL3YP) and ab initio (MP2) calculations to study energetics of cluster formation for (NH3)m(H2SO4) and (NH3)(H2SO4)n (m, n = 1-6) in the temperature range from 200-300 K. For the model (NH3)m(H2SO4) clusters, bindings were predicted to increase from m = 1 to 6 at 200 K, while the most stable complex at 300 K was found to be at m = 2. For the (NH3)(H2SO4)n complexes, enthalpic contributions dominated and the binding is more stable for larger n. The temperature dependency has stronger effects on the (NH3)m(H2SO4) complexes, among which the lowest free energy shifts from m = 6 at T = 200 K to m = 5 around T = 240 K and further to m = 2 at T ≥ 280 K. The effects on the (NH3)(H2SO4)n complexes are much smaller, while there are similar trends that favor larger n for all temperatures between 200 and 300 K. These results thus indicate that the role of ammonia in atmospheric aerosol nucleation is critical in a wide range of atmospheric temperature conditions.

  16. 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.

  17. Measurement of OH, H2SO4, MSA, NH3 and DMSO Aboard the NASA P-3B Aircraft

    NASA Technical Reports Server (NTRS)

    Eisele, Fred

    2001-01-01

    This project involved the installation of a downsized multichannel mass spectrometer instrument on the NASA P-3B aircraft and its subsequent use on the PEM-Tropics B mission. The new instrument performed well, measuring a number of difficult-to-measure compounds and providing much new photochemical and sulfur data as well as possibly uncovering a new nighttime DMSO source. The details of this effort are discussed.

  18. Nitrogen and oxygen functionalized hollow carbon materials: The capacitive enhancement by simply incorporating novel redox additives into H2SO4 electrolyte

    NASA Astrophysics Data System (ADS)

    Nie, Yong Fu; Wang, Qian; Chen, Xiang Ying; Zhang, Zhong Jie

    2016-07-01

    In present work, we have developed a simple but effective template carbonization method for producing hollow carbon materials with high content of nitrogen and oxygen from thiocarbanilide. Among all samples, the NPC-1 exhibits high specific surface area (736 m2 g-1) and large pore volume (5.93 cm3 g-1) with high content of heteroatoms (∼11.25 at% nitrogen and ∼5.74 at% oxygen), which is conducive to the improvement of electrochemical performance. Specifically, the high specific capacitance and excellent cycling stability over 5000 cycles of the NPC-1-based electrode are achieved in 1 mol L-1 H2SO4 electrolyte. Additionally, pyrocatechol and rutin as novel redox additives that can easily cause redox-reactions have been incorporated into H2SO4 electrolyte to improve the capacitances. As a result, the NPC-1-R-0.15 and NPC-1-P-0.15 samples deliver high specific capacitances of 120.5 and 368.7 F g-1 at 2 A g-1, respectively, which are much higher than that of the NPC-1 sample (66.2 F g-1) without redox-additives at same current density. Furthermore, the large energy density of 18.9 and 11.9 Wh kg-1 of the NPC-1-based symmetric supercapacitors have been obtained in H2SO4+pyrocatechol and H2SO4+rutin electrolyte, respectively, and both samples also demonstrate excellent cyclic performance for 5000 cycles.

  19. A comparative study of ORR at the Pt electrode in ammonium ion-contaminated H2SO4 and HClO4 solutions

    NASA Astrophysics Data System (ADS)

    Rahman, Mohammad R.; Awad, Mohamed I.; Kitamura, Fusao; Okajima, Takeyoshi; Ohsaka, Takeo

    2012-12-01

    Poisoning of the poly-Pt electrode by low concentration ammonium ion was investigated in H2SO4 and HClO4 solutions and a significant poisoning was observed in H2SO4 solution. An extraordinary recovery of the poisoned electrode was achieved in HClO4 solution by cycling the electrode potential between the onset potentials of the hydrogen and oxygen evolution. The extent of recovery was marked using the oxygen reduction reaction (ORR) as a probing reaction. Ammonium ion poisoning of the electrodes in H2SO4 caused a significant contribution of the two-electron reduction of O2 to hydrogen peroxide, as indicated by the rotating ring-disk voltammetry. The Tafel slopes at the low and high current densities were also affected by the presence of ammonium ion in H2SO4 solution and an increase in the Tafel slope was recognized with increasing the concentration of ammonium ion. However, the Tafel slopes at the low and high current densities were hardly affected by the ammonium ion in HClO4 solution.

  20. Effect of concentration and cumulative exposure of inhaled sulfuric acid on tracheobronchial particle clearance in healthy humans.

    PubMed

    Spektor, D M; Yen, B M; Lippmann, M

    1989-02-01

    We have previously shown that 1-hr exposures to 0.5 microns sulfuric acid (H2SO4) mist at 100 and 1000 micrograms/m3 produced transient alterations of bronchial mucociliary clearance of monodispersed 7.6 and 4.2 microns mass median aerodynamic diameter gamma-tagged ferric oxide (Fe2O3) in healthy nonsmoking humans in a dose-dependent manner. To determine the role, if any, of the length of exposure, 10 healthy volunteers were exposed to 100 micrograms/m3 H2SO4 for 1 hr and 2 hr on separate occasions, 1 week apart, with measurements of their mucociliary clearance of 5.2 microns Fe2O3 particles inhaled both before and after the inhalation of the H2SO4. Their rate of bronchial mucociliary clearance was markedly reduced for both Fe2O3 aerosols, with slower clearance of the aerosol inhaled after the H2SO4 exposure. For the tagged Fe2O3 aerosol inhaled after exposure for 2 hr at 100 micrograms/m3 H2SO4, the tracheobronchial clearance halftime, (T50), tripled from control, and the reduced rate of clearance was still evident 3 hr after the end of exposure. The 1-hr 100 micrograms/m3 H2SO4 exposure doubled T50 from control, and the reduced rate of clearance lasted for about 2 hr after the end of exposure. These results indicate that the effect of doubling the length of exposure was as great or greater than an order of magnitude increase in the concentration of H2SO4.

  1. Improvement in the etching performance of the acrylonitrile-butadiene-styrene resin by MnO2-H3PO4-H2SO4 colloid.

    PubMed

    Zhao, Wenxia; Ding, Jie; Wang, Zenglin

    2013-05-21

    The present study aimed to evaluate the surface etching of the acrylonitrile-butadiene-styrene (ABS) resin in the MnO2-H3PO4-H2SO4 colloid. To enhance the soluble Mn(IV) ion concentration and improve the etching performance of ABS resin, H3PO4 was added as a complexing agent into the MnO2-H2SO4 etching system. The effects of the H2SO4 concentration and etching time on the surface topography, surface roughness, adhesion strength, and the surface chemistry of the ABS substrates were investigated. The optimal oxidation potentials of MnO2 in the colloids decreased from 1.426 to 1.369 V with the addition of H3PO4. Though the etching conditions changed from 70 °C for 20 min to 60 °C for 10 min, the adhesion strength between the ABS substrates and electroless copper film increased from 1.19 to 1.33 KN/m after etching treatment. This could be attributed to the significant increase of the soluble Mn(IV) ion concentration in the MnO2-H3PO4-H2SO4 colloid. The surface chemistry results demonstrated that the oxidation reaction of -C═C- bonds in the polybutadiene phase was accelerated in the etching process by the addition of H3PO4, and the abundant -COOH and -OH groups were formed rapidly on the ABS surface with the etching treatment. These results were in agreement with the results of surface scanning electron microscopic observations and adhesion strength measurement. The results suggested that the MnO2-H3PO4-H2SO4 colloid was an effective surface etching system for the ABS surface roughness. PMID:23611532

  2. Single-Particle Laboratory Studies of Heterogeneous H2O and HCl Processing on Clean and H2SO4-Coated Aluminum Oxide Particles

    NASA Astrophysics Data System (ADS)

    Hunter, A. J.; Sonnenfroh, D. M.; Rawlins, W. T.

    2001-12-01

    Aluminum oxide particles exhausted from solid rocket motors may affect tropospheric and stratospheric radiative balance through nucleation and growth of water ice clouds, both locally in launch corridors and globally. These particles also are active toward chemisorption of HCl and dissociative chemisorption of CFCs. Plume particle surfaces are likely to contain H2SO4, possibly altering their activities toward uptake and chemical processing of HCl and HNO3. We have investigated activities of different types of aluminum oxide particles for uptake of gas-phase H2O and HCl, using a single-particle electrodynamic levitation apparatus. The particle types investigated were clean and H2SO4-treated alpha-Al2O3 and gamma-Al2O3. We also investigated metastable Al2O3 particles formed by rapid cooling from molten particles in a shock tube, analogous to particle processing in a rocket exhaust nozzle. Particles were treated with H2SO4 by vapor deposition in an oven. The kinetic measurements consisted of independent, simultaneous observations of mass uptake and particle size increase upon exposure of single levitated particles to fixed concentrations of H2O or HCl in slowly flowing gas mixtures at 1 atm. Alpha and gamma Al2O3 were essentially inert toward H2O and HCl uptake, however they readily adsorbed monolayer-equivalent levels of H2SO4 vapor. H2SO4-coated and metastable particles were active toward H2O and HCl uptake. The measured uptake efficiencies imply fast reaction rates within rocket exhaust plumes, potentially leading to CCN behavior as well as heterogeneous chlorine activation by these particles. This research was supported by the Air Force Office of Scientific Research.

  3. 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.

  4. 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.

  5. 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

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

    PubMed

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

    2016-02-18

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

  7. Phase equilibria of H2SO4, HNO3, and HCl hydrates and the composition of polar stratospheric clouds

    NASA Technical Reports Server (NTRS)

    Wooldridge, Paul J.; Zhang, Renyi; Molina, Mario J.

    1995-01-01

    Thermodynamic properties and phase equilibria behavior for the hydrates and coexisting pairs of hydrates of common acids which exist in the stratosphere are assembled from new laboratory measurements and standard literature data. The analysis focuses upon solid-vapor and solid-solid-vapor equilibria at temperatures around 200 K and includes new calorimetric and vapor pressure data. Calculated partial pressures versus 1/T slopes for the hydrates and coexisting hydrates agree well with experimental data where available.

  8. Phase Equilibria of H2SO4, HNO3, and HCl Hydrates and the Composition of Polar Stratospheric Clouds

    NASA Technical Reports Server (NTRS)

    Wooldridge, Paul J.; Zhang, Renyi; Molina, Mario J.

    1995-01-01

    Thermodynamic properties and phase equilibria behavior for the hydrates and coexisting pairs of hydrates of common acids which exist in the stratosphere are assembled from new laboratory measurements and standard literature data. The analysis focuses upon solid-vapor and solid-solid-vapor equilibria at temperatures around 200 K and includes new calorimetric and vapor pressure data. Calculated partial pressures versus 1/T slopes for the hydrates and coexisting hydrates agree well with experimental data where available.

  9. Sulfuric acid-induced changes in the physiology and structure of the tracheobronchial airways.

    PubMed

    Gearhart, J M; Schlesinger, R B

    1989-02-01

    Sulfuric acid aerosols occur in the ambient particulate mode due to atmospheric conversion from sulfur dioxide (SO2). This paper describes the response of the rabbit tracheobronchial tree to daily exposures to sulfuric acid (H2SO4) aerosol, relating physiological and morphological parameters. Rabbits were exposed to filtered air (sham control) or to submicrometer-sized H2SO4 at 250 micrograms/m3 H2SO4, for 1 hr/day, 5 days/week, with sacrifices after 4, 8, and 12 months of acid (or sham) exposure; some rabbits were allowed a 3-month recovery after all exposures ended. H2SO4 produced a slowing of tracheobronchial mucociliary clearance during the first weeks of exposure; this change became significantly greater with continued exposures and did not improve after exposures ended. Airway hyperresponsiveness was evident by 4 months of acid exposure; the condition worsened by 8 months of exposure and appeared to stabilize after this time. Standard pulmonary mechanics parameters showed no significant trends with repeated acid exposure, except for a decline in dynamic lung compliance in animals exposed to acid for 12 months. Lung tissue samples obtained from exposed animals showed a shift toward a greater frequency of smaller airways compared to control, an increase in epithelial secretory cell density in smaller airways, and a shift from neutral to acidic glycoproteins in the secretory cells. The effect on airway diameter resolved after the exposures ceased, but the secretory cell response did not return to normal within the recovery period. No evidence of inflammatory cell infiltration was found due to H2SO4 exposure. Thus, significant alterations in the physiology of the tracheobronchial tree have been demonstrated due to repeated 1-hr exposures to a concentration of H2SO4 that is one-fourth the current 8-hr threshold limit value for exposure in the work environment. The cumulative dose inhaled by the rabbits is similar to current peak daily doses from ambient exposure

  10. Sulfuric acid vapor in the atmosphere of Venus as observed by the Venus Express Radio Science experiment VeRa

    NASA Astrophysics Data System (ADS)

    Oschlisniok, Janusz; Pätzold, Martin; Häusler, Bernd; Tellmann, Silvia; Bird, Mike; Andert, Tom

    2016-04-01

    The cloud deck within Venus' atmosphere, which covers the entire planet between approx. 50 and 70 km altitude, consists mostly of liquid and gaseous sulfuric acid. The gaseous part increases strongly just below the main clouds and builds an approx. 15 km thick haze layer of H2SO4. This region is responsible for a strong absorption of radio waves as seen in VeRa radio science observations. The amount of the absorption, which is used to derive the abundance of gaseous sulfuric acid, depends on the signal frequency. VeRa probed the atmosphere of Venus between 2006 and 2015 with radio signals at 13 cm (S-band) and 3.6 cm (X-band) wavelengths. We present H2SO4 profiles derived from S-band and X-band absorption during the first occultation season in 2006. The comparison of the H2SO4 profiles derived from both frequency bands provides a reliable picture of the H2SO4 abundance. Distinct differences in the S- and X-band profiles may give a clue to increased SO2 abundances. The derived VeRa results shall be compared with results provided by other experiments onboard Venus Express as well as with previous missions.

  11. Kinetic study of esterification of sulfuric acid with alcohols in aerosol bulk phase

    NASA Astrophysics Data System (ADS)

    Li, J.; Jang, M.

    2013-09-01

    In this study, we hypothesize that the formation of organosulfates through the reactions between sulfuric acid and alcohols in the aerosol bulk phase is more efficient than that in solution chemistry. To prove this hypothesis, the kinetics of the organosulfate formation was investigated for both aliphatic alcohol with single OH group (e.g., 1-heptanol) and the multialcohols ranging from semivolatiles (e.g., hydrated-glyoxal and glycerol) to nonvolatiles (e.g., sucrose) using analytical techniques directly monitoring aerosol bulk phase. Both the forward (k1) and the backward (k-1) reaction rate constants of organosulfate formation via the particle phase esterification of 1-heptanol with sulfuric acid were estimated using a Fourier Transform Infrared (FTIR) spectrometer equipped with a flow chamber under varying humidities. Both k1 and k-1 are in orders of 10-3 L mol-1 min-1, which are three orders of magnitude higher than the reported values obtained in solution chemistry. The formation of organosulfate in the H2SO4 aerosol internally mixed with multialcohols was studied by measuring the proton concentration of the aerosol collected on the filter using a newly developed Colorimetry integrated with a Reflectance UV-Visible spectrometer (C-RUV). The formation of organosulfate significantly decreases aerosol acidity due to the transformation of H2SO4 into dialkylsulfates. The forward reaction rate constants for the dialkylsulfate formation in the multialcohol-H2SO4 aerosols were also three orders of magnitude greater than the reported values in solution chemistry. The water content (MH2O) in the multialcohol-H2SO4 particle was monitored using the FTIR spectrometer. A large reduction of MH2O accords with the high yield of organosulfate in aerosol. Based on this study, we conclude that organosulfate formation in atmospheric aerosol, where both alcohols and sulfuric acid are found together, is significant.

  12. 30 CFR 7.48 - Acid resistance test.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Acid resistance test. 7.48 Section 7.48 Mineral... MINING PRODUCTS TESTING BY APPLICANT OR THIRD PARTY Battery Assemblies § 7.48 Acid resistance test. (a... solution of sulfuric acid (H2 SO4) by mixing 853 ml of water with 199 ml of sulfuric acid (H2 SO4) with...

  13. 30 CFR 7.48 - Acid resistance test.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Acid resistance test. 7.48 Section 7.48 Mineral... MINING PRODUCTS TESTING BY APPLICANT OR THIRD PARTY Battery Assemblies § 7.48 Acid resistance test. (a... solution of sulfuric acid (H2 SO4) by mixing 853 ml of water with 199 ml of sulfuric acid (H2 SO4) with...

  14. 30 CFR 7.48 - Acid resistance test.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 30 Mineral Resources 1 2014-07-01 2014-07-01 false Acid resistance test. 7.48 Section 7.48 Mineral... MINING PRODUCTS TESTING BY APPLICANT OR THIRD PARTY Battery Assemblies § 7.48 Acid resistance test. (a... solution of sulfuric acid (H2 SO4) by mixing 853 ml of water with 199 ml of sulfuric acid (H2 SO4) with...

  15. 30 CFR 7.48 - Acid resistance test.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 30 Mineral Resources 1 2012-07-01 2012-07-01 false Acid resistance test. 7.48 Section 7.48 Mineral... MINING PRODUCTS TESTING BY APPLICANT OR THIRD PARTY Battery Assemblies § 7.48 Acid resistance test. (a... solution of sulfuric acid (H2 SO4) by mixing 853 ml of water with 199 ml of sulfuric acid (H2 SO4) with...

  16. 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.

  17. Rapid food decomposition by H2O2-H2SO4 for determination of total mercury by flow injection cold vapor atomic absorption spectrometry.

    PubMed

    Zenebon, Odair; Sakuma, Alice M; Dovidauskas, Sergio; Okada, Isaura A; de, MaioFrancaD; Lichtig, Jaim

    2002-01-01

    A mixture of 50% H2O2-H2SO4 (3 + 1, v/v) was used for decomposition of food in open vessels at 80 degrees C. The treatment allowed rapid total mercury determination by flow injection cold vapor atomic absorption spectrometry. Cabbage, potatoes, peanuts paste, hazelnuts paste, oats, tomatoes and their derivatives, oysters, shrimps, prawns, shellfish, marine algae, and many kinds of fish were analyzed by the proposed methodology with a limit of quantitation of 0.86 +/- 0.08 microg/L mercury in the final solution. Reference materials tested also gave excellent recovery.

  18. 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).

  19. 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.

  20. Effects of HNO3 concentration on the pit morphologies of aluminum foil etched in HNO3-HCl and HNO3-H2SO4-HCl solutions

    NASA Astrophysics Data System (ADS)

    Yi, Quan-xiu; He, Ye-dong; Peng, Ning; Song, Hong-zhou; Yang, Xiao-fei; Cai, Xiao-yu

    2016-01-01

    In this work, the effects of HNO3 concentration on the pit morphologies of high-cubic-texture aluminum foil etched in HNO3-HCl and HNO3-H2SO4-HCl solutions were investigated. When the aluminum foil was etched in HNO3-HCl solutions, the morphologies of pits transformed from irregular tunnels to typical tunnels (as inverted pyramids) and shallow cuboids as the HNO3 concentration in the etchant solution was increased. However, as the HCl concentration in the etchant solution was increased, the morphologies of pits transformed from shallow cuboids to typical tunnels (as inverted pyramids) and irregular tunnels. When the aluminum foil was etched in n N HNO3-(7.2- n) N H2SO4-0.8 N HCl solutions, the morphologies of the pits transformed from typical tunnels (i.e., the number of sub-tunnels formed on the main tunnels increased) to irregular tunnels (corrugated tunnels and polyline tunnels) as the HNO3 concentration in the etchant solution was increased. These effects are attributed primarily to corrosion on the (100) and (010) faces of pits being accelerated and to the (001) faces being prone to passivation to different degrees when various concentrations of HNO3 are added to the etchant solutions.

  1. Why sulfuric acid forms particles so extremely well, and how organics might still compete

    NASA Astrophysics Data System (ADS)

    Kurten, T.; Ehn, M.; Kupiainen, O.; Olenius, T.; Rissanen, M.; Thornton, J. A.; Nielsen, L.; Jørgensen, S.; Ortega Colomer, I. K.; Kjaergaard, H. G.; Vehkamäki, H.

    2013-12-01

    It is a well-known result in aerosol science that the single most important molecule for the first steps of new-particle formation in our atmosphere is sulfuric acid, H2SO4. From a chemical perspective, this seems somewhat counterintuitive: the atmosphere contains thousands of different organic compounds, many of which can potentially form oxidation products with even lower volatility than H2SO4. The unique role of sulfuric acid is due to its formation kinetics. The conversion of sulfur dioxide, SO2 to H2SO4 requires only a single oxidant molecule (e.g. OH), as subsequent steps are extremely rapid. Still, the saturation vapor pressure of H2SO4 is over 108 times lower than that of SO2. In contrast, the oxidation reactions of organic molecules typically lower their saturation vapor pressure by only a factor of 10-1000 per oxidation step. Therefore, organic compounds are usually lost to pre-existing aerosol surfaces before they have undergone sufficiently many oxidation reactions to nucleate on their own. The presence of strong nitrogen-containing base molecules such as amines enhances the particle-forming advantages of sulfuric acid even further. Quantum chemical calculations indicate that the evaporation rate of sulfuric acid from key clusters containing two acid molecules may decrease by a factor of 108 in the presence of ppt-level concentrations of amines, implying a total decrease of up to 1016 in the effective vapor pressure going from SO2 to H2SO4. In some circumstances, this decrease causes the energy barrier for new-particle formation to disappear: the process is no longer nucleation, and some common applications of e.g. the nucleation theorem cease to apply. Cluster kinetic models combined with first-principles evaporation rates appear to describe this sulfuric acid - base clustering reasonably well, and result in cluster formation rates close to those measured at the CLOUD experiment in CERN. There may nevertheless exist exceptions to the general rule that

  2. 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

  3. Application of Essential Oil of Artemisia Herba Alba as Green Corrosion Inhibitor for Steel in 0.5 M H2SO4

    NASA Astrophysics Data System (ADS)

    Ouachikh, O.; Bouyanzer, A.; Bouklah, M.; Desjobert, J.-M.; Costa, J.; Hammouti, B.; Majidi, L.

    Essential oil from Artemisia herba alba (Art) was hydrodistilled and tested as corrosion inhibitor of steel in 0.5 M H2SO4 using weight loss measurements and electrochemical polarization methods. Results gathered show that this natural oil reduced the corrosion rate by the cathodic action. Its inhibition efficiency attains the maximum (74%) at 1 g/L. The inhibition efficiency of Arm oil increases with the rise of temperature. The adsorption isotherm of natural product on the steel has been determined. A. herba alba essential oil was obtained by hydrodistillation and its chemical composition oil was investigated by capillary GC and GC/MS. The major components were chrysanthenone (30.6%) and camphor (24.4%).

  4. Improved direct bonding of Si and SiO2 surfaces by cleaning in H2SO4:H2O2:HF

    NASA Astrophysics Data System (ADS)

    Ljungberg, Karin; Söderbärg, Anders; Jansson, Ulf

    1995-07-01

    A method for silicon surface preparation prior to wafer bonding is presented. By cleaning the wafers in a H2SO4:H2O2 mixture in which a small amount of HF is added, and then rinsing in H2O, the bonding behavior of the surfaces is improved, compared to other pretreatments used for bonding. The modified SPM cleaning results in a highly fluorinated chemical oxide on the Si surface. A subsequent water rinse causes substitution of F by OH groups, which increase the initial attraction of the mating surfaces. Higher contact wave velocities and bond strengths than reported for other surface pretreatments have been measured, both for bare and thermally oxidized silicon surfaces.

  5. HCl Vapour Pressures and Reaction Probabilities for ClONO2 + HCl on Liquid H2SO4-HNO3-HCl-H20 Solutions

    NASA Technical Reports Server (NTRS)

    Elrod, M. J.; Koch, R. E.; Kim, J. E.; Molina, M. J.

    1995-01-01

    Henry's Law solubility constants for HCl have been measured for liquid H2SO4-HNO3-HCl-H2O solutions; the results are in good agreement with predictions from published semiempirical models. The ClONO2 + HCl reaction on the surfaces of such solutions with compositions simulating those of stratospheric aerosols has been investigated; as the composition changes following the temperature drop characteristic of the high-latitude stratosphere the reaction probability gamma increases rapidly. Furthermore, the gamma values remain essentially unchanged when HN03 uptake is neglected; the controlling factor appears to be the solubility of HCl. These results corroborate our earlier suggestion that supercooled liquid sulfate aerosols promote chlorine activation at low temperatures as efficiently as solid polar stratospheric cloud particles.

  6. Arabinose substitution degree in xylan positively affects lignocellulose enzymatic digestibility after various NaOH/H2SO4 pretreatments in Miscanthus.

    PubMed

    Li, Fengcheng; Ren, Shuangfeng; Zhang, Wei; Xu, Zhengdan; Xie, Guosheng; Chen, Yan; Tu, Yuanyuan; Li, Qing; Zhou, Shiguang; Li, Yu; Tu, Fen; Liu, Lin; Wang, Yanting; Jiang, Jianxiong; Qin, Jingping; Li, Shizhong; Li, Qiwei; Jing, Hai-Chun; Zhou, Fasong; Gutterson, Neal; Peng, Liangcai

    2013-02-01

    Xylans are the major hemicelluloses in grasses, but their effects on biomass saccharification remain unclear. In this study, we examined the 79 representative Miscanthus accessions that displayed a diverse cell wall composition and varied biomass digestibility. Correlation analysis showed that hemicelluloses level has a strong positive effect on lignocellulose enzymatic digestion after NaOH or H(2)SO(4) pretreatment. Characterization of the monosaccharide compositions in the KOH-extractable and non-KOH-extractable hemicelluloses indicated that arabinose substitution degree of xylan is the key factor that positively affects biomass saccharification. The xylose/arabinose ratio after individual enzyme digestion revealed that the arabinose in xylan is partially associated with cellulose in the amorphous regions, which negatively affects cellulose crystallinity for high biomass digestibility. The results provide insights into the mechanism of lignocellulose enzymatic digestion upon pretreatment, and also suggest a goal for the genetic modification of hemicelluloses towards the bioenergy crop breeding of Miscanthus and grasses.

  7. Effect of leaching with 5-6 N H2SO4 on thermal kinetics of rice husk during pure silica recovery.

    PubMed

    Ali, Muhammad; Ul Haq, Ehsan; Abdul Karim, Muhammad R; Ahmed, Sajjad; Ibrahim, Ather; Ahmad, Waheed; Baig, Waqas M

    2016-01-01

    Rice husk is a potential source for renewable energy and silica. To extract the maximum amount of silica, usually the rice husk is treated with strong acids that burn the organic part leaving behind a black residue. In this research, sulfuric acid is used as an oxidizing agent. Efforts are focused to find out more about the behavior of acid-treated rice husk by using thermal exposure, and results are compared with results for raw rice husk which is thermally exposed but not acid treated. Reaction ratio of rice husk combustion and energy of activation were calculated using the thermogravimetric data. Acid treatment was found influential in initiating degradation earlier compared to raw husk and an overall increase in value of activation energy was observed when heating rate was increased. PMID:26843969

  8. Effect of leaching with 5–6 N H2SO4 on thermal kinetics of rice husk during pure silica recovery

    PubMed Central

    Ali, Muhammad; Ul Haq, Ehsan; Abdul Karim, Muhammad R.; Ahmed, Sajjad; Ibrahim, Ather; Ahmad, Waheed; Baig, Waqas M.

    2015-01-01

    Rice husk is a potential source for renewable energy and silica. To extract the maximum amount of silica, usually the rice husk is treated with strong acids that burn the organic part leaving behind a black residue. In this research, sulfuric acid is used as an oxidizing agent. Efforts are focused to find out more about the behavior of acid-treated rice husk by using thermal exposure, and results are compared with results for raw rice husk which is thermally exposed but not acid treated. Reaction ratio of rice husk combustion and energy of activation were calculated using the thermogravimetric data. Acid treatment was found influential in initiating degradation earlier compared to raw husk and an overall increase in value of activation energy was observed when heating rate was increased. PMID:26843969

  9. Experimental study and neural network modeling of sugarcane bagasse pretreatment with H2SO4 and O3 for cellulosic material conversion to sugar.

    PubMed

    Gitifar, Vahid; Eslamloueyan, Reza; Sarshar, Mohammad

    2013-11-01

    In this study, pretreatment of sugarcane bagasse and subsequent enzymatic hydrolysis is investigated using two categories of pretreatment methods: dilute acid (DA) pretreatment and combined DA-ozonolysis (DAO) method. Both methods are accomplished at different solid ratios, sulfuric acid concentrations, autoclave residence times, bagasse moisture content, and ozonolysis time. The results show that the DAO pretreatment can significantly increase the production of glucose compared to DA method. Applying k-fold cross validation method, two optimal artificial neural networks (ANNs) are trained for estimations of glucose concentrations for DA and DAO pretreatment methods. Comparing the modeling results with experimental data indicates that the proposed ANNs have good estimation abilities. PMID:24035818

  10. Experimental study and neural network modeling of sugarcane bagasse pretreatment with H2SO4 and O3 for cellulosic material conversion to sugar.

    PubMed

    Gitifar, Vahid; Eslamloueyan, Reza; Sarshar, Mohammad

    2013-11-01

    In this study, pretreatment of sugarcane bagasse and subsequent enzymatic hydrolysis is investigated using two categories of pretreatment methods: dilute acid (DA) pretreatment and combined DA-ozonolysis (DAO) method. Both methods are accomplished at different solid ratios, sulfuric acid concentrations, autoclave residence times, bagasse moisture content, and ozonolysis time. The results show that the DAO pretreatment can significantly increase the production of glucose compared to DA method. Applying k-fold cross validation method, two optimal artificial neural networks (ANNs) are trained for estimations of glucose concentrations for DA and DAO pretreatment methods. Comparing the modeling results with experimental data indicates that the proposed ANNs have good estimation abilities.

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

    PubMed

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

    2015-11-01

    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

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

    PubMed

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

    2015-11-01

    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

  13. 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

  14. Total sulfate vs. sulfuric acid monomer concenterations in nucleation studies

    NASA Astrophysics Data System (ADS)

    Neitola, K.; Brus, D.; Makkonen, U.; Sipilä, M.; Mauldin, R. L., III; Sarnela, N.; Jokinen, T.; Lihavainen, H.; Kulmala, M.

    2015-03-01

    Sulfuric acid is known to be a key component for atmospheric nucleation. Precise determination of sulfuric-acid concentration is a crucial factor for prediction of nucleation rates and subsequent growth. In our study, we have noticed a substantial discrepancy between sulfuric-acid monomer concentrations and total-sulfate concentrations measured from the same source of sulfuric-acid vapor. The discrepancy of about 1-2 orders of magnitude was found with similar particle-formation rates. To investigate this discrepancy, and its effect on nucleation, a method of thermally controlled saturator filled with pure sulfuric acid (97% wt.) for production of sulfuric-acid vapor is applied and rigorously tested. The saturator provided an independent vapor-production method, compared to our previous method of the furnace (Brus et al., 2010, 2011), to find out if the discrepancy is caused by the production method itself. The saturator was used in a H2SO4-H2O nucleation experiment, using a laminar flow tube to check reproducibility of the nucleation results with the saturator method, compared to the furnace. Two independent methods of mass spectrometry and online ion chromatography were used for detecting sulfuric-acid or sulfate concentrations. Measured sulfuric-acid or total-sulfate concentrations are compared to theoretical predictions calculated using vapor pressure and a mixing law. The calculated prediction of sulfuric-acid concentrations agrees very well with the measured values when total sulfate is considered. Sulfuric-acid monomer concentration was found to be about 2 orders of magnitude lower than theoretical predictions, but with a temperature dependency similar to the predictions and the results obtained with the ion-chromatograph method. Formation rates are reproducible when compared to our previous results with both sulfuric-acid or total-sulfate detection and sulfuric-acid production methods separately, removing any doubts that the vapor-production method would

  15. Effect of electrochemical treatment in H2SO4 aqueous solution on carbon material derived from cellulose with added guanidine phosphate

    NASA Astrophysics Data System (ADS)

    Tsubota, Toshiki; Wang, Chuanshu; Murakami, Naoya; Ohno, Teruhisa

    2013-03-01

    The electrochemical treatment in a 1 M H2SO4 aqueous solution is applied to the carbon material synthesized from cellulose mixed with guanidine phosphate. The capacitance value increased by the addition of guanidine phosphate; furthermore, the value significantly increased by the electrochemical treatment and was higher than 350 F g-1 at 50 mA g-1. The process used in this study, that is, removing the lignin from wood waste products, such as bamboo, and then mixing with guanidine phosphate before the heat treatment followed by an electrochemical treatment, should be of benefit for the synthesis of a high performance material for the electrodes of electrochemical capacitors. The significant enhancement of the capacitance value appears in the range of 1.5 V∼2.8 V vs. Ag/AgCl for the applied maximum voltage. This voltage range is consistent with the voltage for the significant enhancement of the current value in the CV curve. The change in the capacitance value should be related to the electrochemical reaction of the water electrolysis. The XPS data indicated that the concentrations of both the N atom and the O atom on the surface increased after the electrochemical process.

  16. X-ray investigation of molten crystal hydrates H2SO4(nH2O) and HNO3(nH2O)

    NASA Technical Reports Server (NTRS)

    Romanova, A. V.; Skryshevskiy, A. F.

    1979-01-01

    Integral analysis of the intensity of the electron density distribution curve in molten crystal hydrates provided by X-ray analysis, permits the following conclusions on the structure of the complex SO and NO ions, and the short-range order in the structure of the solution. The SO4 ion in the solution has a tetrahedral structure with an S to O distance equal to 1.5 A. For the NO3 in the solution, a planar triangular shape is probable, with an N to O distance equal to 1.2 A. Preferential distances between each of the oxygens of the SO ion and the nearest molecules of water proved near to the corresponding distances in solid crystal hydrates. For an (H2SO4)(H2O) solution, the average number of water molecules surrounding each oxygen atom of the SO4 (--) ion was on the order of 1.3 molecules. Hence the preferential distances between the water molecules and the oxygen atoms of the SO ion, and the preference of their mutual position, correspond to the fixed position of these same elements of the structure in the solid crystal hydrate.

  17. A variable temperature study of the transport properties of aqueous solutions of VOSO4 and NH4VO3 in 2 M H2SO4

    NASA Astrophysics Data System (ADS)

    Suarez, Sophia; Sahin, Meriam; Adam, Yara; Moussignac, Lucy; Cuffari, David; Paterno, Domenec

    2015-02-01

    Variable temperature ionic conductivity, viscosity and 1H NMR spin-lattice relaxation times, linewidths and chemical shifts measurements were determined for various concentrations of aqueous ammonium metavanadate (NH4VO3) and vanadyl sulfate (VOSO4) over the temperature range of 20-100 °C. Concentration ranges of 0.05-2 M and 0.05-0.2 M were investigated for VOSO4 and NH4VO3 respectively in 2 M H2SO4. Results show ion and proton transport processes that are mediated strongly by increasing solution viscosity, especially in the case of VOSO4. Activation energies calculated from ionic conductivity and solution viscosity show greater energy being needed for translational ion dynamics with increasing concentration for both solutions. Additionally, data suggest that with greater metal ion concentration ion association is more prevalent for the vanadyl ion. The differences between the transport capabilities of the two solution are discussed in terms of the 1H NMR, ionic conductivity and viscosity data.

  18. Ternary H2SO4-H2O-NH3 neutral and charged nucleation rates for a wide range of atmospheric conditions

    NASA Astrophysics Data System (ADS)

    Kürten, Andreas; Bianchi, Federico; Almeida, Joao; Duplissy, Jonathan; Dunne, Eimear M.; Breitenlechner, Martin; Praplan, Arnaud P.; Ortega, Ismael K.; Kupiainen, Oona; Rondo, Linda; Ehrhart, Sebastian; Kirkby, Jasper; Curtius, Joachim; Cloud Collaboration

    2013-05-01

    The formation of new particles for the ternary system involving sulfuric acid, water vapor and ammonia has been studied in detail. The nucleation rates were obtained from experiments at the CERN CLOUD chamber which allows the measurement of new particle formation under very well defined conditions. Some of its key features are the suppression of contaminants at the technological limit and a very precise control of a wide range of temperatures, trace gas concentrations and nucleation rates. The effect of ionizing radiation on the ternary nucleation rates was investigated by using the CERN proton synchrotron beam (beam conditions), natural galactic cosmic rays (gcr conditions) as well as the high voltage clearing field inside the chamber to suppress the effect of charges (neutral conditions). The dependence of the nucleation rate on ion concentration, sulfuric acid and ammonia concentration as well as temperature was studied extensively. This way, an unprecedented set of data was collected giving insight into the role of neutral and charged ternary NH3 nucleation and the relative importance of the different parameters.

  19. Toward elimination of discrepancies between theory and experiment: the rate constant of the atmospheric conversion of SO3 to H2SO4.

    PubMed

    Loerting, T; Liedl, K R

    2000-08-01

    The hydration rate constant of sulfur trioxide to sulfuric acid is shown to depend sensitively on water vapor pressure. In the 1:1 SO3-H2O complex, the rate is predicted to be slower by about 25 orders of magnitude compared with laboratory results [Lovejoy, E. R., Hanson, D. R. & Huey, L. G. (1996) J. Phys. Chem. 100, 19911-19916; Jayne, J. T., Poschl, U., Chen, Y.-m., Dai, D., Molina, L. T., Worsnop, D. R., Kolb, C. E. & Molina, M. J. (1997) J. Phys. Chem. A 101, 10000-10011]. This discrepancy is removed mostly by allowing a second and third water molecule to participate. An asynchronous water-mediated double proton transfer concerted with the nucleophilic attack and a double proton transfer accompanied by a transient H3O+ rotation are predicted to be the fastest reaction mechanisms. Comparison of the predicted negative apparent "activation" energies with the experimental finding indicates that in our atmosphere, different reaction paths involving two and three water molecules are taken in the process of forming sulfate aerosols and consequently acid rain.

  20. Stratospheric sulfuric acid fraction and mass estimate for the 1982 volcanic eruption of El Chichon

    NASA Technical Reports Server (NTRS)

    Hofmann, D. J.; Rosen, J. M.

    1983-01-01

    The stratospheric sulfuric acid fraction and mass for the 1982 volcanic eruptions of El Chichon are investigated using data from balloon soundings at Laramie (41 deg N) and in southern Texas (27-29 deg N). The total stratospheric mass of these eruptions is estimated to be approximately 8 Tg about 6.5 months after the eruption with possibly as much as 20 Tg in the stratosphere about 45 days after the eruption. Observations of the aerosol in Texas revealed two primary layers, both highly volatile at 150 C. Aerosol in the upper layer at about 25 km was composed of an approximately 80 percent H2SO4 solution while the lower layer at approximately 18 km was composed of a 60-65 percent H2SO4 solution aerosol. It is calculated that an H2SO4 vapor concentration of at least 3 x 10 to the 7th molecules/cu cm is needed to sustain the large droplets in the upper layer. An early bi-modal nature in the size distribution indicates droplet nucleation from the gas phase during the first 3 months, while the similarity of the large particle profiles 2 months apart shows continued particle growth 6.5 months after the explosion.

  1. An Experimental Study of Single Suspended H2so4/nh3/h2o-aerosols : Atmospheric Relevance of Letovicite

    NASA Astrophysics Data System (ADS)

    Colberg, C. A.; Krieger, U. K.; Luo, B.; Wernli, H.; Peter, Th.

    Aerosols in the atmosphere have a large effect on the radiative balance of the earth due to their scattering and absorbing properties. Some aerosols can also act as cloud con- densation nuclei (CCN) of cirrus clouds which play an important role for the global climate. The influence of NH3 and H2SO4 containing aerosols on cirrus formation are discussed. The thermodynamic and kinetic behavior of the H2SO4/NH3/H2O-system at atmospheric conditions is poorly understood. The reason for this uncertainty is that thermodynamic models are mainly based on experimental data obtained at room tem- perature and that the conditions at which aerosols crystallize cannot be predicted re- liably. Hence, laboratory experiments are needed to improve our knowledge of the chemical and physical state of inorganic aerosols in the atmosphere. In the present work laboratory measurements of individual H2SO4/NH3/H2O-aerosols in an electrodynamic particle trap are performed. The trap is located in a thermally in- sulated chamber where the relative humidity (RH), the total pressure and temperature are controlled. The DC-Voltage is used as a direct measure for the mass of the parti- cles. The radii of liquid droplets are determined by Mie-phase-function-analysis and RMS-deviation measurements of the intensity fluctuations provide information on the aerosol morphology. Raman-spectroscopy is used to identify liquid and solid parti- cles chemically. These four analytical tools provide independent information on the aerosol composition and structure. The thermodynamic behavior of single suspended particles is examined for different stoichiometries at different temperatures and relative humidities. The deliquescence and efflorescence relative humidities (DRH and ERH), as well as the water uptake and loss are studied. In general the thermodynamic data of the present work is in good agreement to the model with Clegg et al. [1998] and existing experimental data. The observed solid phases are, surprisingly

  2. Controls and rates of acid production in commercial-scale sulfur blocks.

    PubMed

    Birkham, T K; Hendry, M J; Barbour, S L; Lawrence, J R

    2010-01-01

    Acidic drainage (pH 0.4-1.0) from oxidizing elemental sulfur (S(0)) blocks is an environmental concern in regions where S(0) is stockpiled. In this study, the locations, controls, and rates of H(2)SO(4) production in commercial-scale S(0) blocks ( approximately 1-2 x 10(6) m(3)) in northern Alberta, Canada, were estimated. In situ modeling of O(2) concentrations ([O(2)]) suggest that 70 to >97% of the annual H(2)SO(4) production occurs in the upper 1 m of the blocks where temperatures increase to >15 degrees C during the summer. Laboratory experiments show that S(0) oxidation rates are sensitive to temperature (Q(10) = 4.3) and dependent on the activity of autotrophic S(0)-oxidizing microbes. The annual efflux of SO(4) in drainage water from a S(0) block (5.5 x 10(5) kg) was within the estimated range of SO(4) production within the block (2.7 x 10(5) to 1.2 x 10(6) kg), suggesting that H(2)SO(4) production and removal rates were approximately equal during the study period. The low mean relative humidity within the block (68%; SD = 17%; n = 21) was attributed to osmotic suction from elevated H(2)SO(4) concentrations and suggests a mean in situ pH of approximately -2.1. The low pH of drainage waters was attributed to the mixing of fresh infiltrating water and low-pH in situ water. Heat generation during S(0) oxidation was an important factor in maintaining elevated temperatures (mean, 11.1 degrees C) within the block. The implications of this research are relevant globally because construction methods and the physical properties of S(0) blocks are similar worldwide.

  3. 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.

  4. 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.

  5. Heterogeneous Reactions of ClONO2, HCl, and HOCl on Liquid Sulfuric Acid Surfaces

    NASA Technical Reports Server (NTRS)

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

    1994-01-01

    The heterogeneous reactions of ClONO2 + H2O yields HNO3 + HOCl (1), ClONO2 + HCl yields C12 + HNO3 (2), and HOCl + HCl yields Cl2 + H2O (3) on liquid sulfuric acid surfaces have been studied using a fast flow reactor coupled to a quadrupole mass spectrometer. The main objectives of the study are to investigate: (a) the temperature dependence of these reactions at a fixed H2O partial pressure typical of the lower stratosphere (that is, by changing temperature at a constant water partial pressure, the H2SO4 content of the surfaces is also changed), (b) the relative importance or competition between reactions 1 and 2, and (c) the effect of HNO3 on the reaction probabilities due to the formation of a H2SO4/HNO3/H2O ternary system. The measurements show that all the reactions depend markedly on temperature at a fixed H2O partial pressure: they proceed efficiently at temperatures near 200 K and much slower at temperatures near 220 K. The reaction probability (gamma(sub 1)) for ClONO2 hydrolysis approaches 0.01 at temperatures below 200 K, whereas the values for gamma(sub 2) and gamma(sub 3) are on the order of a few tenths at 200 K. Although detailed mechanisms for these reactions are still unknown, the present data indicate that the competition between ClONO2 hydrolysis and ClONO2 reaction with HCl may depend on temperature (or H2SO4 Wt %): in the presence of gaseous HCl at stratospheric concentrations, reaction 2 is dominant at lower temperatures (less than 200 K), but reaction 1 becomes important at temperatures above 210 K. Furthermore, reaction probability measurements performed on the H2SO4/HNO3/ H2O ternary solutions do not exhibit noticeable deviation from those performed on the H2SO4/H2O binary system, suggesting little effect of HNO3 in sulfate aerosols on the ClONO2 and HOCl reactions with HCl. The results reveal that significant reductions in the chlorine-containing reservoir species (such as ClONO2 and HCl) can take place on stratospheric sulfate aerosols at

  6. 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.

  7. The uptake of 2-methyl-3-buten-2-ol into aqueous mixed solutions of sulfuric acid and hydrogen peroxide.

    PubMed

    Liu, Ze; Ge, Maofa; Wang, Weigang; Yin, Shi; Tong, Shengrui

    2011-02-14

    Multiphase acid-catalyzed oxidation with hydrogen peroxide (H(2)O(2)) has been suggested recently to be a potential route to SOA formation from isoprene and its gas-phase oxidation products, the kinetics and chemical mechanism of this process have not been well-known yet. In this work, the uptake of 2-methyl-3-buten-2-ol (MBO), an important biogenic hydrocarbon and structurally similar to isoprene, into aqueous mixed solutions of H(2)O(2) and sulfuric acid (H(2)SO(4)) was performed using a rotated wetted-wall reactor coupled to a differentially pumped single-photon ionization time of flight mass spectrometer (RWW-SPI-TOFMS). The reactive uptake coefficients (γ) were acquired for the first time and the reaction pathways were deduced according to products information. The reactive uptake coefficients of MBO into H(2)SO(4)-H(2)O(2) mixed solutions are much greater than that into H(2)SO(4) solutions. Acetaldehyde, acetone and an on-line product, which transformed to isoprene readily in the duration of an off-line experiment, were suggested as products in this process. The further reactions of the carbonyl products can occur in acidic solution, which may play a role in SOA formation. Additionally, in real atmosphere the on-line product is apt to transform to isoprene, an acknowledged precursor of biogenic SOA. Thus, the multiphase acid-catalyzed oxidation of MBO with H(2)O(2) might be a potential contributor to SOA loading.

  8. [Uptake of 3-methyl-3-buten-1-ol into aqueous mixed solution of sulfuric acid and hydrogen peroxide].

    PubMed

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

    2011-12-01

    Multiphase acid-catalyzed oxidation with hydrogen peroxide (H2O2) has been suggested recently to be a potential route to SOA formation, but the kinetics and chemical mechanism of this process have not been well-known yet. In this work, the uptake of 3-methyl-3-buten-1-ol (MBO331) into aqueous mixed solutions of H2O2, and sulfuric acid (H2SO4) was performed using a rotated wetted-wall reactor coupled to a VUV single-photon ionization time of flight mass spectrometer (VUV-SPI-TOFMS). The reactive uptake coefficients (gamma) were acquired for the first time and the reaction pathways were deduced according to products information. The uptake of MBO331 into H2SO4/H2O2 was fast, resulting in gamma reaching 2.52 x 10(-4)-1.05 x 10(-2) for 40%-60% H2SO4. Acetaldehyde, acetone and 3-methyl-3, 4-expoxybutane-1-ol were suggested as gas-phase products in this process. 3-methyl-3,4-expoxybutane-1-ol can transform into polyhydroxy compounds while the further reactions of the carbonyl products can occur in acidic solution, which may play a role in SOA formation. Thus, the heterogeneous acid-catalyzed oxidation of MBO331 with H2O2 might be a significant contributor to SOA loading.

  9. Flexible all-solid-state supercapacitors based on graphene/carbon black nanoparticle film electrodes and cross-linked poly(vinyl alcohol)-H2SO4 porous gel electrolytes

    NASA Astrophysics Data System (ADS)

    Fei, Haojie; Yang, Chongyang; Bao, Hua; Wang, Gengchao

    2014-11-01

    Flexible all-solid-state supercapacitors (SCs) are fabricated using graphene/carbon black nanoparticle (GCB) film electrodes and cross-linked poly(vinyl alcohol)-H2SO4 porous gel electrolytes (gPVAP-H2SO4). The GCB composite films, with carbon black (CB) nanoparticles uniformly distributed in the graphene nanosheets, greatly improve the active surface areas and ion transportation of pristine graphene film. The porous structure of as-prepared gPVAP-H2SO4 membrane improves the equilibrium swelling ratio in electrolyte and provides interconnected ion transport channels. The chemical crosslinking solves the fluidity problem of PVA-H2SO4 gel electrolyte at high temperature. As-fabricated GCB//gPVAP(20)-H2SO4//GCB flexible SC displays an increased specific capacitance (144.5 F g-1 at 0.5 A g-1) and a higher specific capacitance retention (67.9% from 0.2 to 4 A g-1). More importantly, the flexible SC possesses good electrochemical performance at high temperature (capacitance retention of 78.3% after 1000 cycles at 70 °C).

  10. Solvent effect on proton transfer in the complexes of N,N-dimethylformamide with sulfuric and phosphoric acid: A DFT investigation

    NASA Astrophysics Data System (ADS)

    Fedorova, Irina V.; Krestyaninov, Michael A.; Kiselev, Michael G.; Safonova, Lyubov P.

    2016-02-01

    Ab initio quantum-chemical calculations of structure and energies of the complexes of N,N-dimethylformamide (DMF) with sulfuric (H2SO4) and phosphoric (H3PO4) acids have been carried out. It has been found that the hydrogen bond between H2SO4 and DMF molecules is a little shorter and stronger than that between H3PO4 and DMF. The H-bond strength is different both in acid-acid and (acid)n-DMF complexes for n = 1, 2. The polar solvent effect is taken into account by using the CPCM approach. The differences of geometric parameters of the H-bonds in the gas phase and DMF are analyzed. The potential energy surface (PES) of the proton transfer reaction in acid-DMF and (acid)2-DMF complexes was calculated. The calculations have shown that the gas phase PES has a single distinct minimum (with the exception of the (H2SO4)2-DMF). In DMF, the proton transfer reaction takes place in all complexes, if OACID … ODMF distance is constrained. The solvent effect favors a proton transfer from sulfuric acid to oxygen atom of DMF molecule and formation of stable ionic pairs.

  11. 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.

  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. 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%.

  14. 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.

  15. Heterogeneous Interactions of ClONO2 and HCl with Sulfuric Acid Tetrahydrate: Implications for the Stratosphere

    NASA Technical Reports Server (NTRS)

    Zhang, Renyi; Jayne, John T.; Molina, Mario J.

    1994-01-01

    The reaction probabilities for ClONO2+H2O- HOCl + HNO3 and ClONO2+ HCl Cl2 +HNO3 have been investigated on sulfuric acid tetrahydrate (SAT, H2SO4-4H2O)surfaces at temperatures between 190 and 230 K and at reactant concentrations that are typical in the lower stratosphere, using a fast-flow reactor coupled to a quadrupole mass spectrometer. The results indicate that the reaction probabilities as well as HCl uptake depend strongly on the thermodynamic state of SAT surface: they decrease significantly with decreasing H2O partial pressure at a given temperature, and decrease with increasing temperature at a given H2O partial pressure, as the SAT changes from the H2O-rich form to the H2SO4-rich form. For H2O-rich SAT at 195 K gamma(sub 1) approx. = -0.01 and gamma(sub 2) greater or equal to 0.1, whereas the values for H2SO4-rich SAT decrease by more than 2 orders of magnitude. At low concentrations of HCl, close to those found in the stratosphere, the amount of HCl taken up by H2O-rich SAT films corresponds to a coverage of the order of a tenth of a monolayer (approx. = 10(exp 14) molecules/sq cm); H2SO4-rich SAT films take up 2 orders of magnitude less HCl (les than 10(exp 12) molecules/sq cm). Substantial HCl uptake at high HCl concentrations is also observed, as a result of surface melting. The data reveal that frozen stratospheric sulfate aerosols may play an important role in chlorine activation in the winter polar stratosphere via processes similar to those occurring on the surfaces of polar stratospheric cloud particles.

  16. Sulfur Cycle

    NASA Technical Reports Server (NTRS)

    Hariss, R.; Niki, H.

    1985-01-01

    Among the general categories of tropospheric sulfur sources, anthropogenic sources have been quantified the most accurately. Research on fluxes of sulfur compounds from volcanic sources is now in progress. Natural sources of reduced sulfur compounds are highly variable in both space and time. Variables, such as soil temperature, hydrology (tidal and water table), and organic flux into the soil, all interact to determine microbial production and subsequent emissions of reduced sulfur compounds from anaerobic soils and sediments. Available information on sources of COS, CS2, DMS, and H2S to the troposphere in the following paragraphs are summarized; these are the major biogenic sulfur species with a clearly identified role in tropospheric chemistry. The oxidation of SO2 to H2SO4 can often have a significant impact on the acidity of precipitation. A schematic representation of some important transformations and sinks for selected sulfur species is illustrated.

  17. 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.

  18. Matrix isolation infrared spectrum of the sulfuric acid-monohydrate complex: new assignments and resolution of the "missing H-Bonded v(OH) band" issue.

    PubMed

    Rozenberg, M; Loewenschuss, A

    2009-04-30

    The matrix isolation infrared spectra of "dry" and "wet" vapors of sulfuric acid have been investigated as trapped in solid argon matrices. The availability of a spectrum of trapped anhydrous acid vapor and its comparison with the spectra of trapped water containing vapors of the acid allowed the identification of the hydrogen-bonding shifted hydroxyl bands for both the acid and the water moieties of the monohydrated H(2)SO(4).H(2)O complex. The experimental results are compared to the various theoretically calculated wavenumber values of the acid and its monohydrated complex. The complex stabilization energies, as obtained from calculations and empirical correlations, are compared.

  19. 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

  20. Synergistic effect of iodide ions on the corrosion inhibition of steel in 0.5 M H 2SO 4 by new chalcone derivatives

    NASA Astrophysics Data System (ADS)

    Bouklah, M.; Hammouti, B.; Aouniti, A.; Benkaddour, M.; Bouyanzer, A.

    2006-07-01

    The effect of addition of 4',4-dihydroxychalcone (P 1), 4-aminochalcone (P 2) and 4-bromo, 4'-methoxychalcone (P 3) on the corrosion of steel in 0.5 M sulphuric acid has been studied by weight loss measurements, potentiodynamic and EIS measurements. We investigate the synergistic effect of iodide ions on the corrosion inhibition of steel in the presence of chalcone derivatives. The corrosion rates of the steel decrease with the increase of the chalcones concentration, while the inhibition efficiencies increase. The addition of iodide ions enhances the inhibition efficiency considerably. The presence of iodide ions increases the degree of surface coverage. The synergism parameters SΘ and SI, calculated from surface coverage and the values of inhibition efficiency, in the case of chalcone derivatives are found to be larger than unity. The enhanced inhibition efficiency in the presence of iodide ions is only due to synergism and there is a definite contribution from the inhibitors molecules. E (%) obtained from the various methods is in good agreement. Polarisation measurements show also that the compounds act as cathodic inhibitors.

  1. 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.

  2. Differential responses of certain lichen species to sulfur-containing solutions under acidic conditions as expressed by the production of stress-ethylene.

    PubMed

    Garty, J; Kauppi, M; Kauppi, A

    1995-05-01

    To determine whether fluctuations in the concentration of ethylene produced by lichens exposed to sulfur-containing solutions at a low pH correlate with the tolerance/sensitivity of these lichens to air pollution, we measured the amount of ethylene produced by thalli soaked in H2SO4 and NaHSO3. The exposure of Hypogymnia physodes, Cladina stellaris, and Bryoria fuscescens to H2SO4 at a pH ranging between 4.0 and 2.0 did not produce changes in the concentration of ethylene in comparison with samples wetted with H2O at pH 6.8. The exposure of two pendulous lichens, Usnea hirta and Alectoria sarmentosa, to 1.0 and 5.0 mM H2SO4 at pH 2.7 and 2.0, respectively, stimulated only a slight increase of ethylene production, whereas another pendulous lichen, Bryoria fremontii, exposed to H2SO4 at pH 4.0-2.0 decreased its production of ethylene. The soaking of H. physodes, U. hirta, C. stellaris, and A. sarmentosa thalli in NaHSO3 at pH 4.0 gradually increased the production of ethylene. The exposure of B. fremontii and B. fuscescens to low NaHSO3 concentrations depressed the production of ethylene in these lichens. The indifference of H. physodes to H2SO4 under strong acidic conditions correlated with its resistance to SO2 in the air. In accordance with a model by D.M. Reid (In "Effects of Atmospheric Pollutants on Forests, Wetlands and Agricultural Ecosystems" (T.C. Hutchinson and K.M. Meema, Eds.), Vol G 16, pp. 241-245. NATO ASI Series, Springer-Verlag, Berlin and Heidelberg, 1987) referring to higher plants, it is suggested that sulfur-containing solutions under acidic conditions increase the solubility of particles containing heavy metals entrapped among the mycobiont hyphae in lichens. This may lead to an increase of the production of endogenous ethylene in lichens as they are exposed to sulfur-containing chemicals, to acidic rain, or to heavy metal-polluted air.

  3. Optimization of thermal-dilute sulfuric acid pretreatment for enhancement of methane production from cassava residues.

    PubMed

    Zhang, Qinghua; Tang, Lei; Zhang, Jianhua; Mao, Zhonggui; Jiang, Li

    2011-02-01

    In this study, the pretreatment of cassava residues by thermal-dilute sulfuric acid (TDSA) hydrolysis was investigated by means of a statistically designed set of experiments. A three-factor central composite design (CCD) was employed to identify the optimum pretreatment condition of cassava residues for methane production. The individual and interactive effects of temperature, H(2)SO(4) concentration and reaction time on increase of methane yield (IMY) were evaluated by applying response surface methodology (RSM). After optimization, the resulting optimum pretreatment condition was 157.84°C, utilizing 2.99% (w/w TS) H(2)SO(4) for 20.15 min, where the maximum methane yield (248 mL/g VS) was 56.96% higher than the control (158 mL/g VS), which was very close to the predict value 56.53%. These results indicate the model obtained through RSM analysis is suit to predict the optimum pretreatment condition and there is great potential of using TDSA pretreatment of cassava residues to enhance methane yield.

  4. 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.

  5. Soot and Sulfuric Acid from Aircraft: Is There Enough to Cause Detrimental Environmental E-kCTSs?

    NASA Technical Reports Server (NTRS)

    Pueschel, R. F.; Strawa, A. W.; Ferry, G. V.; Howard, S. D.; Verma, S.

    1998-01-01

    Aerosol from aircraft can affect the environment in three ways: First, soot aerosol has been implicated to cause Icing-tern ozone depletion at mid-latitudes in the lower stratosphere at a rate of approx. 5% per decade. This effect is in addition and unrelated to the polar ozone holes which are strongly influenced by heterogeneous chemistry on polar stratospheric clouds. Second, the most obvious effect of jet aircraft is the formation of visible contrails in the upper troposphere. The Salt Lake City region experienced an 8% increase in cirrus cloud cover over a 15-year period which covariates with an increase in regional commercial air traffic. If soot particles act as freezing nuclei to cause contrail formation heterogeneously, they would be linked to a secondary effect to cloud modification that very likely is climatologically important. Third, a buildup of soot aerosol could reduce the single scatter albedo of stratospheric aerosol from 0.993+0.004 to 0.98, a critical value that has been postulated to separate stratospheric cooling from warming. Thus arises an important question: Do aircraft emit sufficient amounts of soot to have detrimental effects and warrant emission controls? During the 1996 SUCCESS field campaign, we sampled aerosols in the exhaust wake of a Boeing 757 aircraft and determined emission indices for sulfuric acid (EI(sub H2SO4) = 9.0E-2 and 5.0E-1 g/kg (sub FUEL) for 75 and 675 ppm fuel-sulfur, respectively) and soot aerosol (2.2E-3 less than EI(sub SOOT) = l.lE-2 g/kg (sub FUEL)). The soot particle analysis accounted for their fractal nature, determined electron-microscopically, which enhanced the surface area by a factor of 26 and the volume 11-fold over equivalent-volume spheres. The corresponding fuel-sulfur to H2SO4 conversion efficiency was 10% (for 675 ppmm fuel-S) and 37% (for 75 ppmm fuel-S). Applying the H2SO4 emission index to the 1990 fuel use by the worlds commercial fleets of 1.3E11 kg, a conversion efficiency of 30% of 500 ppmm

  6. Galvanic interaction between chalcopyrite and manganese dioxide in sulfuric acid medium

    NASA Astrophysics Data System (ADS)

    Gantayat, B. P.; Rath, P. C.; Paramguru, R. K.; Rao, S. B.

    2000-02-01

    Dissolution of chalcopyrite and managanese dioxide minerals in the presence of each other in sulfuric acid medium was studied using compact disc electrodes of the minerals under various H2SO4 concentrations (0.05 to 0.5 M). [H+] had a positive effect on the reaction rate. Strong galvanic interaction was observed to take place between chalcopyrite and manganese dioxide, the galvanic interaction predominating over the individual dissolution (self-corrosion) rates. Evans diagrams constructed from polarization curves of the two minerals were helpful in interpreting the leaching data. The electrochemical nature of the dissolution reaction was analyzed through application of the Butler-Volmer equation and was confirmed from polarization measurements conducted with the respective mineral electrodes.

  7. Phyllanthus muellerianus and C6H15NO3 synergistic effects on 0.5 M H2SO4-immersed steel-reinforced concrete: Implication for clean corrosion-protection of wind energy structures in industrial environment

    NASA Astrophysics Data System (ADS)

    Okeniyi, Joshua Olusegun; Omotosho, Olugbenga Adeshola; Popoola, Abimbola Patricia Idowu; Loto, Cleophas Akintoye

    2016-07-01

    This paper investigates Phyllanthus muellerianus leaf-extract and C6H15NO3 (triethanolamine: TEA) synergistic effects on reinforcing-steel corrosion-inhibition and the compressive-strength of steel-reinforced concrete immersed in 0.5 M H2SO4. This is to assess suitability of the synergistic admixture usage for wind-energy steel-reinforced concrete structures designed for industrial environments. Steel-reinforced concrete specimens were admixed with individual and synergistic designs of Phyllanthus muellerianus leaf-extract and C6H15NO3 admixtures and immersed in the 0.5 M H2SO4. Electrochemical monitoring of corrosion potential, as per ASTM C876-91 R99, and corrosion current were obtained and statistically analysed, as per ASTM G16-95 R04, for modelling noise resistance. Post-immersion compressive-strength testing then followed, as per ASTM C39/C39M-03, for detailing the admixture effect on load-bearing strength of the steel-reinforced concrete specimens. Results showed that while individual Phyllanthus muellerianus leaf-extract concentrations exhibited better inhibition-efficiency performance than C6H15NO3, synergistic additions of C6H15NO3 to Phyllanthus muellerianus leaf-extract improved steel-rebar corrosion-inhibition. Thus, 6 g Phyllanthus muellerianus + 2 g C6H15NO3 synergistically improved inhibition-efficiency to η = 84.17%, from η = 55.28% by the optimal chemical or from η = 74.72% by the optimal plant-extract admixtures. The study also established that improved compressive strength of steel-reinforced concrete with acceptable inhibition of the steel-rebar corrosion could be attained through optimal combination of the Phyllanthus muellerianus leaf-extract and C6H15NO3 admixtures.

  8. 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.

  9. Ion mobility spectrometry-mass spectrometry examination of the structures, stabilities, and extents of hydration of dimethylamine-sulfuric acid clusters.

    PubMed

    Thomas, Jikku M; He, Siqin; Larriba-Andaluz, Carlos; DePalma, Joseph W; Johnston, Murray V; Hogan, Christopher J

    2016-08-17

    We applied an atmospheric pressure differential mobility analyzer (DMA) coupled to a time-of-flight mass spectrometer to examine the stability, mass-mobility relationship, and extent of hydration of dimethylamine-sulfuric acid cluster ions, which are of relevance to nucleation in ambient air. Cluster ions were generated by electrospray ionization and were of the form: [H((CH3)2NH)x(H2SO4)y](+) and [(HSO4)((CH3)2NH)x(H2SO4)y](-), where 4 ≤ x ≤ 8, and 5 ≤ y ≤ 12. Under dry conditions, we find that positively charged cluster ions dissociated via loss of both multiple dimethylamine and sulfuric acid molecules after mobility analysis but prior to mass analysis, and few parent ions were detected in the mass spectrometer. Dissociation also occurred for negative ions, but to a lesser extent than for positive ions for the same mass spectrometer inlet conditions. Under humidified conditions (relative humidities up to 30% in the DMA), positively charged cluster ion dissociation in the mass spectrometer inlet was mitigated and occurred primarily by H2SO4 loss from ions containing excess acid molecules. DMA measurements were used to infer collision cross sections (CCSs) for all identifiable cluster ions. Stokes-Millikan equation and diffuse/inelastic gas molecule scattering predicted CCSs overestimate measured CCSs by more than 15%, while elastic-specular collision model predictions are in good agreement with measurements. Finally, cluster ion hydration was examined by monitoring changes in CCSs with increasing relative humidity. All examined cluster ions showed a modest amount of water molecule adsorption, with percentage increases in CCS smaller than 10%. The extent of hydration correlates directly with cluster ion acidity for positive ions. PMID:27485283

  10. Sulfuric acid baking and leaching of spent Co-Mo/Al2O3 catalyst.

    PubMed

    Kim, Hong-In; Park, Kyung-Ho; Mishra, Devabrata

    2009-07-30

    Dissolution of metals from a pre-oxidized refinery plant spent Co-Mo/Al(2)O(3) catalyst have been tried through low temperature (200-450 degrees C) sulfuric acid baking followed by mild leaching process. Direct sulfuric acid leaching of the same sample, resulted poor Al and Mo recoveries, whereas leaching after sulfuric acid baking significantly improved the recoveries of above two metals. The pre-oxidized spent catalyst, obtained from a Korean refinery plant found to contain 40% Al, 9.92% Mo, 2.28% Co, 2.5% C and trace amount of other elements such as Fe, Ni, S and P. XRD results indicated the host matrix to be poorly crystalline gamma- Al(2)O(3). The effect of various baking parameters such as catalyst-to-acid ratio, baking temperature and baking time on percentage dissolutions of metals has been studied. It was observed that, metals dissolution increases with increase in the baking temperature up to 300 degrees C, then decreases with further increase in the baking temperature. Under optimum baking condition more than 90% Co and Mo, and 93% Al could be dissolved from the spent catalyst with the following leaching condition: H(2)SO(4)=2% (v/v), temperature=95 degrees C, time=60 min and Pulp density=5%.

  11. Utilization of crude karanj (Pongamia pinnata) oil as a potential feedstock for the synthesis of fatty acid methyl esters.

    PubMed

    Khayoon, M S; Olutoye, M A; Hameed, B H

    2012-05-01

    Methyl esters were synthesized from crude karanj oil (CKO) by single step esterification with methanol using sulfuric acid (H(2)SO(4)) and phosphoric acid (H(3)PO(4)) as catalysts in a homogeneous batch process. H(3)PO(4) was less active than H(2)SO(4) during the process as it presented very low ester yields (<20%) for the various molar ratios of fatty acid to alcohol studied. With H(2)SO(4) as catalyst, the yield was as high as 89.8% at 65°C after 5h. The fatty acids profile of the oil (palmitic acid: ≈ 12%; stearic acid: ≈ 8%; oleic acid: ≈ 52% and linolenic acid of 17%) and the different reactivities of the acids were responsible for the observed differences in conversion to methyl esters. The findings attained with this study might contribute to the economic utilization of a non-edible feedstock. PMID:22405756

  12. Atmospheric Measurements Aboard C-130 During the Pacific Atmospheric Sulfur Experiment

    NASA Astrophysics Data System (ADS)

    Yanchilina, A. G.; Mauldin, L.; Anderson, R.

    2007-12-01

    The Pacific Atmospheric Sulfur Experiment (PASE) is a study with a primary goal aimed at understanding the sulfur cycle in a remote marine atmosphere. The study will be conducted in August and September months of 2007 at Christmas Island on board the NSF/NCAR C-130 aircraft. It will foremost focus on measurements of DMS (dimethyl sulfide) and its contribution to formation of H2SO4 (sulfuric acid) and MSA (methane-sulfonic acid) by reaction with OH (hydroxyl). PASE will also concentrate on subsequent production of aerosols and cloud condensation nuclei from H2SO4, MSA, and NH3 concentrations in a cloud free convective boundary layer (CBL) and in outflow of marine cumulus. This study explains the measurement technique for OH, H2SO4, MSA, HO2, HO2+RO2 (peroxy radicals), and NH3 (ammonia) using the SICIMS (Selected ion chemical ionization mass spectrometer). It also presents sample measurements from research flights of OH, H2SO4, MSA, HO2, and HO2+RO2. In addition, this paper discusses the measurement technique utilized aboard the C-130 in testing SO2, DMS, DMSO (dimethyl sulfoxide), DMSO2 (dimethyl sulfone), O3 (ozone), aerosols, and cloud condensation nuclei. It includes several adaptations to technique and instrumentation from previous studies conducted: the First Aerosol Characterization Experiment (ACE-1) in 1998, the Pacific Exploratory Missions A and B (PEM- Tropics) in 1996, and the Intercontinental Transport Experiment (INTEX-B) in 2006.

  13. The future of airborne sulfur-containing particles in the absence of fossil fuel sulfur dioxide emissions.

    PubMed

    Perraud, Véronique; Horne, Jeremy R; Martinez, Andrew S; Kalinowski, Jaroslaw; Meinardi, Simone; Dawson, Matthew L; Wingen, Lisa M; Dabdub, Donald; Blake, Donald R; Gerber, R Benny; Finlayson-Pitts, Barbara J

    2015-11-01

    Sulfuric acid (H2SO4), formed from oxidation of sulfur dioxide (SO2) emitted during fossil fuel combustion, is a major precursor of new airborne particles, which have well-documented detrimental effects on health, air quality, and climate. Another precursor is methanesulfonic acid (MSA), produced simultaneously with SO2 during the atmospheric oxidation of organosulfur compounds (OSCs), such as dimethyl sulfide. In the present work, a multidisciplinary approach is used to examine how contributions of H2SO4 and MSA to particle formation will change in a large coastal urban area as anthropogenic fossil fuel emissions of SO2 decline. The 3-dimensional University of California Irvine-California Institute of Technology airshed model is used to compare atmospheric concentrations of gas phase MSA, H2SO4, and SO2 under current emissions of fossil fuel-associated SO2 and a best-case futuristic scenario with zero fossil fuel sulfur emissions. Model additions include results from (i) quantum chemical calculations that clarify the previously uncertain gas phase mechanism of formation of MSA and (ii) a combination of published and experimental estimates of OSC emissions, such as those from marine, agricultural, and urban processes, which include pet waste and human breath. Results show that in the zero anthropogenic SO2 emissions case, particle formation potential from H2SO4 will drop by about two orders of magnitude compared with the current situation. However, particles will continue to be generated from the oxidation of natural and anthropogenic sources of OSCs, with contributions from MSA and H2SO4 of a similar order of magnitude. This could be particularly important in agricultural areas where there are significant sources of OSCs.

  14. The future of airborne sulfur-containing particles in the absence of fossil fuel sulfur dioxide emissions

    PubMed Central

    Perraud, Véronique; Horne, Jeremy R.; Martinez, Andrew S.; Kalinowski, Jaroslaw; Meinardi, Simone; Dawson, Matthew L.; Wingen, Lisa M.; Dabdub, Donald; Blake, Donald R.; Gerber, R. Benny; Finlayson-Pitts, Barbara J.

    2015-01-01

    Sulfuric acid (H2SO4), formed from oxidation of sulfur dioxide (SO2) emitted during fossil fuel combustion, is a major precursor of new airborne particles, which have well-documented detrimental effects on health, air quality, and climate. Another precursor is methanesulfonic acid (MSA), produced simultaneously with SO2 during the atmospheric oxidation of organosulfur compounds (OSCs), such as dimethyl sulfide. In the present work, a multidisciplinary approach is used to examine how contributions of H2SO4 and MSA to particle formation will change in a large coastal urban area as anthropogenic fossil fuel emissions of SO2 decline. The 3-dimensional University of California Irvine–California Institute of Technology airshed model is used to compare atmospheric concentrations of gas phase MSA, H2SO4, and SO2 under current emissions of fossil fuel-associated SO2 and a best-case futuristic scenario with zero fossil fuel sulfur emissions. Model additions include results from (i) quantum chemical calculations that clarify the previously uncertain gas phase mechanism of formation of MSA and (ii) a combination of published and experimental estimates of OSC emissions, such as those from marine, agricultural, and urban processes, which include pet waste and human breath. Results show that in the zero anthropogenic SO2 emissions case, particle formation potential from H2SO4 will drop by about two orders of magnitude compared with the current situation. However, particles will continue to be generated from the oxidation of natural and anthropogenic sources of OSCs, with contributions from MSA and H2SO4 of a similar order of magnitude. This could be particularly important in agricultural areas where there are significant sources of OSCs. PMID:26483454

  15. High yield production of sugars from deproteinated palm kernel cake under microwave irradiation via dilute sulfuric acid hydrolysis.

    PubMed

    Fan, Suet-Pin; Jiang, Li-Qun; Chia, Chin-Hua; Fang, Zhen; Zakaria, Sarani; Chee, Kah-Leong

    2014-02-01

    Recent years, great interest has been devoted to the conversion of biomass-derived carbohydrate into sugars, such as glucose, mannose and fructose. These are important versatile intermediate products that are easily processed into high value-added biofuels. In this work, microwave-assisted dilute sulfuric acid hydrolysis of deproteinated palm kernel cake (DPKC) was systematically studied using Response Surface Methodology. The highest mannose yield (92.11%) was achieved at the optimized condition of 148°C, 0.75N H2SO4, 10min 31s and substrate to solvent (SS) ratio (w/v) of 1:49.69. Besides that, total fermentable sugars yield (77.11%), was obtained at 170°C, 0.181N H2SO4, 6min 6s and SS ratio (w/v) of 1:40. Ridge analysis was employed to further verify the optimum conditions. Thus, this work provides fundamental data of the practical use of DPKC as low cost, high yield and environmental-friendly material for the production of mannose and other sugars.

  16. Long-term variations in abundance and distribution of sulfuric acid vapor in the Venus atmosphere inferred from Pioneer Venus and Magellan radio occultation studies

    NASA Technical Reports Server (NTRS)

    Jenkins, J. M.; Steffes, P. G.

    1992-01-01

    Radio occultation experiments have been used to study various properties of planetary atmospheres, including pressure and temperature profiles, and the abundance profiles of absorbing constituents in those planetary atmospheres. However, the reduction of amplitude data from such experiments to determine abundance profiles requires the application of the inverse Abel transform (IAT) and numerical differentiation of experimental data. These two operations preferentially amplify measurement errors above the true signal underlying the data. A new technique for processing radio occultation data has been developed that greatly reduces the errors in the derived absorptivity and abundance profiles. This technique has been applied to datasets acquired from Pioneer Venus Orbiter radio occultation studies and more recently to experiments conducted with the Magellan spacecraft. While primarily designed for radar studies of the Venus surface, the high radiated power (EIRP) from the Magellan spacecraft makes it an ideal transmitter for measuring the refractivity and absorptivity of the Venus atmosphere by such experiments. The longevity of the Pioneer Venus Orbiter has made it possible to study long-term changes in the abundance and distribution of sulfuric acid vapor, H2SO4(g), in the Venus atmosphere between 1979 and 1992. The abundance of H2SO4(g) can be inferred from vertical profiles of 13-cm absorptivity profiles retrieved from radio occultation experiments. Data from 1979 and 1986-87 suggest that the abundance of H2SO4(g) at latitudes northward of 70 deg decreased over this time period. This change may be due to a period of active volcanism in the late 1970s followed by a relative quiescent period, or some other dynamic process in the Venus atmosphere. While the cause is not certain, such changes must be incorporated into dynamic models of the Venus atmosphere. Potentially, the Magellan spacecraft will extend the results of Pioneer Venus Orbiter and allow the continued

  17. Hydrothermal synthesis of Na 2(MoOPO 4) 2(HPO 4) · 2H 2O: A layered molybdenum (V) phosphate structure and its relationship to 2VOSO 4 · H 2SO 4

    NASA Astrophysics Data System (ADS)

    Peascoe, R.; Clearfield, A.

    1991-12-01

    The hydrothermal synthesis and structure of the molybdenum (V) phosphate, Na 2(MoOPO 4) 2(HPO 4) · 2H 2O, was determined and compared to the closely related 2VOSO 4 · H 2SO 4 ( B. JORDAN AND C. CALVO, Can. J. Chem.51, 2621 (1973)). Na 2(MoOPO 4) 2(HPO 4) · 2H 2O crystallizes with lattice parameters a = 6.452(2)Å, c = 15.999(1)Å, and z = 2 in the tetragonal space group {I4}/{mmm} and was refined to Rf = 0.041 and Rwf = 0.044 with 426 reflections for which I > 2 σ. The structure is made up of layers of MoOPO 4 composed of alternating molybdenum oxygen octahedra and phosphate tetrahedra. The layers are linked by disordered phosphorus tetrahedra forming tunnels. Thermogravimetric analysis, infrared, solid state, NMR, and ESR spectra indicate the presence of water in the tunnels and molybdenum with an oxidation state of (V).

  18. Mediated proton transport through Nafion 117 membranes imbibed with varying concentrations of aqueous VOSO4 (VO2+) and NH4VO3 (VO2+) in 2 M H2SO4

    NASA Astrophysics Data System (ADS)

    Suarez, Sophia; Paterno, Domenec

    2016-11-01

    We performed an extensive study on Nafion 117 membrane imbibed with various concentrations of aqueous ammonium metavanadate (NH4VO3), and vanadyl sulfate (VOSO4), in 2 M H2SO4 over the temperature range of 20-100 °C, using 1H NMR and AC Impedance spectroscopies. The objective was to determine the effect of the tetravalent (VO2+) and pentavalent (VO2+) vanadium ions on the proton transport of Nafion 117.1H NMR chemical shift and linewidth data show greater short-range proton transport for the VO2+ imbibed membranes compared with the VO2+. However, the local environments seem to differ in that while the data for VO2+ imbibed membranes seem to follow more the trends observed for water hydrated Nafion 117, those for the VO2+ followed the trend of its aqueous bulk vanadium solvents, indicating that viscosity plays a larger role for the VO2+ imbibed membranes compared to the VO2+.

  19. Inhibition of mild steel corrosion by 1,4,6-trimethyl-2-oxo-1,2-dihydropyridine-3-carbonitrile and synergistic effect of halide ion in 0.5 M H2SO4

    NASA Astrophysics Data System (ADS)

    Mourya, Punita; Singh, Praveen; Rastogi, R. B.; Singh, M. M.

    2016-09-01

    The effect of iodide ions on inhibitive performance of 1,4,6-trimethyl-2-oxo-1,2-dihydropyridine-3-carbonitrile (TODPCN) on mild steel (MS) corrosion in 0.5 M H2SO4 was studied using gravimetric and electrochemical measurements. TODPCN inhibits the corrosion of MS to the extent of 62.3% at its lowest concentration (0.5 mM) and its inhibition efficiency (η) further increases on increasing concentration at 298 K. The adsorption of TODPCN on MS was found to follow the Langmuir adsorption isotherm. The value of η increased on the addition of 2.0 mM KI. The value of synergism parameter being more than unity indicates that the enhanced η value in the presence of iodide ions is only due to synergism. Thus, a cooperative mechanism of inhibition exists between the iodide anion and TODPCN cations. The increase in surface coverage in the presence of KI indicates that iodide ions enhance the adsorption of TODPCN. The surface morphology of corroded/inhibited MS was studied by atomic force microscopy. X-ray photoelectron spectroscopy of inhibited MS surface was carried out to determine the composition of the adsorbed film. Some quantum chemical parameters and the Mulliken charge densities for TODPCN calculated by density functional theory provided further insight into the mechanism of inhibition.

  20. The clouds of Venus - Sulfuric acid by the lead chamber process

    NASA Technical Reports Server (NTRS)

    Sill, G. T.

    1983-01-01

    The Pioneer Venus atmospheric probe provided new data on the clouds of Venus. A model consistent with this data involves SO2 being oxidized to H2SO4 by NO(x) in the presence of H2O. NO(x) also forms nitrosylsulfuric acid (NOHSO4) dissolved in the H2SO4 droplets. This acid solution, along with SO2 and perhaps NO2, can explain the UV and visible reflection spectrum of Venus. In the middle and lower clouds, NOHSO4 forms solid particles.

  1. Removal of sulfuric acid mist from lead-acid battery plants by coal fly ash-based sorbents.

    PubMed

    Shu, Yuehong; Wei, Xiangyu; Fang, Yu; Lan, Bingyan; Chen, Hongyu

    2015-04-01

    Sorbents from coal fly ash (CFA) activated by NaOH, CaO and H2O were prepared for H2SO4 mist removal from lead-acid battery plants. The effects of parameters including temperature, time, the ratios of CFA/activator and water/solid during sorbent preparation were investigated. It is found that the synthesized sorbents exhibit much higher removal capacity for H2SO4 mist when compared with that of raw coal fly ash and CaO except for H2O activated sorbent and this sorbent was hence excluded from the study because of its low capacity. The H2SO4 mist removal efficiency increases with the increasing of preparation time length and temperature. In addition, the ratios of CFA/activator and water/solid also impact the removal efficiency, and the optimum preparation conditions are identified as: a water/solid ratio of 10:1 at 120 °C for 10h, a CFA:CaO weight ratio of 10:1, and a NaOH solution concentration of 3 mol/L. The formation of rough surface structure and an increased surface area after NaOH/CaO activation favor the sorption of H2SO4 mist and possible sorption mechanisms might be electrostatic attractions and chemical precipitation between the surface of sorbents and H2SO4 mist.

  2. 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...

  3. 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...

  4. 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...

  5. 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...

  6. 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...

  7. 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...

  8. 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...

  9. 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...

  10. 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...

  11. 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...

  12. Sulfur Based Thermochemical Heat Storage for Baseload Concentrated Solar Power Generation

    SciTech Connect

    wong, bunsen

    2014-11-20

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

  13. 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.

  14. Effect of Sulfuric and Triflic Acids on the Hydration of Vanadium Cations: An ab Initio Study.

    PubMed

    Sepehr, Fatemeh; Paddison, Stephen J

    2015-06-01

    Vanadium redox flow batteries (VRFBs) may be a promising solution for large-scale energy storage applications, but the crossover of any of the redox active species V(2+), V(3+), VO(2+), and VO2(+) through the ion exchange membrane will result in self-discharge of the battery. Hence, a molecular level understanding of the states of vanadium cations in the highly acidic environment of a VRFB is needed. We examine the effects of sulfuric and triflic (CF3SO3H) acids on the hydration of vanadium species as they mimic the electrolyte and functional group of perfluorosulfonic acid (PFSA) membranes. Hybrid density functional theory in conjunction with a continuum solvation model was utilized to obtain the local structures of the hydrated vanadium cations in proximity to H2SO4, CF3SO3H, and their conjugate anions. The results indicate that none of these species covalently bond to the vanadium cations. The hydration structure of V(3+) is more distorted than that of V(2+) in an acidic medium. The oxo-group of VO2(+) is protonated by either acid, in contrast to VO(2+) which is not protonated. The atomic partial charge of the four oxidation states of vanadium varies from +1.7 to +2.0. These results provide the local solvation structures of vanadium cations in the VRFBs environment that are directly related to the electrolytes stability and diffusion of vanadium ions into the membrane. PMID:25954916

  15. Effect of Sulfuric and Triflic Acids on the Hydration of Vanadium Cations: An ab Initio Study.

    PubMed

    Sepehr, Fatemeh; Paddison, Stephen J

    2015-06-01

    Vanadium redox flow batteries (VRFBs) may be a promising solution for large-scale energy storage applications, but the crossover of any of the redox active species V(2+), V(3+), VO(2+), and VO2(+) through the ion exchange membrane will result in self-discharge of the battery. Hence, a molecular level understanding of the states of vanadium cations in the highly acidic environment of a VRFB is needed. We examine the effects of sulfuric and triflic (CF3SO3H) acids on the hydration of vanadium species as they mimic the electrolyte and functional group of perfluorosulfonic acid (PFSA) membranes. Hybrid density functional theory in conjunction with a continuum solvation model was utilized to obtain the local structures of the hydrated vanadium cations in proximity to H2SO4, CF3SO3H, and their conjugate anions. The results indicate that none of these species covalently bond to the vanadium cations. The hydration structure of V(3+) is more distorted than that of V(2+) in an acidic medium. The oxo-group of VO2(+) is protonated by either acid, in contrast to VO(2+) which is not protonated. The atomic partial charge of the four oxidation states of vanadium varies from +1.7 to +2.0. These results provide the local solvation structures of vanadium cations in the VRFBs environment that are directly related to the electrolytes stability and diffusion of vanadium ions into the membrane.

  16. Inhibition of cold rolled steel corrosion by Tween-20 in sulfuric acid: weight loss, electrochemical and AFM approaches.

    PubMed

    Mu, Guannan; Li, Xianghong

    2005-09-01

    The inhibiting action of a nonionic surfactant of Tween-20 on the corrosion of cold rolled steel (CRS) in 0.5-7.0 M sulfuric acid (H(2)SO(4)) was studied by weight loss and potentiodynamic polarization methods. Atomic force microscope (AFM) provided the surface conditions. The results show that inhibition efficiency increases with the inhibitor concentration, while it decreases with the sulfuric acid concentration. The adsorption of inhibitor on the cold rolled steel surface obeys the Langmuir adsorption isotherm equation. Effect of immersion time was studied and discussed. The effect of temperature on the corrosion behavior of cold rolled steel was also studied at four temperatures ranging from 30 to 60 degrees C, the thermodynamic parameters such as adsorption heat, adsorption free energy, and adsorption entropy were calculated. The results revealed that the adsorption was physisorption mechanism. A kinetic study of cold rolled steel in uninhibited and inhibited acid was also discussed. The kinetic parameters such as apparent activation energy, pre-exponential factor, rate constant, and reaction constant were calculated for the reactions of corrosion. The inhibition effect is satisfactorily explained by both thermodynamic and kinetic models. Polarization curves show that Tween-20 is a cathodic-type inhibitor in sulfuric acid. The results obtained from weight loss and potentiodynamic polarization are in good agreement, and the Tween-20 inhibition action could also be evidenced by surface AFM images.

  17. Effects of inhalation of acidic compounds on pulmonary function in allergic adolescent subjects.

    PubMed

    Koenig, J Q; Covert, D S; Pierson, W E

    1989-02-01

    There is concern about the human health effects of inhalation of acid compounds found in urban air pollution. It was the purpose of this study to investigate three of these acid compounds, sulfur dioxide (SO2), sulfuric acid (H2SO4), and nitric acid (HNO3) in a group of allergic adolescent subjects. Subjects were exposed during rest and moderate exercise to 0.7 mumole/m3 (68 micrograms/m3) H2SO4, 4.0 mumole/m3 (0.1 ppm) SO2, or 2.0 mumole/m3 (0.05 ppm) HNO3. Pulmonary functions (FEV1, total respiratory resistance, and maximal flow) were measured before and after exposure. Preliminary analysis based on nine subjects indicates that exposure to 0.7 mumole/m3 H2SO4 alone and in combination with SO2 caused significant changes in pulmonary function, whereas exposure to air or SO2 alone did not. FEV1 decreased an average of 6% after exposure to H2SO4 alone and 4% when the aerosol was combined with SO2. The FEV1 decrease was 2% after both air and SO2 exposures. Total respiratory resistance (RT) increased 15% after the combined H2SO4 exposures, 12% after H2SO4 alone, and 7% after exposure to air. After exposures to HNO3 alone, FEV1 decreased by 4%, and RT increased by 23%. These results are preliminary; final conclusions must wait for completion of the study.

  18. Dilute-sulfuric acid pretreatment of corn stover in pilot-scale reactor: investigation of yields, kinetics, and enzymatic digestibilities of solids.

    PubMed

    Schell, Daniel J; Farmer, Jody; Newman, Millie; McMillan, James D

    2003-01-01

    Corn stover is a domestic feedstock that has potential to produce significant quantities of fuel ethanol and other bioenergy and biobased products. However, comprehensive yield and carbon mass balance information and validated kinetic models for dilute-sulfuric acid (H2SO4) pretreatment of corn stover have not been available. This has hindered the estimation of process economics and also limited the ability to perform technoeconomic modeling to guide research. To better characterize pretreatment and assess its kinetics, we pretreated corn stover in a continuous 1 t/d reactor. Corn stover was pretreated at 20% (w/w) solids concentration over a range of conditions encompassing residence times of 3-12 min, temperatures of 165- 195 degrees C, and H2SO4 concentrations of 0.5-1.4% (w/w). Xylan conversion yield and carbon mass balance data were collected at each run condition. Performance results were used to estimate kinetic model parameters assuming biphasic hemicellulose hydrolysis and a hydrolysis mechanism incorporating formation of intermediate xylo-oligomers. In addition, some of the pretreated solids were tested in a simultaneous saccharification and fermentation (SSF) process to measure the reactivity of their cellulose component to enzymatic digestion by cellulase enzymes. Monomeric xylose yields of 69-71% and total xylose yields (monomers and oligomers) of 70-77% were achieved with performance level depending on pretreatment severity. Cellulose conversion yields in SSF of 80-87% were obtained for some of the most digestible pretreated solids.

  19. 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…

  20. Microwave Remote Sensing of the Temperature and Distribution of Sulfur Compounds in the Lower Atmosphere of Venus

    NASA Astrophysics Data System (ADS)

    Jenkins, Jon M.; Kolodner, Marc A.; Butler, Bryan J.; Suleiman, Shady H.; Steffes, Paul G.

    2002-08-01

    A multi-wavelength radio frequency observation of Venus was performed on April 5, 1996, with the Very Large Array to investigate potential variations in the vertical and horizontal distribution of temperature and the sulfur compounds sulfur dioxide (SO 2) and sulfuric acid vapor (H 2SO 4(g)) in the atmosphere of the planet. Brightness temperature maps were produced which feature significantly darkened polar regions compared to the brighter low-latitude regions at both observed frequencies. This is the first time such polar features have been seen unambiguously in radio wavelength observations of Venus. The limb-darkening displayed in the maps helps to constrain the vertical profile of H 2SO 4(g), temperature, and to some degree SO 2. The maps were interpreted by applying a retrieval algorithm to produce vertical profiles of temperature and abundance of H 2SO 4(g) given an assumed sub-cloud abundance of SO 2. The results indicate a substantially higher abundance of H 2SO 4(g) at high latitudes (above 45°) than in the low-latitude regions. The retrieved temperature profiles are up to 25 K warmer than the profile obtained by the Pioneer Venus sounder probe at altitudes below 40 km (depending on location and assumed SO 2 abundance). For 150 ppm of SO 2, it is more consistent with the temperature profile obtained by Mariner 5, extrapolated to the surface via a dry adiabat. The profiles obtained for H 2SO 4(g) at high latitudes are consistent with those derived from the Magellan radio occultation experiments, peaking at around 8 ppm at an altitude of 46 km and decaying rapidly away from that altitude. At low latitudes, no significant H 2SO 4(g) is observed, regardless of the assumed SO 2 content. This is well below that measured by Mariner 10 (Lipa and Tyler 1979, Icarus39, 192-208), which peaked at ˜14 ppm near 47 km. Our results favor ≤100 ppm of SO 2 at low latitudes and ≤50 ppm in polar regions. The low-latitude value is statistically consistent with the

  1. 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.

  2. Recovery of water and acid from leach solutions using direct contact membrane distillation.

    PubMed

    Kesieme, Uchenna K; Milne, Nicholas; Cheng, Chu Yong; Aral, Hal; Duke, Mikel

    2014-01-01

    This paper describes for the first time the use of direct contact membrane distillation (DCMD) for acid and water recovery from a real leach solution generated by a hydrometallurgical plant. The leach solutions considered contained H2SO4 or HCl. In all tests the temperature of the feed solution was kept at 60 °C. The test work showed that fluxes were within the range of 18-33 kg/m(2)/h and 15-35 kg/m(2)/h for the H2SO4 and HCl systems, respectively. In the H2SO4 leach system, the final concentration of free acid in the sample solution increased on the concentrate side of the DCMD system from 1.04 M up to 4.60 M. The sulfate separation efficiency was over 99.9% and overall water recovery exceeded 80%. In the HCl leach system, HCl vapour passed through the membrane from the feed side to the permeate. The concentration of HCl captured in the permeate was about 1.10 M leaving behind only 0.41 M in the feed from the initial concentration of 2.13 M. In all the experiments, salt rejection was >99.9%. DCMD is clearly viable for high recovery of high quality water and concentrated H2SO4 from spent sulfuric acid leach solution where solvent extraction could then be applied to recover the sulfuric acid and metals. While HCl can be recovered for reuse using only DCMD.

  3. Chemical weathering and the role of sulfuric and nitric acids in carbonate weathering: Isotopes (13C, 15N, 34S, and 18O) and chemical constraints

    NASA Astrophysics Data System (ADS)

    Li, Cai; Ji, Hongbing

    2016-05-01

    Multiple isotopes (13C-DIC, 34S and 18O-SO42-, 15N and 18O-NO3-) and water chemistry were used to evaluate weathering rates and associated CO2 consumption by carbonic acid and strong acids (H2SO4 and HNO3) in a typical karst watershed (Wujiang River, Southwest China). The dual sulfate isotopes indicate that sulfate is mainly derived from sulfide oxidation in coal stratum and sulfide-containing minerals, and dual nitrate isotopes indicate that nitrate is mainly derived from soil N and nitrification. The correlation between isotopic compositions and water chemistry suggests that sulfuric and nitric acids, in addition to carbonic acid, are involved in carbonate weathering. The silicate and carbonate weathering rates are 7.2 t km-2 yr-1 and 76 t km-2 yr-1, respectively. In comparison with carbonate weathering rates (43 t km-2 yr-1) by carbonic acid alone, the subsequent increase in rates indicates significant enhancement of weathering when combined with sulfuric and nitric acids. Therefore, the role of sulfuric and nitric acids in the rock weathering should be considered in the global carbon cycle.

  4. Recovery of manganese and zinc from spent Zn-C cell powder: Experimental design of leaching by sulfuric acid solution containing glucose.

    PubMed

    Biswas, Ranjit K; Karmakar, Aneek K; Kumar, Sree L

    2016-05-01

    The spent Zn-C cell powder, containing ZnMn2O4, ZnO, MnO(OH) and possibly Mn2O3 and Mn3O4, can be leached by a sulfuric acid solution mixed with some glucose. The leaching is found to be dependent on solid to liquid (S/L) ratio, amount of glucose, concentration of sulfuric acid solution, time and pulp agitation speed. For 5g powder (S), 1h leaching time and 300rpm pulp agitation speed, two-level four-factor (2(4)) experimental designs have been carried out to derive models for extraction of both Mn(II) and Zn(II). Amount of glucose (G, g), concentration of H2SO4 solution (C, mol/L), volume of H2SO4 solution as leachant (L, mL) and leaching temperature (T, °C) are considered as factors (variables). The model in both cases consists of mean, factor effects and interaction effects. The four-factor interaction effect is observed in neither of the cases. Some two-factor and three-factor effects are found to have produced positive or negative contributions to dissolution percentage in both cases. The models are examined for comparison with experimental results with good fits and also used for optimization of factors. At optimized condition (G=0.50g, C=2mol/L, L=250mL and T=100°C), an aliquot of 5g powder in 1h and at 300rpm produces a solution containing (7.08±0.10)g/L Mn(II) and (2.20±0.06)g/L Zn(II) corresponding to almost 100% extraction of both metal ions. PMID:26564257

  5. Modification of the surface chemistry of single- and multi-walled carbon nanotubes by HNO3 and H2SO4 hydrothermal oxidation for application in direct contact membrane distillation.

    PubMed

    Morales-Torres, Sergio; Silva, Tânia L S; Pastrana-Martínez, Luisa M; Brandão, Ana T S C; Figueiredo, José L; Silva, Adrián M T

    2014-06-28

    A specific methodology based on nitric acid hydrothermal oxidation was used to control the surface chemistry of multi-walled (MWCNTs) and single-walled (SWCNTs) carbon nanotubes (CNTs) with different lengths, and this methodology was adapted to the use of sulphuric acid containing ammonium persulfate as an oxidizing agent. The amount of oxygen-containing surface groups depends on the number and length of the graphene layers of the CNTs, thicker and shorter CNTs having more reactive sites for surface functionalization. In particular, the oxidation of MWCNTs was more pronounced than that of short SWCNTs and less surface groups were introduced into long SWCNTs, regardless of the acid used at any fixed concentration. It was also possible to tailor the surface chemistry of both SWCNTs and MWCNTs by using the adopted methodologies, and the amount of both oxygen- and sulphur-containing functional groups was correlated with the concentration of each oxidizing agent used. Mathematical functions that allow precise control of the amount and type of the surface groups introduced into carbon nanotubes were obtained. Buckypapers were also prepared over a polytetrafluoroethylene commercial membrane. These membranes were tested in direct contact membrane distillation and, under salinity conditions, the membrane prepared using oxidized MWCNTs (instead of SWCNTs) was the most efficient, the permeate flux of the commercial membrane significantly increasing in the presence of these CNTs, while completely rejecting chloride ions. In addition, the permeate flux was precisely correlated with the amount of oxygenated functional surface groups (as well as with the pH of point of zero charge) of the oxidized MWCNTs. PMID:24821484

  6. Effects of sulfur oxides on nasal and lung function in adolescents with extrinsic asthma

    SciTech Connect

    Koenig, J.Q.; Morgan, M.S.; Horike, M.; Pierson, W.E.

    1985-12-01

    Ten adolescent subjects with extrinsic asthma were exposed during intermittent exercise to filtered air, 0.5 ppm of sulfur dioxide (SO2), or 100 micrograms/m3 of sulfuric acid (H2SO4) on 5 separate days. The purpose of the study was to compare changes in nasal power (the work of nose breathing) with pulmonary functional changes depending on the route of inhalation of the sulfur oxide pollutants, oral inhalation through a rubber mouthpiece or oronasal inhalation via a face mask. Nasal power was measured with a modified skin diving mask equipped with two differential pressure transducers. Statistically significant changes in total respiratory resistance, FEV1, and maximum flow calculated at 50% and 75% vital capacity were observed after all exposures to SO2 and H2SO4. The magnitude of change in FEV1 and maximum flow calculated at 50% vital capacity was higher after oral compared to oronasal inhalation of SO2. The nasal work of breathing increased 32% after SO2 exposure by mouthpiece and 30% after SO2 exposure via face mask (p less than 0.05). The nasal power changes after the H2SO4 exposures were not different from the sham exposures. We conclude that oronasal inhalation of 0.5 ppm of SO2 produces a significant increase in the nasal work of breathing and that the route of exposure reduces but does not eliminate the lower airway reactions observed on oral exposure.

  7. Sedimentation of sulfuric acid in acid tars from current production

    SciTech Connect

    Denisova, T.L.; Frolov, A.F.; Aminov, A.N.; Novosel'tsev, S.P.

    1987-09-01

    Acid tars obtained in treating T-750, KhF-12, and I-8A oils were investigated for purposes of recovering sulfuric acid and asphalt binders from the compositions and of determining the effects of storage time on the recovery. The consumption and sedimentation levels of sulfuric acid during storage for different periods and at different temperatures were assessed. The characteristics of an asphalt binder obtained by neutralizing acid tar with a paste consisting of asphalts from deasphalting operations and slaked lime, followed by oxidation of the mixture with atmospheric air, were determined. The sulfuric acid recovered in the settling process could be burned in order to purify it of organic contaminants.

  8. Sulfur Dioxide variability in the Venus Atmosphere

    NASA Astrophysics Data System (ADS)

    Vandaele, A. C.; Korablev, O.; Mahieux, A.; Wilquet, V.; Chamberlain, S.; Belayev, D.; Encrenaz, Th.; Esposito, L.; Jessup, K. L.; Lefèvre, F.; Limaye, S.; Marcq, E.; Mils, F.; Parkinson, C.; Sandor, B.; Stolzenbach, A.; Wilson, C.

    2015-10-01

    Recent observations of sulfur oxides (SO2, SO, OCS, and H2 SO4) in Venus' mesosphere have generated controversy and great interest in the scientific community. These observations revealed u nexpected spatial patterns and spatial/temporal variability that have not been satisfactorily explained by models. Particularly intriguing are the layer of enhanced gas-phase SO2 and SO in the upper mesosphere, and variability in the maximum observed SO2 a bundance and the equator -to-pole SO2 abundance gradient, seemingly on multi-year cycles, that is not uniquely linked to local time variations. Sulfur oxide chemistry on Venus is closely linked to the global-scale cloud and haze layers, which are composed primarily of concentrated sulfuric acid. Consequently, sulfur oxide observations provide important insight into the ongoing chemical evolution of Venus' atmosphere, atmospheric dynamics, and possible volcanism.

  9. 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.

  10. Surfactant control of gas transport and reactions at the surface of sulfuric acid.

    PubMed

    Park, Seong-Chan; Burden, Daniel K; Nathanson, Gilbert M

    2009-02-17

    Aerosol particles in the atmosphere are tiny chemical reactors that catalyze numerous reactions, including the conversion of benign gases into ozone-destroying ones. In the lower stratosphere, these particles are often supercooled mixtures of water and sulfuric acid. The different species present at the surface of these droplets (H(2)O, H(3)O(+), HSO(4)(-), H(2)SO(4), and SO(4)(2-)) stand at the "gas-liquid frontier"; as the first to be struck by impinging molecules, these species provide the initial environment for solvation and reaction. Furthermore, aerosol particles may contain a wide range of organic molecules, some of which migrate to the surface and coat the droplet. How do ambient gases dissolve in the droplet if it is coated with an organic layer? At one extreme, monolayer films of insoluble, long-chain alcohols can dramatically reduce gas transport, packing so tightly at the surface of water that they impede water evaporation by factors of 10,000 or more. Shorter chain surfactants are expected to pack less tightly, but we wondered whether these incomplete monolayers also block gas transport and whether this system could serve as a model for understanding the surfaces of atmospheric aerosol particles. To address these questions, our research focuses on small, soluble surfactants such as butanol and hexanol dissolved in supercooled sulfuric acid. These amphiphilic molecules spontaneously segregate to the surface and coat the acid but only to a degree. Gas-liquid scattering experiments reveal that these porous films behave in surprisingly diverse ways: they can impose a barrier (to N(2)O(5) hydrolysis), be "invisible" (to water evaporation), or even enhance gas uptake (of HCl). The transition from obstacle to catalyst can be traced to specific interactions between the surfactant and each gas. For example, the hydrolysis of N(2)O(5) may be impeded because of its large size and because alcohol molecules that straddle the interface limit contact between N(2)O(5

  11. Surfactant control of gas transport and reactions at the surface of sulfuric acid.

    PubMed

    Park, Seong-Chan; Burden, Daniel K; Nathanson, Gilbert M

    2009-02-17

    Aerosol particles in the atmosphere are tiny chemical reactors that catalyze numerous reactions, including the conversion of benign gases into ozone-destroying ones. In the lower stratosphere, these particles are often supercooled mixtures of water and sulfuric acid. The different species present at the surface of these droplets (H(2)O, H(3)O(+), HSO(4)(-), H(2)SO(4), and SO(4)(2-)) stand at the "gas-liquid frontier"; as the first to be struck by impinging molecules, these species provide the initial environment for solvation and reaction. Furthermore, aerosol particles may contain a wide range of organic molecules, some of which migrate to the surface and coat the droplet. How do ambient gases dissolve in the droplet if it is coated with an organic layer? At one extreme, monolayer films of insoluble, long-chain alcohols can dramatically reduce gas transport, packing so tightly at the surface of water that they impede water evaporation by factors of 10,000 or more. Shorter chain surfactants are expected to pack less tightly, but we wondered whether these incomplete monolayers also block gas transport and whether this system could serve as a model for understanding the surfaces of atmospheric aerosol particles. To address these questions, our research focuses on small, soluble surfactants such as butanol and hexanol dissolved in supercooled sulfuric acid. These amphiphilic molecules spontaneously segregate to the surface and coat the acid but only to a degree. Gas-liquid scattering experiments reveal that these porous films behave in surprisingly diverse ways: they can impose a barrier (to N(2)O(5) hydrolysis), be "invisible" (to water evaporation), or even enhance gas uptake (of HCl). The transition from obstacle to catalyst can be traced to specific interactions between the surfactant and each gas. For example, the hydrolysis of N(2)O(5) may be impeded because of its large size and because alcohol molecules that straddle the interface limit contact between N(2)O(5

  12. 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)

  13. 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.

  14. Sulfur Oxidation and Contrail Precursor Chemistry

    NASA Technical Reports Server (NTRS)

    DeWitt, Kenneth; Hwang, Soon M.

    2005-01-01

    Sulfuric acid (H2SO4), formed in commercial aircraft operations via Fuel-S (right arrow) SO2 + SO3 (right arrow) H2SO4, plays an important role in affecting the global climate change through atmospheric chemical reactions and radiative forcing. Measurement of the sulfur oxidation rates is critical to the understanding of the contrail formation. The principle reaction pathway is SO2 + O + M (right arrow) SO3 + M. Although there are many measurements for the rates of this reaction, it has never been measured in the temperature and pressure regime available to aircraft operation. In this investigation, a series of experiments were performed behind the reflected shock waves in a shock tube. OH radicals were produced in lean, shock heated SO2/H2/O2/Ar mixtures. The reaction progress was followed using OH absorption spectroscopy at 310 nm. The data were analyzed with the aid of computer modeling/simulation. The mean value of the rate coefficients of R21 determined is k(sub 21,0)/[M]= 3.9 x 10(exp 15) cm(sup 6) per square mole per second at T = 960 - 1150 K and rho = 16-30 micromole per cubic centimeter with uncertainty limits of plus or minus 30%. A non-Arrhenius fit to our data together with all existing data gives k(sub 21,0)/[M] = 1.3 x 10(exp 24) T (exp -2.5) exp(-2350 K/T) cm(sup 6) per square mole per second at T = 300 - 2500 K with the same uncertainty limits given above. The calculated conversion of S(IV)(SO2) to S(VI) (SO3 + H2SO4) was about 2% in our experimental conditions.

  15. Sulfur Reduction in Acid Rock Drainage Environments.

    PubMed

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

    2015-10-01

    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.

  16. Sulfur geochemistry of hydrothermal waters in Yellowstone National Park: IV Acid-sulfate waters

    USGS Publications Warehouse

    Kirk, Nordstrom D.; Blaine, McCleskey R.; Ball, J.W.

    2009-01-01

    Many waters sampled in Yellowstone National Park, both high-temperature (30-94 ??C) and low-temperature (0-30 ??C), are acid-sulfate type with pH values of 1-5. Sulfuric acid is the dominant component, especially as pH values decrease below 3, and it forms from the oxidation of elemental S whose origin is H2S in hot gases derived from boiling of hydrothermal waters at depth. Four determinations of pH were obtained: (1) field pH at field temperature, (2) laboratory pH at laboratory temperature, (3) pH based on acidity titration, and (4) pH based on charge imbalance (at both laboratory and field temperatures). Laboratory pH, charge imbalance pH (at laboratory temperature), and acidity pH were in close agreement for pH ??10%, a selection process was used to compare acidity, laboratory, and charge balance pH to arrive at the best estimate. Differences between laboratory and field pH can be explained based on Fe oxidation, H2S or S2O3 oxidation, CO2 degassing, and the temperature-dependence of pK2 for H2SO4. Charge imbalances are shown to be dependent on a speciation model for pH values 350 mg/L Cl) decrease as the Cl- concentration increases from boiling which appears inconsistent with the hypothesis of H2S oxidation as a source of hydrothermal SO4. This trend is consistent with the alternate hypothesis of anhydrite solubility equilibrium. Acid-sulfate water analyses are occasionally high in As, Hg, and NH3 concentrations but in contrast to acid mine waters they are low to below detection in Cu, Zn, Cd, and Pb concentrations. Even concentrations of SO4, Fe, and Al are much lower in thermal waters than acid mine waters of the same pH. This difference in water chemistry may explain why certain species of fly larvae live comfortably in Yellowstone's acid waters but have not been observed in acid rock drainage of the same pH.

  17. 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.

  18. Benevolent behavior of Kleinia grandiflora leaf extract as a green corrosion inhibitor for mild steel in sulfuric acid solution

    NASA Astrophysics Data System (ADS)

    Pitchaipillai, Muthukrishnan; Raj, Karthik; Balasubramanian, Jeyaprabha; Periakaruppan, Prakash

    2014-11-01

    The ethanolic extract of Kleinia grandiflora leaves was characterized and tested for its potential anticorrosion properties on mild steel in 1 M H2SO4 medium using mass-loss analysis, potentiodynamic polarization measurements, electrochemical impedance spectroscopy, Fourier-transform infrared spectroscopy, scanning electron microscopy, UV-visible spectroscopy, and X-ray diffraction analysis. The effect of temperature on the corrosion behavior of mild steel was studied in the range of 308 to 328 K. The inhibition efficiency was observed to increase with increasing concentration of the extract. Polarization curves revealed that the Kleinia grandiflora leaf extract is a mixed inhibitor. Impedance diagrams revealed that an increase of Kleinia grandiflora leaf extract concentration increased the charge transfer resistance and decreased the double-layer capacitance. The adsorption process obeys Langmuir's model, with a standard free energy of adsorption (Δ G ads) of -18.62 kJ/mol. The obtained results indicate that the Kleinia grandiflora leaf extract can serve as an effective inhibitor for the corrosion of mild steel in a sulfuric acid medium.

  19. A new facile route for synthesizing of graphene oxide using mixture of sulfuric-nitric-phosphoric acids as intercalating agent

    NASA Astrophysics Data System (ADS)

    Panwar, Vinay; Chattree, Ananya; Pal, Kaushik

    2015-09-01

    In this work, graphene oxide (GO) has been prepared through three different processes namely, eco-friendly Hummers method, modification in improved Hummers method and a new approach. This new approach has been designed by changing some processing parameters and intercalating agent for significant reduction in processing time and to improve the quantity of GO in comparison to the other two methods. This has been achieved through better oxidization of graphite using nitric-sulfuric acid (HNO3-H2SO4) as intercalating agent. X-ray diffraction (XRD), Field Emission Scanning Electron Microscopy (FESEM), Energy-dispersive X-ray spectroscopy (EDX), Raman spectroscopy, Atomic Force Microscopy (AFM), X-ray photoelectron spectroscopy (XPS), UV-visible spectroscopy, and Thermogravimetric analysis (TGA) are used to characterize the GO prepared through different processes. These characterizations have confirmed an improved exfoliation of graphite, using addition of HNO3 in intercalating agent, in a short processing time and bring on higher yield of GO via this new process.

  20. 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.

  1. 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.

  2. Optimization of dilute acid hydrolysis of Enteromorpha

    NASA Astrophysics Data System (ADS)

    Feng, Dawei; Liu, Haiyan; Li, Fuchao; Jiang, Peng; Qin, Song

    2011-11-01

    Acid hydrolysis is a simple and direct way to hydrolyze polysaccharides in biomass into fermentable sugars. To produce fermentable sugars effectively and economically for fuel ethanol, we have investigated the hydrolysis of Enteromorpha using acids that are typically used to hydrolyze biomass: H2SO4, HCl, H3PO4 and C4H4O4 (maleic acid). 5%(w/w) Enteromorpha biomass was treated for different times (30, 60, and 90 min) and with different acid concentrations (0.6, 1.0, 1.4, 1.8, and 2.2%, w/w) at 121°C. H2SO4 was the most effective acid in this experiment. We then analyzed the hydrolysis process in H2SO4 in detail using high performance liquid chromatography. At a sulfuric acid concentration of 1.8% and treatment time of 60 min, the yield of ethanol fermentable sugars (glucose and xylose) was high, (230.5 mg/g dry biomass, comprising 175.2 mg/g glucose and 55.3 mg/g xylose), with 48.6% of total reducing sugars being ethanol fermentable. Therefore, Enteromorpha could be a good candidate for production of fuel ethanol. In future work, the effects of temperature and biomass concentration on hydrolysis, and also the fermentation of the hydrolysates to ethanol fuel should be focused on.

  3. 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.

  4. 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…

  5. Acid-catalyzed hot-water extraction of lipids from Chlorella vulgaris.

    PubMed

    Park, Ji-Yeon; Oh, You-Kwan; Lee, Jin-Suk; Lee, Kyubock; Jeong, Min-Ji; Choi, Sun-A

    2014-02-01

    Acid-catalyzed hot-water treatment for efficient extraction of lipids from a wet microalga, Chlorella vulgaris, was investigated. For an initial fatty acids content of 381.6mg/g cell, the extracted-lipid yield with no heating and no catalyst was 83.2mg/g cell. Under a 1% H2SO4 concentration heated at 120°C for 60min, however, the lipid-extraction yield was 337.4mg/g cell. The fatty acids content, meanwhile, was 935mg fatty acid/g lipid. According to the severity index formula, 337.5mg/g cell of yield under the 1% H2SO4 concentration heated at 150°C for 8min, and 334.2mg/g cell of yield under the 0.5% H2SO4 concentration heated at 150°C for 16min, were obtained. The lipids extracted by acid-catalyzed hot-water treatment were converted to biodiesel. The biodiesel's fatty acid methyl ester (FAME) content after esterification of the microalgal lipids was increased to 79.2% by the addition of excess methanol and sulfuric acid.

  6. Recovery of water and acid from leach solutions using direct contact membrane distillation.

    PubMed

    Kesieme, Uchenna K; Milne, Nicholas; Cheng, Chu Yong; Aral, Hal; Duke, Mikel

    2014-01-01

    This paper describes for the first time the use of direct contact membrane distillation (DCMD) for acid and water recovery from a real leach solution generated by a hydrometallurgical plant. The leach solutions considered contained H2SO4 or HCl. In all tests the temperature of the feed solution was kept at 60 °C. The test work showed that fluxes were within the range of 18-33 kg/m(2)/h and 15-35 kg/m(2)/h for the H2SO4 and HCl systems, respectively. In the H2SO4 leach system, the final concentration of free acid in the sample solution increased on the concentrate side of the DCMD system from 1.04 M up to 4.60 M. The sulfate separation efficiency was over 99.9% and overall water recovery exceeded 80%. In the HCl leach system, HCl vapour passed through the membrane from the feed side to the permeate. The concentration of HCl captured in the permeate was about 1.10 M leaving behind only 0.41 M in the feed from the initial concentration of 2.13 M. In all the experiments, salt rejection was >99.9%. DCMD is clearly viable for high recovery of high quality water and concentrated H2SO4 from spent sulfuric acid leach solution where solvent extraction could then be applied to recover the sulfuric acid and metals. While HCl can be recovered for reuse using only DCMD. PMID:24569289

  7. Sulfur Oxidation and Contrail Precursor Chemistry

    NASA Technical Reports Server (NTRS)

    DeWitt, Kenneth J.

    2003-01-01

    Sulfuric acid (H2SO4), formed in commercial aircraft operations via fuel-S (goes to) SO2 (goes to) SO3 (goes to) H2SO4 plays an important role in the formation of contrails. It is believed that the first step occurs inside the combustor, the second step in the engine exit nozzle, and the third step in the exhaust plume. Thus, measurements of the sulfur oxidation rates are critical to the understanding of contrail formation. Field measurements of contrails formed behind commercial aircraft indicate that significantly greater conversion of fuel-bound sulfur to sulfate aerosol occurs than can be explained by our current knowledge of contrail physics and chemistry. The conversion of sulfur from S(IV) to S(VI) oxidation state, required for sulfate aerosol formation, is thermodynamically favored for the conditions that exist within jet engines but is kinetically disfavored. The principal reaction pathway is O+SO2+M (goes to) SO3+M. The rates of this reaction have never been measured in the temperature and pressure regimes available to aircraft operation. In the first year (FY02) of this project, we performed a series of experiments to elucidate the rate information for the O+SO2+M (goes to) SO3+M reaction. The work performed is described following the proposed work plan. Because we used the H2/O2 system for an O-atom source and rate coefficients were obtained via computer simulation, construction of a reaction mechanism and either recalculation or estimation of thermodynamic properties of H(x)SO(y) species are described first.

  8. 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.

  9. Corrosion inhibition in 2.0 M sulfuric acid solutions of high strength maraging steel by aminophenyl tetrazole as a corrosion inhibitor

    NASA Astrophysics Data System (ADS)

    Sherif, El-Sayed M.

    2014-02-01

    The corrosion of high strength maraging steel after varied immersion times in concentrated solution, 2.0 M, of sulfuric acid has been investigated. The work was also extended to study the effect of 5-(3-aminophenyl)-tetrazole (APTA) on the inhibition of the steel corrosion. The study has been carried out using electrochemical impedance spectroscopy (EIS), potentiodynamic polarization and scanning electron microscope (SEM) along with energy dispersive X-ray analyzer (EDX) investigations. EIS spectra showed that the corrosion and polarization resistances decrease with increasing the immersion time of the steel before measurement and increase in the presence of APTA and the increase of its concentration. Polarization data agreed with the EIS measurements and indicated that the increase of immersion time increases the corrosion of steel by increasing its corrosion current and corrosion rate and lowering its polarization resistance. On the other hand, the addition of APTA and the increase of its concentration minimized the corrosion of steel through decreasing the corrosion current and corrosion rate and increasing the polarization resistance at all exposure test periods. SEM and EDX investigations confirmed that the inhibition of the maraging steel in the 2.0 M H2SO4 solutions is achieved via the adsorption of the APTA molecules onto the steel protecting its surface from being dissolved easily.

  10. Adsorption of sulfur dioxide on ammonia-treated activated carbon fibers

    USGS Publications Warehouse

    Mangun, C.L.; DeBarr, J.A.; Economy, J.

    2001-01-01

    A series of activated carbon fibers (ACFs) and ammonia-treated ACFs prepared from phenolic fiber precursors have been studied to elucidate the role of pore size, pore volume, and pore surface chemistry on adsorption of sulfur dioxide and its catalytic conversion to sulfuric acid. As expected, the incorporation of basic functional groups into the ACFs was shown as an effective method for increasing adsorption of sulfur dioxide. The adsorption capacity for dry SO2 did not follow specific trends; however the adsorption energies calculated from the DR equation were found to increase linearly with nitrogen content for each series of ACFs. Much higher adsorption capacities were achieved for SO2 in the presence of oxygen and water due to its catalytic conversion to H2SO4. The dominant factor for increasing adsorption of SO2 from simulated flue gas for each series of fibers studied was the weight percent of basic nitrogen groups present. In addition, the adsorption energies calculated for dry SO2 were shown to be linearly related to the adsorption capacity of H2SO4 from this flue gas for all fibers. It was shown that optimization of this parameter along with the pore volume results in higher adsorption capacities for removal of SO2 from flue gases. ?? 2001 Elsevier Science Ltd. All rights reserved.

  11. Theoretical study of the hydration of atmospheric nucleation precursors with acetic acid.

    PubMed

    Zhu, Yu-Peng; Liu, Yi-Rong; Huang, Teng; Jiang, Shuai; Xu, Kang-Ming; Wen, Hui; Zhang, Wei-Jun; Huang, Wei

    2014-09-11

    While atmosphere is known to contain a significant fraction of organic substance and the effect of acetic acid to stabilize hydrated sulfuric acids is found to be close that of ammonia, the details about the hydration of (CH3COOH)(H2SO4)2 are poorly understood, especially for the larger clusters with more water molecules. We have investigated structural characteristics and thermodynamics of the hydrates using density functional theory (DFT) at PW91PW91/6-311++G(3df,3pd) level. The phenomena of the structural evolution may exist during the early stage of the clusters formation, and we tentatively proposed a calculation path for the Gibbs free energies of the clusters formation via the structural evolution. The results in this study supply a picture of the first deprotonation of sulfuric acids for a system consisting of two sulfuric acid molecules, an acetic acid molecule, and up to three waters at 0 and 298.15 K, respectively. We also replace one of the sulfuric acids with a bisulfate anion in (CH3COOH)(H2SO4)2 to explore the difference of acid dissociation between two series of clusters and interaction of performance in clusters growth between ion-mediated nucleation and organics-enhanced nucleation.

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

    PubMed Central

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

    2016-01-01

    Particles in the upper troposphere and lower stratosphere (UT/LS) consist mostly of concentrated sulfuric acid (40–80 wt %) in water. However, airborne measurements have shown that these particles also contain a significant fraction of organic compounds of unknown chemical composition. Acid-catalyzed reactions of carbonyl species are believed to be responsible for significant transfer of gas phase organic species into tropospheric aerosols and are potentially more important at the high acidities characteristic of UT/LS particles. In this study, experiments combining sulfuric acid (H2SO4) with propanal and with mixtures of propanal with glyoxal and/or methylglyoxal at acidities typical of UT/LS aerosols produced highly colored surface films (and solutions) that may have implications for aerosol properties. In order to identify the chemical processes responsible for the formation of the surface films, attenuated total reflectance–Fourier transform infrared (ATR-FTIR) and 1H nuclear magnetic resonance (NMR) spectroscopies were used to analyze the chemical composition of the films. Films formed from propanal were a complex mixture of aldol condensation products, acetals and propanal itself. The major aldol condensation products were the dimer (2-methyl-2-pentenal) and 1,3,5-trimethylbenzene that was formed by cyclization of the linear aldol condensation trimer. Additionally, the strong visible absorption of the films indicates that higher-order aldol condensation products must also be present as minor species. The major acetal species were 2,4,6-triethyl-1,3,5-trioxane and longer-chain linear polyacetals which are likely to separate from the aqueous phase. Films formed on mixtures of propanal with glyoxal and/or methylglyoxal also showed evidence of products of cross-reactions. Since cross-reactions would be more likely than self-reactions under atmospheric conditions, similar reactions of aldehydes like propanal with common aerosol organic species like glyoxal and

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

    NASA Astrophysics Data System (ADS)

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

    2014-11-01

    Particles in the upper troposphere and lower stratosphere (UT/LS) consist mostly of concentrated sulfuric acid (40-80 wt %) in water. However, airborne measurements have shown that these particles also contain a significant fraction of organic compounds of unknown chemical composition. Acid-catalyzed reactions of carbonyl species are believed to be responsible for significant transfer of gas phase organic species into tropospheric aerosols and are potentially more important at the high acidities characteristic of UT/LS particles. In this study, experiments combining sulfuric acid (H2SO4) with propanal and with mixtures of propanal with glyoxal and/or methylglyoxal at acidities typical of UT/LS aerosols produced highly colored surface films (and solutions) that may have implications for aerosol properties. In order to identify the chemical processes responsible for the formation of the surface films, Attenuated Total Reflectance-Fourier Transform Infrared and 1H Nuclear Magnetic Resonance spectroscopies were used to analyze the chemical composition of the films. Films formed from propanal were a complex mixture of aldol condensation products, acetals and propanal itself. The major aldol condensation products were the dimer (2-methyl-2-pentenal) and 1,3,5-trimethylbenzene, which was formed by cyclization of the linear aldol condensation trimer. Additionally, the strong visible absorption of the films indicates that higher order aldol condensation products must also be present as minor species. The major acetal species were 2,4,6-triethyl-1,3,5-trioxane and longer-chain linear polyacetals which are likely to separate from the aqueous phase. Films formed on mixtures of propanal with glyoxal and/or methylglyoxal also showed evidence for products of cross-reactions. Since cross-reactions would be more likely than self-reactions under atmospheric conditions, similar reactions of aldehydes like propanal with common aerosol organic species like glyoxal and methylglyoxal

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

    Particles in the upper troposphere and lower stratosphere (UT/LS) consist mostly of concentrated sulfuric acid (40-80 wt%) in water. However, airborne measurements have shown that these particles also contain a significant fraction of organic compounds of unknown chemical composition. Acid-catalyzed reactions of carbonyl species are believed to be responsible for significant transfer of gas phase organic species into tropospheric aerosols and are potentially more important at the high acidities characteristic of UT/LS particles. In this study, experiments combining sulfuric acid (H2SO4) with propanal and with mixtures of propanal with glyoxal and/or methylglyoxal at acidities typical of UT/LS aerosols produced highly colored surface films (and solutions) that may have implications for aerosol properties. In order to identify the chemical processes responsible for the formation of the surface films, attenuated total reflectance-Fourier transform infrared (ATR-FTIR) and 1H nuclear magnetic resonance (NMR) spectroscopies were used to analyze the chemical composition of the films. Films formed from propanal were a complex mixture of aldol condensation products, acetals and propanal itself. The major aldol condensation products were the dimer (2-methyl-2-pentenal) and 1,3,5-trimethylbenzene that was formed by cyclization of the linear aldol condensation trimer. Additionally, the strong visible absorption of the films indicates that higher-order aldol condensation products must also be present as minor species. The major acetal species were 2,4,6-triethyl-1,3,5-trioxane and longer-chain linear polyacetals which are likely to separate from the aqueous phase. Films formed on mixtures of propanal with glyoxal and/or methylglyoxal also showed evidence of products of cross-reactions. Since cross-reactions would be more likely than self-reactions under atmospheric conditions, similar reactions of aldehydes like propanal with common aerosol organic species like glyoxal and

  15. Sulfur and hydrogen isotope anomalies in meteorite sulfonic acids.

    PubMed

    Cooper, G W; Thiemens, M H; Jackson, T L; Chang, S

    1997-08-22

    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.

  16. 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.

  17. 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.

  18. 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.

  19. The effect of duration of exposure on sulfuric acid-induced pulmonary function changes in asthmatic adolescent subjects: A dose-response study

    SciTech Connect

    Koenig, J.Q.; Covert, D.S.; Larson, T.V.; Pierson, W.E. )

    1992-09-01

    To evaluate the pulmonary effects of varying doses of sulfuric acid, adolescent subjects with asthma were exposed to 35 or 70 micrograms/m3 sulfuric acid for 45 or 90 min. Exposure was carried out during intermittent moderate exercise. The pulmonary functions measured before and after exposure were FEV1, FVC, and total respiratory resistance. The 45 min exposures were associated with larger decreases in FEV1 (-6% or -3%) than the 90 min exposures (-1% or +2%). Analysis of variance of the change in FEV1 among the exposures revealed that the 45 min exposure to 35 micrograms/m3 was significant (p = 0.03). The p value for 45 min exposure to 70 micrograms/m3 was not significant (p = 0.08). Using analysis of variance, neither of the 90 min exposures was associated with a significant decrease in FEV1 compared to air exposure. Also, none of the changes in FVC or RT was significant. When baseline to post-exposure changes were compared for each of the five test atmospheres using paired t tests, both of the 45 min exposures were associated with statistical significance (p < 0.001 for 35 micrograms/m3 and p < 0.005 for 70 micrograms/m3). This baseline to post exposure change was not statistically significant for the 90 min exposures. The reason for the lesser effect on pulmonary function at increased exposure duration is not known; it may be due to changes in either varying deposition patterns or changes in buffering capacity of the cells lining the airways. With respect to individual sensitivities to H2SO4, the data showed a significant consistency across test atmospheres.

  20. 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.

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

    PubMed

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

    2009-03-01

    A simple and convenient methodology for selective sulfonation of aromatic compounds using sulfuric acid under sonication is described. The present methodology shows a considerable enhancement in the reaction rate along with improved selectivity compared with the reactions performed under silent conditions. The effect of various parameters such as agitation speed, sulfuric acid concentration, and temperature on reaction system have been investigated and are explained on the basis of ultrasonically generated cavitational effects. PMID:19014895

  2. Influence of liquid density on the parametric shape instability of sonoluminescence bubbles in water and sulfuric acid.

    PubMed

    Godínez, F A; Navarrete, M

    2011-07-01

    Parametric shape instability of sonoluminescing argon bubbles in water and aqueous H(2)SO(4) was numerically analyzed considering gas and liquid density variations. The employed model couples Gilmore, Tait (liquid) and van der Waals (gas) equations to simulate radial dynamics and density changes, respectively. Shape stability-instability zones in the P(a)-R(0) space resulted from a linear stability analysis. For the argon-water and argon-water-acid systems, numerical results indicate a rapid rise in both gas and liquid densities during final stages of bubble implosion which result in a stabilizing effect on the parametric instability.

  3. 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)

  4. 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.

  5. Monitoring of sulfuric acid episodes in St. Louis, Missouri

    SciTech Connect

    Husar, R.B.; Cobourn, W.G.; Djukic-Husar, J.; Husar, R.B.

    1980-08-20

    During July 1977 and again in February 1978 in St. Louis, Missouri, episodes of about 3-day duration occurred in which sulfuric acid persisted as part of the regional haze aerosol. These sulfuric acid episodes were monitored with 15-min time resolution by a thermal analysis--flame photometric detection particulate sulfur monitor. The measurement technique detects the concentration of total particulate sulfur as well as the fraction as H/sub 2/SO/sub 4/. However, it cannot distinguish between (NH/sub 4/)/sub 2/SO/sub 4/ and NH/sub 4/HSO/sub 4/; thus it is not specific for the detection of total hydrogen ion concentration associated with particulate sulfur. In the summer, July--August 1977, total particulate sulfur average was 3.8 ..mu..gS/m/sup 3/, and the H/sub 2/SO/sub 4/ (measured as sulfur) average was below 0.5 ..mu..gS/m/sup 3/, while in the winter, February--March 1978, it was 3.2 and 0.8 ..mu..gS/m/sup 3/, respectively. During the summer episode the H/sub 2/SO/sub 4/ (as sulfur) peaked at about 10 ..mu..gS/m/sup 3/, compared to a total particulate sulfur peak concentration of 20 ..mu..gS/m/sup 3/. During the winter episode the H/sub 2/SO/sub 4/ concentration peaked at about 4 ..mu..gS/m/sup 3/, compared to a particulate sulfur peak concentration of 6 ..mu..gS/m/sup 3/. Daily average particulate sulfur and light scattering from July--August 1977 and February--March 1978 show a strong correlation (r>0.8). There were several general differences between the summer and winter data which suggest chemical and physical changes in the atmospheric aerosol. Analysis of the summer data revealed overall diurnal patterns in particulate sulfur and acidity, but these patterns did not show up with the winter data. The strong correlation between light scattering and particulate sulfur indicates that sulfur compounds play a prominent role in visibility degradation by fine particles.

  6. 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.

  7. 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...

  8. 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...

  9. 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...

  10. 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...

  11. 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...

  12. 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.

  13. 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.

  14. 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.

  15. Speciation of technetium peroxo complexes in sulfuric acid revisited

    DOE PAGES

    Poineau, Frederic; German, Konstantin E.; Burton-Pye, Benjamin P.; Weck, Philippe F.; Kim, Eunja; Kriyzhovets, Olga; Safonov, Aleksey; Ilin, Viktor; Francesconi, Lynn C.; Sattelberger, Alfred P.; et al

    2014-08-24

    We found that the reaction of Tc(+7) with H2O2 has been studied in H2SO4 and the speciation of technetium performed by UV–visible and 99-Tc NMR spectroscopy. UV–visible measurements show that for H2SO4 ≥ 9 M and H2O2 = 0.17 M, TcO3(OH)(H2O)2 reacts immediately and blue solutions are obtained, while no reaction occurs for H2SO42SO44 - begins to react for H2O2 = 2.12 M and red solutions are obtained. The UV–visible spectra of the red species are identical to the one obtained from the reaction of TcO4 - with H2O2 in HNO3 and consistent with the presence of TcO(O2)2(H2O)(OH). The 99-Tcmore » NMR spectrum of the red solution exhibits a broad signal centered at +5.5 ppm vs TcO4 - and is consistent with the presence of a low symmetry Tc(+7) molecule.« less

  16. 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.

  17. 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.

  18. 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...

  19. Diffusion of benzoic acid (1); sulfur hexafluoride (2)

    NASA Astrophysics Data System (ADS)

    Winkelmann, J.

    This document is part of Subvolume A `Gases in Gases, Liquids and their Mixtures' of Volume 15 `Diffusion in Gases, Liquids and Electrolytes' of Landolt-Börnstein Group IV `Physical Chemistry'. It is part of the chapter of the chapter `Diffusion in Pure Gases' and contains data on diffusion of (1) benzoic acid; (2) sulfur hexafluoride

  20. Hydrogen peroxide in sulfuric acid extraction of uranium ores

    SciTech Connect

    DeVries, F.W.

    1984-01-10

    Uranium can be extracted from its ores at a pH of 2.5 to 5.5 using sulfuric acid, hydrogen peroxide, trace of iron and a sulfate. The extraction process is applicable to both tank leaching of conventionally mined ores and in situ leaching.

  1. 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.

  2. 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.

  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.

    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.

  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.

    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.

  5. 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

  6. Effects of nitrogen oxides, sulfur dioxide, and ferric ions on the corrosion of mild steel in concentrated sulfuric acid

    NASA Astrophysics Data System (ADS)

    Andersen, Terrell N.; Vanorden, Naola; Schlitt, W. Joseph

    1980-08-01

    Effects of nitrate ions, nitrous acid, sulfur dioxide, and ferric ions on the corrosion of mild steel in unstirred, concentrated sulfuric acid were determined in laboratory tests. Nitrate and nitrous acid at levels up to 1000 ppm accelerate corrosion. At concentrations greater than 1000 ppm nitrate passivates the steel. Sulfur dioxide and ferric ions have no detectable influence on the corrosion. Reaction mechanisms are presented to explain the observed effects. The impact of nitrogen oxides on the storage and handling of sulfide smelter by-product acid is discussed.

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. FURNACE INJECTION OF ALKALINE SORBENTS FOR SULFURIC ACID CONTROL

    SciTech Connect

    Gary M. Blythe

    2002-04-29

    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, 2001 through March 31, 2002. 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 Corporation is the prime contractor. This is the fifth reporting period for the subject Cooperative Agreement. During the previous (fourth) 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 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 (at both Gavin 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

  12. Dilute Sulfuric Acid Pretreatment of Agricultural and Agro-Industrial Residues for Ethanol Production

    NASA Astrophysics Data System (ADS)

    Martin, Carlos; Alriksson, Björn; Sjöde, Anders; Nilvebrant, Nils-Olof; Jönsson, Leif J.

    The potential of dilute-acid prehydrolysis as a pretreatment method for sugarcane bagasse, rice hulls, peanut shells, and cassava stalks was investigated. The prehydrolysis was performed at 122°C during 20, 40, or 60 min using 2% H2SO4 at a solid-to-liquid ratio of 1∶10. Sugar formation increased with increasing reaction time. Xylose, glucose, arabinose, and galactose were detected in all of the prehydrolysates, whereas mannose was found only in the prehydrolysates of peanut shells and cassava stalks. The hemicelluloses of bagasse were hydrolyzed to a high-extent yielding concentrations of xylose and arabinose of 19.1 and 2.2 g/L, respectively, and a xylan conversion of more than 80%. High-glucose concentrations (26-33.5 g/L) were found in the prehydrolysates of rice hulls, probably because of hydrolysis of starch of grain remains in the hulls. Peanut shells and cassava stalks rendered low amounts of sugars on prehydrolysis, indicating that the conditions were not severe enough to hydrolyze the hemicelluloses in these materials quantitatively. All prehydrolysates were readily fermentable by Saccharomyces cerevisiae. The dilute-acid prehydrolysis resulted in a 2.7-to 3.7-fold increase of the enzymatic convertibility of bagasse, but was not efficient for improving the enzymatic hydrolysis of peanut shells, cassava stalks, or rice hulls.

  13. 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.

  14. 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.

  15. 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.

  16. Sulfuric Acid Intercalated Graphite Oxide for Graphene Preparation

    NASA Astrophysics Data System (ADS)

    Hong, Yanzhong; Wang, Zhiyong; Jin, Xianbo

    2013-12-01

    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.

  17. 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

  18. 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

  19. Process for producing and recovering elemental sulfur from acid gas

    SciTech Connect

    Reed, R. L.

    1985-03-26

    A system and process produce high actual levels of sulfur recovery from acid gas. The system includes two conventional Claus reactors and two cold bed adsorption (CBA) reactors. Four condensers are provided, one disposed before each of the catalytic reactors, and one disposed after the CBA reactor. The system includes a gas clean-up treatment zone for hydrogenation, drying and oxidation of gas to provide stoichiometric ratio of H/sub 2/S and SO/sub 2/. The gas is passed through the clean-up treatment zone prior to being fed to the first of the CBA reactors. The system is designed to operate either in a recovery mode or in a regeneration mode. In the recovery mode, the reactors are in series and the CBA reactors are operated below dew point of sulfur. In regeneration mode, effluent from the clean-up treatment zone is heated in a heat exchanger using effluent from the first catalytic reactor as the heat source. The resulting regeneration gas is fed to one of the two CBA reactors to vaporize sulfur and regenerate the catalyst. The vaporized sulfur is recovered in the condenser. The effluent from the condenser is passed to the other CBA reactor which is operated in the recovery mode during regeneration.

  20. A molal-based model for strong acid chemistry at low temperatures (<200 to 298 K)

    NASA Astrophysics Data System (ADS)

    Marion, Giles M.

    2002-07-01

    Geochemical processes occurring in cold environments on Earth, Mars, and Europa have elicited considerable interest in the application of geochemical models to subzero temperatures. Few existing geochemical models explicitly include acid chemistry and those that do are largely restricted to temperatures ≥0°C or rely on the mole-fraction scale rather than the more common molal scale. This paper describes (1) use of the Clegg mole-fraction acid models to develop a molal-based model for hydrochloric, nitric, and sulfuric acids at low temperatures; (2) incorporation of acid chemistry and nitrate minerals into the FREZCHEM model; (3) validation and limitations of the derived acid model; and (4) simulation of hypothetical acidic brines for Europa. The Clegg mole-fraction acid models were used to estimate activities of water and mean ionic activity coefficients that serve as the database for estimating molal Pitzer-equation parameters for HCl (188 to 298 K), HNO 3 (228 to 298 K), and H 2SO 4 (208 to 298 K). Model eutectics for HNO 3 and H 2SO 4 agree with experimental measurements to within ± 0.2°C. In agreement with previous work, the experimental freezing point depression (fpd) data for pure HCl at subzero temperatures were judged to be flawed and unreliable. Three alternatives are discussed for handling HCl chemistry at subzero temperatures. In addition to defining the solubility of solid-phase acids, this work also adds three new nitrate minerals and six new acid salts to the FREZCHEM model and refines equilibria among water ice, liquid water, and water vapor over the temperature range from 180 to 298 K. The final system is parameterized for Na-K-Mg-Ca-H-Cl-SO 4-NO 3-OH-HCO 3-CO 3-CO 2-H 2O. Simulations of hypothetical MgSO 4-H 2SO 4-H 2O and Na 2SO 4-MgSO 4-H 2SO 4-H 2O brines for Europa demonstrate how freezing can convert a predominantly salt solution into a predominantly acid solution at subzero temperatures. This result has consequences for the effects of

  1. 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.

  2. 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.

  3. Efficient production of bioethanol from corn stover by pretreatment with a combination of sulfuric acid and sodium hydroxide.

    PubMed

    Tan, Li; Tang, Yue-Qin; Nishimura, Hiroto; Takei, Shouta; Morimura, Shigeru; Kida, Kenji

    2013-01-01

    Corn stover is the most abundant agricultural residue in China and a valuable reservoir for bioethanol production. In this study, we proposed a process for producing bioethanol from corn stover; the pretreatment prior to presaccharification, followed by simultaneous saccharification and fermentation (SSF) by using a flocculating Saccharomyces cerevisiae strain, was optimized. Pretreatment with acid-alkali combination (1% H2SO4, 150 °C, 10 min, followed by 1% NaOH, 80°C, 60 min) resulted in efficient lignin removal and excellent recovery of xylose and glucose. A glucose recovery efficiency of 92.3% was obtained by enzymatic saccharification, when the pretreated solid load was 15%. SSF was carried out at 35 °C for 36 hr after presaccharification at 50 °C for 24 hr, and an ethanol yield of 88.2% was achieved at a solid load of 15% and an enzyme dosage of 15 FPU/g pretreated corn stover.

  4. Low-cost silica, calcite and metal sulfide scale control through on-site production of sulfurous acid from H{sub 2}S or elemental sulfur

    SciTech Connect

    Gallup, D.L.; Kitz, K.

    1997-12-31

    UNOCAL Corporation currently utilizes brine pH modification technology to control scale deposition. Acids utilized in commercial operations include, sulfuric and hydrochloric. A new process reduces costs by producing acid on-site by burning hydrogen sulfide or elemental sulfur. Hydrogen sulfide in non-condensible gas emissions is reduced by oxidization to sulfurous acid. Brine or condensate is treated with sulfurous acid to control scale deposition, mitigate corrosion and improve gas partitioning in condensers.

  5. 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

  6. 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

  7. 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

  8. Sulfur-containing amino acid requirements of growing dogs.

    PubMed

    Blaza, S E; Burger, I H; Holme, D W; Kendall, P T

    1982-11-01

    Three experiments were undertaken to establish the total sulfur-containing amino acid requirement of growing dogs. In experiment 1, six Labradors failed to grow normally when fed a soy isolate diet of 0.28% methionine with 0.18% cystine but grow well when the food was supplemented to either 0.57% or 0.74% methionine. In the next experiment, 12 Labradors and 21 beagles were fed the soy isolate diet containing either 0.39%, 0.57% or 0.74% methionine in the presence of 0.15% cystine for 12 weeks. Dogs fed 0.39% methionine had significantly lower body weights, nitrogen retentions, food intakes and feed efficiencies than their littermates fed the two higher levels. This diet provided 468 kcal metabolizable energy (ME) per 100 g, therefore a level of 116 mg total sulfur-containing amino acids (TSAA)/100 kcal ME was not adequate for growth. The lowest level found to be adequate was 0.57% methionine, or 154 mg TSAA/100 kcal ME, which is similar to the requirement of other young omnivores. A final experiment with a free amino acid diet indicated that a level of 117 mg TSAA/100 kcal ME while inadequate for Labradors, may be sufficient for some beagles, highlighting differences between intact protein and free amino acid diets and suggesting possible breed differences.

  9. To bridge or not to bridge: The role of sulfuric acid in the Beckmann rearrangement

    NASA Astrophysics Data System (ADS)

    Lin, Chester R.; Yu, Li-Juan; Li, Shuhua; Karton, Amir

    2016-08-01

    Based on ab initio calculations using the Gaussian-4 method, we propose a new catalytic mechanism for the Beckmann rearrangement in concentrated H2SO4. Our calculations suggest that H2SO4 catalyzes the 1,2-proton-shift step via a cyclic transition structure, in which H2SO4 acts as a proton-transfer bridge. The reaction barrier for this mechanism is lower by 48.1 kJ mol-1 than the barrier for the previously suggested catalytic mechanism, which involves a strained 3-memberd-ring transition structure. According to the previous mechanism the 1,2-proton shift has the highest activation energy, while in the revised mechanism the highest activation energy is obtained for the ensuing rearrangement/dehydration step.

  10. 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

  11. 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

  12. 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

  13. Acute exposure to acid fog. Effects on mucociliary clearance

    SciTech Connect

    Laube, B.L.; Bowes, S.M. III; Links, J.M.; Thomas, K.K.; Frank, R. )

    1993-05-01

    Submicrometric sulfuric acid (H2SO4) aerosol can affect mucociliary clearance without eliciting irritative symptoms or changes in pulmonary function. The effect of larger fog droplets containing H2SO4 on mucociliary clearance is unknown. We quantified mucociliary clearance from the trachea (n = 4) and small airways (n = 7) of young healthy male adults after an acute exposure to H2SO4 fog (MMAD = 10.3 microns; pH = 2.0; liquid water content = 481 +/- 65 mg/m3; osmolarity = 30 mOsm). Acid fog (AF) or saline fog (SF) (10.9 microns; 492 +/- 116 mg/m3; 30 mOsm) was administered for 40 min of unencumbered breathing (no mouth-piece) at rest and for 20 min of exercise sufficient to produce oronasal breathing. Fog exposures were followed by a methacholine (MCh) challenge (a measure of airway reactivity) or inhalation of technetium-99M radioaerosol (MMAD = 3.4 microns) on 2 study days each. Changes in symptoms and forced ventilatory function were also assessed. Clearance was quantified from computer-assisted analyses of gamma camera images of the lower respiratory tract in terms of %removal/min of the radiolabel from the trachea 25 min after inhalation and from the outer zone of the right lung after 1.9 to 3 h. Symptoms, forced ventilatory function, and MCh response were unaffected by either fog. Tracheal clearance was more rapid in four of four subjects after AF (0.83 +/- 1.58% removal/min) compared with that after SF (-0.54 +/- 0.85% removal/min). Outer zone clearance was more rapid in six of seven subjects after AF (0.22 +/- 0.15% removal/min) compared with that after SF (0.01 +/- 0.09% removal/min).

  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. Heterogeneous chemical reaction of chlorine nitrate and water on sulfuric-acid surfaces at room temperature

    NASA Technical Reports Server (NTRS)

    Rossi, Michel J.; Malhotra, Ripudaman; Golden, David M.

    1987-01-01

    The use of H2SO4 as a catalyst for aerosol production of chlorine compounds in the chemistry of the antarctic stratosphere was investigated in laboratory trials. The experiments involved the gas surface collision rate of a molecule on a given surface during its residence time in a Knudsen cell in molecular flow conditions. Chlorine nitrate gas was made to flow through a chamber exposed to a container holding a 95.6 pct H2SO4 solution. Gas leaving the cell was scanned with a mass spectrometer. A sticking coefficient of 0.00032 was found for the chlorine nitrate, a value five times that previously reported.

  16. Sulfuric acid deposition from stratospheric geoengineering with sulfate aerosols

    NASA Astrophysics Data System (ADS)

    Kravitz, Ben; Robock, Alan; Oman, Luke; Stenchikov, Georgiy; Marquardt, Allison B.

    2009-07-01

    We used a general circulation model of Earth's climate to conduct geoengineering experiments involving stratospheric injection of sulfur dioxide and analyzed the resulting deposition of sulfate. When sulfur dioxide is injected into the tropical or Arctic stratosphere, the main additional surface deposition of sulfate occurs in midlatitude bands, because of strong cross-tropopause flux in the jet stream regions. We used critical load studies to determine the effects of this increase in sulfate deposition on terrestrial ecosystems by assuming the upper limit of hydration of all sulfate aerosols into sulfuric acid. For annual injection of 5 Tg of SO2 into the tropical stratosphere or 3 Tg of SO2 into the Arctic stratosphere, neither the maximum point value of sulfate deposition of approximately 1.5 mEq m-2 a-1 nor the largest additional deposition that would result from geoengineering of approximately 0.05 mEq m-2 a-1 is enough to negatively impact most ecosystems.

  17. Electrical conductivity of acidic sulfate solution

    NASA Astrophysics Data System (ADS)

    Majima, Hiroshi; Peters, Ernest; Awakura, Yasuhiro; Park, Sung Kook

    1987-03-01

    The electrical conductivities of the aqueous solution system of H2SO4-MSO4 (involving ZnSO4, MgSO4, Na2SO4, and (NH4)2SO4), reported by Tozawa et al., were examined in terms of a (H2O) and H+ ion concentration. The equations to compute the concentrations of various species in aqueous sulfuric acid solutions containing metal sulfates were derived for a typical example of the H2SO4-ZnSO4-MgSO4-(Na2SO4)-H2O system. It was found that the H+ ion concentrations in concentrated sulfuric acid solutions corresponding to practical zinc electrowinning solutions are very high and remain almost constant with or without the addition of metal sulfates. The addition of metal sulfates to aqueous sulfuric acid solution causes a decrease in electrical conductivity, and this phenomenon is attributed to a decrease in water activity, which reflects a decrease in the amount of free water. The relationship between conductivity and water activity at a constant H+ ion concentration is independent of the kind of sulfates added. On the other hand, any increase in H+ ion concentration results in an increase in electrical conductivity. A novel method for the prediction of electrical conductivity of acidic sulfate solution is proposed that uses the calculated data of water activity and the calculated H+ ion concentration. Also, the authors examined an extension of the Robinson-Bower equation to calculate water activity in quarternary solutions based on molarity instead of molality, and found that such calculated values are in satisfactory agreement with those determined experimentally by a transpiration method.

  18. Materials Data on H2SO4 (SG:9) by Materials Project

    SciTech Connect

    Kristin Persson

    2014-07-09

    Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

  19. Materials Data on H2SO4 (SG:5) by Materials Project

    SciTech Connect

    Kristin Persson

    2014-07-09

    Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

  20. Materials Data on MnH2(SO4)2 (SG:14) by Materials Project

    SciTech Connect

    Kristin Persson

    2014-11-02

    Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

  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. 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. PMID:22444067

  3. 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.

  4. 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.

  5. 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

  6. 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

  7. 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.

  8. Composition of acid tars from sulfuric acid treatment of petroleum oils

    SciTech Connect

    Frolov, A.F.; Denisova, T.L.; Karpova, I.V.; Titova, T.S.

    1986-01-01

    This paper examines the composition of freshly produced acid tars and pond tars, gives an analysis of the acid part of the tars, and obtains data on the change in composition of the acid tar in the course of storage--data that are needed in developing methods for utilizing the tar. The acid-pond tars consist of a mixture of hydrocarbons with a very low content of acids, whereas the freshly produced acid tars consist mainly of sulfuric acid, sulfonic acids, and carboxylic acids. In the course of storage, hardening of acid tars in the volume proceeds through reactions of polymerization, condensation, and oxidation of the surface layer that is in contact with air.

  9. The formation of sulfate and elemental sulfur aerosols under varying laboratory conditions: implications for early earth.

    PubMed

    DeWitt, H Langley; Hasenkopf, Christa A; Trainer, Melissa G; Farmer, Delphine K; Jimenez, Jose L; McKay, Christopher P; Toon, Owen B; Tolbert, Margaret A

    2010-10-01

    The presence of sulfur mass-independent fractionation (S-MIF) in sediments more than 2.45 × 10(9) years old is thought to be evidence for an early anoxic atmosphere. Photolysis of sulfur dioxide (SO(2)) by UV light with λ < 220 nm has been shown in models and some initial laboratory studies to create a S-MIF; however, sulfur must leave the atmosphere in at least two chemically different forms to preserve any S-MIF signature. Two commonly cited examples of chemically different sulfur species that could have exited the atmosphere are elemental sulfur (S(8)) and sulfuric acid (H(2)SO(4)) aerosols. Here, we use real-time aerosol mass spectrometry to directly detect the sulfur-containing aerosols formed when SO(2) either photolyzes at wavelengths from 115 to 400 nm, to simulate the UV solar spectrum, or interacts with high-energy electrons, to simulate lightning. We found that sulfur-containing aerosols form under all laboratory conditions. Further, the addition of a reducing gas, in our experiments hydrogen (H(2)) or methane (CH(4)), increased the formation of S(8). With UV photolysis, formation of S(8) aerosols is highly dependent on the initial SO(2) pressure; and S(8) is only formed at a 2% SO(2) mixing ratio and greater in the absence of a reductant, and at a 0.2% SO(2) mixing ratio and greater in the presence of 1000 ppmv CH(4). We also found that organosulfur compounds are formed from the photolysis of CH(4) and moderate amounts of SO(2). The implications for sulfur aerosols on early Earth are discussed. Key Words: S-MIF-Archean atmosphere-Early Earth-Sulfur aerosols.

  10. The Other Chemistry of the Jovian Icy Satellites - Low Energy and Sulfurous

    NASA Technical Reports Server (NTRS)

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

    2010-01-01

    Spectra of Jupiter's icy satellites reveal surfaces dominated by H2O-ice with minor amounts of SO2 and other materials. The co-existence of H2O and SO2 in surfaces exposed to jovian magnetospheric radiation suggests that sulfuric acid (H2SO4) also could be present. This was noted by Carlson et al. (1999), who supported this suggestion with assignments of near-IR bands in Europa spectra to hydrated H2SO4. Laboratory experiments since have demonstrated radiolytically-driven syntheses in S- and SO2-containing H2O-Ices (Carlson et al., 2002; Moore et al., 2006). In the Cosmic Ice Laboratory, we recently have investigated the thermal chemistry of SO2 trapped in H2O-ice. IR spectra of H2O + SO2 mixtures recorded at 10 to 230 K were used to follow low-temperature reactions in the absence of radiation effects. No SO2 reactions were found at 10 K, but warming to more-relevant Europa temperatures produced both HSO3(-) and S2O5(2-). Added NH3 shifted the product composition toward SO3(2-) and away from the other ions. We find that H2O and SO2 react to produce sulfur oxyanions, such as bisulfite, that as much as 30% of the SO2 can be consumed through this reaction, and that the products remain in the ice when the temperature is lowered, indicating that these reactions are irreversible. Our results suggest that thermally-induced reactions can alter the chemistry at and below the surfaces of the icy satellites in the jovian system.

  11. Molecular dynamic simulations of OH-stretching overtone induced photodissociation of fluorosulfonic and chlorosulfonic acid.

    PubMed

    Gupta, Priyanka; Lane, Joseph R; Kjaergaard, Henrik G

    2010-08-01

    We investigate the OH-stretching overtone dynamics of fluorosulfonic acid (FSO(3)H) and chlorosulfonic acid (ClSO(3)H) using classical trajectory simulations. The initial nuclear coordinates and momenta for the trajectories are sampled from anharmonic correlation-corrected vibrational self consistent field (CC-VSCF) wavefunctions. We consider both OH-stretching overtone states and combination states containing a mix of OH-stretching overtones and SOH-bending or OSOH-torsional modes. Our molecular dynamics simulations confirm that photodissociation of these sulfonic acids to form the corresponding hydrogen halides and sulfur trioxide (HF + SO(3) and HCl + SO(3)), is possible via highly vibrationally excited states on a picosecond timescale. Hydrogen-hopping events are also observed in the trajectories whereby the hydrogen atom of the excited OH group is found to migrate to one of the adjacent S=O groups. The transition states, activation energies and dissociation dynamics of FSO(3)H and ClSO(3)H are found to be similar to those of H(2)SO(4). We suggest that these halogenated sulfonic acids should be suitable proxy molecules for an experimental investigation of the OH-stretching overtone induced photodissociation of H(2)SO(4) thought to be important in Earths' atmosphere. PMID:20526505

  12. HTR Fuel Waste Management: TRISO separation and acid-graphite intercalation compounds preparation

    NASA Astrophysics Data System (ADS)

    Guittonneau, Fabrice; Abdelouas, Abdesselam; Grambow, Bernd

    2010-12-01

    Considering the need to reduce waste production and greenhouse emissions and still keeping high energy efficiency, various 4th generation nuclear energy systems have been proposed. As far as graphite-moderated reactors are concerned (future high temperature fast or thermal reactors), one of the key issues is the large volumes of irradiated graphite encountered. With the objective to reduce volume of waste in the HTR concept, it is very important to be able to separate the fuel from low level activity graphite representing a large volume. The separated TRISO particles can then be reprocessed for waste separation or disposed off in geological repository. In addition, preparation of acid-GICs from the separated graphite may constitute a way to recycle this waste. We used HTR-type compact fuel with ZrO 2 TRISO particles to test two separation methods: low (H 2SO 4 + H 2O 2) and high (H 2SO 4 + HNO 3) temperature acid treatments. In both cases the TRISO separation was complete but some TRISO layers oxidized at high temperature. At low temperature, the desegregation of graphite grains is facilitated by intercalation of sulfuric acid between the graphene layers. The acid-GIC obtained consists of pure phases of high quality suggesting their potential industrial recycling.

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

    SciTech Connect

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

    1995-03-01

    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.

  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. 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. PMID:11068828

  16. 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.

  17. Sulfur Oxidation, Microbes And Acidity In A Mine Tailings Lake

    NASA Astrophysics Data System (ADS)

    Warren, L. A.; Bernier, L.

    2003-12-01

    Disposal of tailings (waste rock) aqueously is a common approach at mine sites to minimize oxidation of the associated sulfur minerals (pyrrhotite, pyrite) and the associated generation of acidity that accompanies this process. The study site, Moose Lake, receives tailings runoff at a nickel mine in Northern Ontario, which has rendered the lake highly acidic (surface pH values less than 3.5) with high metal loads and on-going acid export to off-site, downstream systems. To investigate the potential influence of microbial processes for acid generation, as well as characterizing any attendant influences for metal behaviour, the biogeochemistry of Moose Lake was characterized on a seasonal and a diel basis during the summer of 2002. Physico-chemical profiles were used to identify the area of strong redox gradient across the thermocline (typically 1 to 2 metres across this zone) on each sampling day. Samples at five depths within this redox gradient, were then collected for Fe3+/Fe2+, SO42-/H2S, metal and microbial samples, in addition to more highly resolved Hydrolab profiling. Samples were collected both during the lighted portion of the day (10am-12pm) and at dusk (6pm-8pm) to evaluate any contributions to S and Fe cycling attributed to photosynthetic activity. Results indicate a clear seasonal increase in acidity in the upper waters of the lake: pH values dropped from 3.19 in May to 2.90 in September. Further, a strong diel trend of increasing acidity (lower pH) from mid morning to dusk was also observed for each sampling period. Biotic control on S processes appears to be important associated with the thermocline region of the lake, whilst surficial processes occurring in the upper one to three meters are more consistent with a dominant abiotic control. Both pathways contribute to acidity generation, however the controls and rates differ. These results and implications for mitigation strategies will be presented.

  18. 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.

  19. 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)

  20. Thermochemical decomposition of spent sulfuric acid on a catalyst

    SciTech Connect

    Perfilev, V.M.; CHapyluk, N.S.; Mel'nikov, S.E.; Sushchev, V.S.

    1986-03-01

    The paper reports on an investigation of the thermocatalytic splitting of SSA obtained as a waste material in the production of liquid paraffins. The studies were performed by a dynamic method in the continuous-flow unit with a quartz reactor in the form of an open tube. These studies are of value because commercial utilization of sulfuric acid wastes is an important ecological and economic problem. The studies of the catalyst behavior in thermocatalytic splitting of SSA established that the specific surface area of the silica gel without impregnation, or impregnated with 1.6% iron(III) oxide, decrease in 20 h of operation. This decrease in surface area is apparently related to recrystallization processes.

  1. Coupling interactions between sulfurous acid and the hydroperoxyl radical.

    PubMed

    Li, Ping; Ma, Zhi-Ying; Wang, Wei-Hua; Shen, Zhi-Tao; Bi, Si-Wei; Sun, Hai-Tao; Bu, Yu-Xiang

    2010-02-22

    Radical-molecule complexes associated with the hydroperoxyl radical (HOO) play an important role in atmospheric chemistry. Herein, the nature of the coupling interactions between sulfurous acid (H(2)SO(3)) and the HOO radical is systematically investigated at the B3LYP/6-311++G(3df,3pd) level of theory in combination with the atoms in molecules (AIM) theory, the natural bond orbital (NBO) method, and energy decomposition analyses (EDA). Eight stable stationary points possessing double H-bonding features were located on the H(2)SO(3)...HOO potential energy surface. The largest binding energies of -12.27 and -11.72 kcal mol(-1) are observed for the two most stable complexes, where both of them possess strong double intermolecular H-bonds of partially covalence. Moreover, the characteristics of the IR spectra for the two most stable complexes are discussed to provide some help for their possible experimental identification. PMID:20041456

  2. ELECTROLYTIC CORROSION OF GOLD AND THE FORMATION OF Au//2(SO//4)//3 IN CONCENTRATED SULFURIC ACID.

    USGS Publications Warehouse

    Senftle, Frank E.; Wright, Donald B.

    1985-01-01

    The authors have examined the direct anodic oxidation of gold in concentrated H//2SO//4 to more fully understand the chemical reactions. Au//2(SO//4)//3 is unstable and cannot be isolated for chemical analysis, but our experiments are consistent with the formation of Au//2(SO//4)//3 in concentrated H//2SO//4, in which it is stable. Equations describing chemical reactions which are compatible with the experimental data are presented.

  3. 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

  4. 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)

  5. 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.

  6. Health effects of air pollutants: sulfuric acid, the old and the new.

    PubMed Central

    Amdur, M O

    1989-01-01

    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. PMID:2667973

  7. 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.

  8. An Investigation of the Acid Rock Drainage Generation from the Road Cut Slope in the Middle Part of South Korea

    NASA Astrophysics Data System (ADS)

    Ji, S.; Cheong, Y.; Yim, G.

    2006-05-01

    To examine the Acid Rock Drainage (ARD) generation from the road cut slope, a prediction study including Acid-Base Accounting (ABA) test and Net Acid Generation (NAG) test was performed for road cut rock samples (20 samples) at the new construction site of a highway in the middle part of South Korea. This slope is composed of slate and phyllite. It was a pit wall which was operated as a quarry which produced materials for roofing. pH1:2 and EC1:2 measurements were performed to evaluate free hydrogen ion contents and salts in samples. ABA test was performed to estimate the balance of the acid generating minerals (mainly pyrite) and the acid neutralizing minerals (mainly carbonates) in rock samples. Total sulfur was analyzed by sulfur analyzer, and then the maximum potential acidity (MPA, kg H2SO4/t) was calculated. X-ray diffraction (XRD) analysis was performed to identify the mineral composition of rock samples. Acid neutralizing capacity (ANC) test, after the Sobek et al. (1978), was performed to estimate the amount of acid originated from the oxidation of sulfide minerals. NAPP (Net Acid Producing Potential) was calculated by total sulfur (MPA) and ANC. NAG test was performed with grounded samples and 15 % hydrogen peroxide, and then NAG was analyzed by measuring pH (NAGpH) of the mixed solution. pH1:2 and EC1:2 ranged from 2.95 to 7.23 and 17.1 to 3070.0 ¥ìS/cm, respectively. MPA of samples was ranged from 0.0 to 79.9 kg H2SO4/t. From the XRD analysis pyrite was found at the most samples. In the sample from highly weathered dike, goethite was found. Results of the ANC tests indicated that the value of ANC reached up to 59.36 kg H2SO4/t. Rock samples could be classified as Potential Acid Forming rock (PAF) and Non- Acid Forming rock (NAF) by plotting NAPP versus NAGpH. In this study 17 samples were classified as PAF rock. It means that this slope would generate ARD when they reacted with rain. Two samples were grouped as NAF. By application this ARD prediction

  9. 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.

  10. CE IGCC Repowering plant sulfuric acid plant. Topical report, June 1993

    SciTech Connect

    Chester, A.M.

    1993-12-01

    A goal of the CE IGCC Repowering project is to demonstrate a hot gas clean-up system (HGCU), for the removal of sulfur from the product gas stream exiting the gasifier island. Combustion Engineering, Inc. (ABB CE) intends to use a HGCU developed by General Electric Environmental Services (GEESI). The original design of this system called for the installation of the HGCU, with a conventional cold gas clean-up system included as a full-load operational back-up. Each of these systems removes sulfur compounds and converts them into an acid off-gas. This report deals with the investigation of equipment to treat this off-gas, recovering these sulfur compounds as elemental sulfur, sulfuric acid or some other form. ABB CE contracted ABB Lummus Crest Inc. (ABB LCI) to perform an engineering evaluation to compare several such process options. This study concluded that the installation of a sulfuric acid plant represented the best option from both a technical and economic point of view. Based on this evaluation, ABB CE specified that a sulfuric acid plant be installed to remove sulfur from off-gas exiling the gas clean-up system. ABB LCI prepared a request for quotation (RFQ) for the construction of a sulfuric acid production plant. Monsanto Enviro-Chem Inc. presented the only proposal, and was eventually selected as the EPC contractor for this system.

  11. Ethanol production from cotton gin trash using optimised dilute acid pretreatment and whole slurry fermentation processes.

    PubMed

    McIntosh, S; Vancov, T; Palmer, J; Morris, S

    2014-12-01

    Cotton ginning trash (CGT) collected from Australian cotton gins was evaluated for bioethanol production. CGT composition varied between ginning operations and contained high levels of extractives (26-28%), acid-insoluble material (17-22%) and holocellulose (42-50%). Pretreatment conditions of time (4-20 min), temperature (160-220 °C) and sulfuric acid concentration (0-2%) were optimised using a central composite design. Response surface modelling revealed that CGT fibre pretreated at 180 °C in 0.8% H2SO4 for 12 min was optimal for maximising enzymatic glucose recoveries and achieved yields of 89% theoretical, whilst the total accumulated levels of furans and acetic acid remained relatively low at <1 and 2 g/L respectively. Response surface modelling also estimated maximum xylose recovery in pretreated liquors (87% theoretical) under the set conditions of 150 °C in 1.9% H2SO4 for 23.8 min. Yeast fermentations yielded high ethanol titres of 85%, 88% and 70% theoretical from glucose generated from: (a) enzymatic hydrolysis of washed pretreated fibres, (b) enzymatic hydrolysis of whole pretreated slurries and (c) simultaneous saccharification fermentations, respectively. PMID:25280112

  12. Ethanol production from cotton gin trash using optimised dilute acid pretreatment and whole slurry fermentation processes.

    PubMed

    McIntosh, S; Vancov, T; Palmer, J; Morris, S

    2014-12-01

    Cotton ginning trash (CGT) collected from Australian cotton gins was evaluated for bioethanol production. CGT composition varied between ginning operations and contained high levels of extractives (26-28%), acid-insoluble material (17-22%) and holocellulose (42-50%). Pretreatment conditions of time (4-20 min), temperature (160-220 °C) and sulfuric acid concentration (0-2%) were optimised using a central composite design. Response surface modelling revealed that CGT fibre pretreated at 180 °C in 0.8% H2SO4 for 12 min was optimal for maximising enzymatic glucose recoveries and achieved yields of 89% theoretical, whilst the total accumulated levels of furans and acetic acid remained relatively low at <1 and 2 g/L respectively. Response surface modelling also estimated maximum xylose recovery in pretreated liquors (87% theoretical) under the set conditions of 150 °C in 1.9% H2SO4 for 23.8 min. Yeast fermentations yielded high ethanol titres of 85%, 88% and 70% theoretical from glucose generated from: (a) enzymatic hydrolysis of washed pretreated fibres, (b) enzymatic hydrolysis of whole pretreated slurries and (c) simultaneous saccharification fermentations, respectively.

  13. 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. PMID:27474618

  14. Heterogeneous reactions of epoxides in acidic media.

    PubMed

    Lal, Vinita; Khalizov, Alexei F; Lin, Yun; Galvan, Maria D; Connell, Brian T; Zhang, Renyi

    2012-06-21

    Epoxides have recently been identified as important intermediates in the gas phase oxidation of hydrocarbons, and their hydrolysis products have been observed in ambient aerosols. To evaluate the role of epoxides in the formation of secondary organic aerosols (SOA), the kinetics and mechanism of heterogeneous reactions of two model epoxides, isoprene oxide and α-pinene oxide, with sulfuric acid, ammonium bisulfate, and ammonium sulfate have been investigated using complementary experimental techniques. Kinetic experiments using a fast flow reactor coupled to an ion drift-chemical ionization mass spectrometer (ID-CIMS) show a fast irreversible loss of the epoxides with the uptake coefficients (γ) of (1.7 ± 0.1) × 10(-2) and (4.6 ± 0.3) × 10(-2) for isoprene oxide and α-pinene oxide, respectively, for 90 wt % H(2)SO(4) and at room temperature. Experiments using attenuated total reflection-Fourier transform infrared spectroscopy (ATR-FTIR) reveal that diols are the major products in ammonium bisulfate and dilute H(2)SO(4) (<25 wt %) solutions for both epoxides. In concentrated H(2)SO(4) (>65 wt %), acetals are formed from isoprene oxide, whereas organosulfates are produced from α-pinene oxide. The reaction of the epoxides with ammonium sulfate is slow and no products are observed. The epoxide reactions using bulk samples and Nuclear Magnetic Resonance (NMR) spectroscopy reveal the presence of diols as the major products for isoprene oxide, accompanied by aldehyde formation. For α-pinene oxide, organosulfate formation is observed with a yield increasing with the acidity. Large yields of organosulfates in all NMR experiments with α-pinene oxide are attributed to the kinetic isotope effect (KIE) from the use of deuterated sulfuric acid and water. Our results suggest that acid-catalyzed hydrolysis of epoxides results in the formation of a wide range of products, and some of the products have low volatility and contribute to SOA growth under ambient conditions

  15. The Measurement of Sulfur Oxidation Products and Their Role in Homogeneous Nucleation

    NASA Technical Reports Server (NTRS)

    Eisele, F. L.

    1997-01-01

    The loss rate of H2SO4 vapor onto submicron particles was measured for three different particle substrates. The experimental technique involved direct flow tube measurements of H2SO4 decay rates onto a polydisperse aerosol using chemical ionization mass spectroscopic detection. The aerosols of this study were partially hydrated crystalline salts with diameters in the size range of 20 to 400 nm. The mass accommodation coefficients, a, were calculated from the first-order rate constants for H2SO4 loss to be 0.73 + 0.21 and 0.79 + 0.23 for loss onto (NH4)2SO4 and NaCl, respectively. Measurements of the loss rate of H2SO4 onto a NaCl aerosol coated with stearic acid resulted in lower mass accommodation coefficients with values of 0.31 and 0.19 for aerosol with high and low stearic acid coverage, respectively. The observed decrease in a on an aerosol with a hydrocarbon coating suggests that aerosol composition is a key factor in H2SO4 adsorption on to a particle surface.

  16. Sulfuric acid dissolution of 4A and Na-Y synthetic zeolites and effects on Na-Y surface and particle properties

    NASA Astrophysics Data System (ADS)

    Wang, Xiaoyu; Wang, Kunping; Plackowski, Chris A.; Nguyen, Anh V.

    2016-03-01

    Sodium rich synthetic zeolites 4A and Na-Y have different silicon-to-aluminium (Si/Al) ratios and are widely used as molecular sieves, catalysts and adsorbents. This study investigates the changes in 4A and Na-Y synthetic zeolites treated by H2SO4 at room temperature. Both zeolite types are examined before and after treatment by following the dissolution and re-crystallisation processes, and Na-Y by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and particle size analysis. Na-Y zeolite (high Si/Al ratio) has stronger acid-resistivity than 4A zeolite (low Si/Al ratio) and can be treated with H2SO4 up to 5 M without complete dissolution, whereas 4A zeolite is completely dissolved by 0.5 M acid. For both zeolites, the treatment generates dissolution (of both Si and Al) of first order fast kinetics, followed by re-crystallization. XRD studies of Na-Y zeolite indicate that acid treatment leads to structural changes where cations are removed and as dissolution progresses de-alumination takes place, thereby altering the main tetrahedral structure. XPS analysis shows the Si/Al atomic ratio for Na-Y zeolite increases from 2.94 at 0 M to 8.18 at 0.1 M, and a significant binding energy (BE) shift of Si and O occurs even at a high Si/Al ratio. The acid treatment increases the surface intermediate electronegativity of Na-Y zeolite, and the BE of each main structural element changes in the same way as the electronegativity ratio (element electronegativity to total surface electronegativity) as the acid concentration increases. Particle size analysis indicates that a recrystallization process occurs during acid treatment, as shown by a shift of the coarse particle distribution peak size to progressively smaller sizes with increasing acid concentration.

  17. Effect of atmospheric sulfur pollutants derived from acid precipitation on the benthic dynamics of lakes

    SciTech Connect

    Mitchell, M.J.

    1982-11-01

    Sulfuric acid is a major contributor to acid precipitation in the United States. The relationship of acid precipitation to the sulfur dynamics of three lakes in New York was studied. For South Lake, which has probably been acidified, the sulfur profile in the sediment corresponded to historical changes in anthropogenic sulfur inputs. In all three study lakes, the organic sulfur constituents, which generally have been ignored in limnological investigations, played a major role in sulfur dynamics. The transformations and fluxes of inorganic and organic sulfur differed among the lakes and reflected characteristic abiotic and biotic properties, including productivity parameters. The community structure and secondary production of the invertebrate benthos were ascertained and, for South Lake, were similar to other acidified lakes. The importance of benthic insects on sulfur dynamics was demonstrated. Further studies on sulfur in lakes will enhance the understanding of the role of these anthropogenic inputs on lake systems and permit a more accurate appraisal of the present and future impacts of acidic deposition on water quality. 10 references.

  18. Pulmonary function and clearance after prolonged sulfuric acid aerosol exposure

    SciTech Connect

    Ives, P.J. ); Gerrity, T.R.; DeWitt, P.; Folinsbee, L.J. )

    1991-03-15

    The authors studied pulmonary function and clearance responses after a 4 H exposure to 75-100 {mu}g/m{sup 3} sulfuric acid aerosol (SAA). Healthy subjects, who exercised for 30 min/H at ventilation of about 25 L/min, were exposed once to clean air and once to SAA. Oral hygiene and acidic juice gargle were used to minimize oral ammonia. Lung function tests, including spirometry, plethysmography, and partial flow-volume (PEFV) curves were performed before and after exposure. Clearance of 99m-Technetium labeled iron oxide was assessed after each exposure. The first moment of fractional tracheobronchial retention (M1TBR), after correcting for 24 H retention and normalizing to time zero, was used as an index of clearance. There were no significant changes in lung volumes, airways resistance, or maximum expiratory flows after SAA exposure. Flow at 40% of total lung capacity on PEFV curves decreased 17% (NS) after SAA exposure. Tracheobronchial clearance was accelerated after a single exposure to SAA; M1TBR decreased from 73 {plus minus} 5 min (air) to 69 {plus minus} 5 min (SAA). These results suggest that acute prolonged exposure to low levels of SAA has minimal effects on lung mechanics in healthy subjects but does produce a modest acceleration of particle clearance.

  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. 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.

  1. 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. PMID:27128188

  2. 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.

  3. Control of acidity development on solid sulfur due to bacterial action.

    PubMed

    Crescenzi, Francesco; Crisari, Antonella; Dangeli, Edoardo; Nardella, Alessandro

    2006-11-01

    The global production of sulfur, which is currently obtained almost exclusively as an involuntary byproduct of the oil and gas industry, is exceeding the market demand so that long term storage or even definitive disposal of elemental sulfur is often needed to handle production surplus. The storage of large quantities of elemental sulfur calls for solidifying liquid sulfur in huge blocks, hundred meters wide on each side and as high as 20 meters. Sulfur, in presence of water and air, can be oxidized to sulfuric acid by a ubiquitous microorganism: Thiobacillus. On large blocks, this natural phenomenon may lead to soil and water acidification. Research projects have addressed suppression of Thiobacilli activity to prevent acidification, but no industrial applications have been reported. This work describes the inhibition of sulfur biological oxidation attainable by exposing sulfur to a high ionic strength environment. The bacteriostatic action is produced by contacting sulfur with a solution of an inorganic salt, such as sodium chloride, having an ionic strength similar to sea water. Possible ways to exploit the inhibitory effect to prevent the generation of acidity from sulfur storage blocks are suggested. PMID:17144310

  4. 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.

  5. Sulfur Dioxide and the Production of Sulfuric Acid on Present-Day and Early Mars: Implications for the Lack of Detected Carbonates on the Surface

    NASA Technical Reports Server (NTRS)

    Levine, Joel S.; Summers, Michael E.

    2008-01-01

    In the early history of Mars, volcanic activity associated with the formation of the Tharsis ridge produced a very large amount of atmospheric SO2--on the order of a bar of atmospheric SO2. In the present-day atmosphere of Mars, the lifetime of SO2 is relatively short with a lifetime of less than a day. The short lifetime of SO2 in the present Mars atmosphere makes the production of significant levels of H2SO4 very difficult since the SO2 may be destroyed by various chemical and photochemical processes before the SO2 can be converted to H2SO4. However, photochemical calculations performed and described here, indicate that enhanced atmospheric levels of CO2 in the early atmosphere of Mars resulted in a significantly enhanced atmospheric lifetime for SO2 up to several years. With a significantly enhanced atmospheric lifetime, SO2 could readily form large amounts of H2SO4, which precipitated out of the atmosphere in the form of droplets. The precipitated H2SO4 then reacted with potential surface carbonates, destroying the carbonates and resulting in the abundant and widespread distribution of sulfates on the surface of Mars as detected by recent Mars missions.

  6. 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.

  7. 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.

  8. 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.

  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. Laboratory studies of nitric acid hydrate and sulfuric acid aerosols: Implications for polar stratospheric cloud formation

    SciTech Connect

    Miller, R.E.

    1995-12-31

    The optical properties of atmospheric aerosols are important in a number of modeling and remote sensing applications. We have devised a new approach for determining the frequency dependent real and imaginary refractive indices directly from the observation of the infrared spectra of the aerosols. We have applied this method to the study of water ice aerosols and comparisons with previous measurements confirm that the method is sound and accurate. The temperature dependence of the refractive index of ice has also been measured over the range 130 K to 210 K, which includes the region of interest for the study of Polar Stratospheric Clouds (PSC`s). The method has also been applied to the study of nitric acid dehydrate (NAD) and nitric acid trihydrate (NAT). Sulfuric acid/nitric acid/water ternary systems are also being studied with the aim of determining the nature of the phases formed and the associated freezing points as a function of the concentrations of the acids.

  11. 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.

  12. 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.

  13. Sulfuric Acid Nucleation with NH3, Methyl, Dimethyl, and Trimethyl Amines

    NASA Astrophysics Data System (ADS)

    Hanson, D. R.; Volz, K.; Glasoe, W.; Panta, B.

    2013-12-01

    Nucleation of particles from sulfuric acid, water, and nitrogen base molecules was studied within a cylindrical flow reactor. The particles formed from these vapors were detected with a nano Mobility Particle Sizer coupled to a Diethylene Glycol Ultrafine Condensation Particle Counter. The effects of ammonia and small alkyl amines on particle formation with sulfuric acid vapor were very large. Enhancements of particle numbers by factors of thousands to millions indicates that these species have powerful effects on nucleation of sulfuric acid molecules. Power dependencies for particle numbers on sulfuric acid and nitrogen bases elucidates the chemical content of the critical clusters and this helps to shed light on the nucleation mechanisms. The details of the particle detection efficiencies, information on the extent of particle growth, and independently determined cluster thermodynamics help to verify these results and to extrapolate them to atmospheric conditions.

  14. 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.

  15. Formation rates, stability and reactivity of sulfuric acid - amine clusters predicted by computational chemistry

    NASA Astrophysics Data System (ADS)

    Kurtén, Theo; Ortega, Ismael; Kupiainen, Oona; Olenius, Tinja; Loukonen, Ville; Reiman, Heidi; McGrath, Matthew; Vehkamäki, Hanna

    2013-04-01

    Despite the importance of atmospheric particle formation for both climate and air quality, both experiments and non-empirical models using e.g. sulfuric acid, ammonia and water as condensing vapors have so far been unable to reproduce atmospheric observations using realistic trace gas concentrations. Recent experimental and theoretical evidence has shown that this mystery is likely resolved by amines. Combining first-principles evaporation rates for sulfuric acid - dimethylamine clusters with cluster kinetic modeling, we show that even sub-ppt concentrations of amines, together with atmospherically realistic concentrations of sulfuric acid, result in formation rates close to those observed in the atmosphere. Our simulated cluster formation rates are also close to, though somewhat larger than, those measured at the CLOUD experiment in CERN for both sulfuric acid - ammonia and sulfuric acid - dimethylamine systems. A sensitivity analysis indicates that the remaining discrepancy for the sulfuric acid - amine particle formation rates is likely caused by steric hindrances to cluster formation (due to alkyl groups of the amine molecules) rather than by significant errors in the evaporation rates. First-principles molecular dynamic and reaction kinetic modeling shed further light on the microscopic physics and chemistry of sulfuric acid - amine clusters. For example, while the number and type of hydrogen bonds in the clusters typically reach their equilibrium values on a picosecond timescale, and the overall bonding patterns predicted by traditional "static" quantum chemical calculations seem to be stable, the individual atoms participating in the hydrogen bonds continuously change at atmospherically realistic temperatures. From a chemical reactivity perspective, we have also discovered a surprising phenomenon: clustering with sulfuric acid molecules slightly increases the activation energy required for the abstraction of alkyl hydrogens from amine molecules. This implies

  16. The reaction probability of N2O5 with sulfuric acid aerosols at stratospheric temperatures and compositions

    NASA Technical Reports Server (NTRS)

    Fried, Alan; Henry, Bruce E.; Calvert, Jack G.; Mozurkewich, Michael

    1994-01-01

    We have measured the rate of reaction of N2O5 with H2O on monodisperse, submicrometer H2SO4 particles in a low-temperature flow reactor. Measurements were carried out at temperatures between 225 K and 293 K on aerosol particles with sizes and compositions comparable to those found in the stratosphere. At 273 K, the reaction probability was found to be 0.103 +/- 0.0006, independent of H2SO4 composition from 64 to 81 wt%. At 230 K, the reaction probability increased from 0.077 for compositions near 60% H2SO4 to 0.146 for compositions near 70% H2SO4. Intermediate conditions gave intermediate results except for low reaction probabilities of about 0.045 at 260 K on aerosols with about 78% H2SO4. The reaction probability did not depend on particle size. These results imply that the reaction occurs essentially at the surface of the particle. A simple model for this type of reaction that reproduces the general trends observed is presented. the presence of formaldehyde did not affect the reaction rate.

  17. 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.

  18. 46 CFR 153.556 - Special requirements for sulfuric acid and oleum.

    Code of Federal Regulations, 2014 CFR

    2014-10-01

    ... basis. (b) A containment system carrying sulfuric acid may be: (1) Made of unlined steel if the cargo composition is between 70 and 80 or between 90 and 100 percent acid by weight; (2) Lined with lead if the cargo composition does not exceed 96 percent acid by weight; or (3) Lined with natural rubber...

  19. 46 CFR 153.556 - Special requirements for sulfuric acid and oleum.

    Code of Federal Regulations, 2011 CFR

    2011-10-01

    ... basis. (b) A containment system carrying sulfuric acid may be: (1) Made of unlined steel if the cargo composition is between 70 and 80 or between 90 and 100 percent acid by weight; (2) Lined with lead if the cargo composition does not exceed 96 percent acid by weight; or (3) Lined with natural rubber...

  20. 46 CFR 153.556 - Special requirements for sulfuric acid and oleum.

    Code of Federal Regulations, 2013 CFR

    2013-10-01

    ... basis. (b) A containment system carrying sulfuric acid may be: (1) Made of unlined steel if the cargo composition is between 70 and 80 or between 90 and 100 percent acid by weight; (2) Lined with lead if the cargo composition does not exceed 96 percent acid by weight; or (3) Lined with natural rubber...

  1. 46 CFR 153.556 - Special requirements for sulfuric acid and oleum.

    Code of Federal Regulations, 2010 CFR

    2010-10-01

    ... basis. (b) A containment system carrying sulfuric acid may be: (1) Made of unlined steel if the cargo composition is between 70 and 80 or between 90 and 100 percent acid by weight; (2) Lined with lead if the cargo composition does not exceed 96 percent acid by weight; or (3) Lined with natural rubber...

  2. 46 CFR 153.556 - Special requirements for sulfuric acid and oleum.

    Code of Federal Regulations, 2012 CFR

    2012-10-01

    ... basis. (b) A containment system carrying sulfuric acid may be: (1) Made of unlined steel if the cargo composition is between 70 and 80 or between 90 and 100 percent acid by weight; (2) Lined with lead if the cargo composition does not exceed 96 percent acid by weight; or (3) Lined with natural rubber...

  3. 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.

  4. 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.

  5. Catalytic effect of water, formic acid, or sulfuric acid on the reaction of formaldehyde with OH radicals.

    PubMed

    Zhang, Weichao; Du, Benni; Qin, Zhenglong

    2014-07-01

    In this paper, for the hydrogen abstraction reaction of HCHO by OH radicals assisted by water, formic acid, or sulfur acid, the possible reaction mechanisms and kinetics have been investigated theoretically using quantum chemistry methods and transition-state theory. The potential energy surfaces calculated at the CCSD(T)/6-311++G(df,pd)//MP2(full)/6-311++G(df,pd) levels of theory reveal that, due to the formation of strong hydrogen bond(s), the relative energies of the transition states involving catalyst are significantly reduced compared to that reaction without catalyst. However, the kinetics calculations show that the rate constants are smaller by about 3, 9, or 10 orders of magnitude for water, formic acid, or sulfur acid assisted reactions than that uncatalyzed reaction, respectively. Consequently, none of the water, formic acid, or sulfur acid can accelerate the title reaction in the atmosphere.

  6. 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.

  7. 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.

  8. 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.

  9. Mass independent fractionation of sulfur isotopes during thermochemical reduction of native sulfur, sulfite and sulfate by amino acids

    NASA Astrophysics Data System (ADS)

    Watanabe, Y.; Naraoka, H.; Ohmoto, H.

    2006-05-01

    Mass independent fractionation of sulfur isotopes (MIF-S) is recognized when the Δ33S value (= δ33S-0.515xδ34S) of a sample falls outside the range of 0±0.2 permil and the 33-34θ value (= ln33α/ ln34α) lies outside the range of 0.515±.005 (Farquhar and Wing, 2003). Previous investigators have concluded that the only mechanisms to create MIF-S are photochemical reactions between sulfur-bearing gases (SO2, H2S) and UV. Based on comparisons of the geochemical characteristics of Archean sedimentary rocks between those with large MIF-S values (e.g., the 2.5 Ga McRae and 2.7 Ga Jeerinah shales) and those with no (or very small) MIF- S values (e.g., 2.76 Ga Hardey shales and 2.92 Ga Mosquito Creek shales), we have developed a hypothesis that MIF-S in sedimentary rocks may have been created by reactions among organic-rich sediments, sulfur- bearing solid compounds, and sulfur-bearing hydrothermal fluids at T = 100-200°C during the early diagenetic stage of sediments. Most abundant organic compounds in immature sediments are amino acids. For these reasons, we have conducted series of laboratory experiments to investigate sulfur isotope fractionations during reactions between a variety of amino acids (alanine, glycine, hystidine, etc.) and native sulfur, sodium sulfite or sodium sulfate at 150-200°C. Previous researchers used a variety of organic compounds (sugars, methane, xylene, etc) and/or ferrous- bearing minerals to investigate non-bacterial sulfate reduction, but they failed to demonstrate thermochemical sulfate reduction at temperatures below 230°C. However, we were able to reduce sulfate (S6+), as well as sulfite (S4+) and native sulfur (S0), to hydrogen sulfide (S2-) even at 150°C using simple and common amino acids (e.g., alanine and glycine). The reduction rates generally decreased: (a) from native sulfur, to sulfite, and to sulfate; (b) from simple amino acids to more complex amino acids (e.g., histidine); and (c) with decreasing temperatures. The

  10. 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.

  11. Sulfuric acid rain effects on crop yield and foliar injury. Final report

    SciTech Connect

    Lee, J.J.; Neely, G.E.; Perrigan, S.C.

    1980-01-01

    A study was undertaken to determine the relative sensitivity of major U.S. crops to sulfuric acid rain. Plants were grown under controlled environmental conditions and exposed to simulated acid rain of three sulfuric acid concentrations (pH 3.0, 3.5, 4.0) or to a control rain (pH 5.7). Injury to foliage and effects on yield were common responses to acid rain. However, foliar injury was not a good indicator of effects on yield.

  12. Enhanced enzymatic hydrolysis of poplar bark by combined use of gamma ray and dilute acid for bioethanol production

    NASA Astrophysics Data System (ADS)

    Chung, Byung Yeoup; Lee, Jae Taek; Bai, Hyoung-Woo; Kim, Ung-Jin; Bae, Hyeun-Jong; Gon Wi, Seung; Cho, Jae-Young

    2012-08-01

    Pretreatment of poplar bark with a combination of sulfuric acid (3%, w/w, H2SO4) and gamma irradiation (0-1000 kGy) was performed in an attempt to enhance enzymatic hydrolysis for bioethanol production. The yields of reducing sugar were slightly increased with an increasing irradiation dose, ranging from 35.4% to 51.5%, with a 56.1% reducing sugar yield observed after dilute acid pretreatment. These results clearly showed that soluble sugars were released faster and to a greater extent in dilute acid-pretreated poplar bark than in gamma irradiation-pretreated bark. When combined pretreatment was carried out, a drastic increase in reducing sugar yield (83.1%) was found compared with individual pretreatment, indicating the possibility of increasing the convertibility of poplar bark following combined pretreatment. These findings are likely associated with cellulose crystallinity, lignin modification, and removal of hemicelluloses.

  13. Backscatter laser depolarization studies of simulated stratospheric aerosols: crystallized sulfuric acid droplets.

    PubMed

    Sassen, K; Zhao, H; Yu, B K

    1989-08-01

    The optical depolarizing properties of simulated stratospheric aerosols were studied in laboratory laser (0.633 microm) 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 delta approximately 0.02, but delta approximately 0.10-0.15 are generated from acid droplet crystallization effects associated with recycled aerosols and 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 delta approximately 0.10 values that have been observed in the lower stratosphere in the absence of the relatively strong backscattering from homogeneous sulfuric acid droplet (delta approximately 0) or ice crystal (delta approximately 0.5) clouds.

  14. 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 %.

  15. 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

  16. Effects of acid treatment duration and sulfuric acid molarity on purification of multi-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Mortazavi, Seyedeh Z.; Novinrooz, Abdul J.; Reyhani, Ali; Mirershadi, Soghra

    2010-12-01

    Multi-walled carbon nanotubes were synthesized using a Fe-Ni bimetallic catalyst supported by MgO using thermal chemical vapor deposition. Purification processes to remove unwanted carbon structures and other metallic impurities were carried out by boiling in sulfuric acid solution. Various analytical techniques such as TGA/DSC, Raman spectroscopy, SEM, HRTEM and EDAX were employed to investigate the morphology, graphitization and quality of the carbon nanotubes. The obtained results reveal the molarity of sulfuric acid and immersed time of the carbon nanotubes in the acid solution is very effective at purifying multi-walled carbon nanotubes. It was also found that 5 M concentration of boiling sulfuric acid for a 3 h treatment duration led to the highest removal of the impurities with the least destructive effect. Moreover, it was observed that acid treatment results in decreasing of CNTs’ diameter.

  17. Effects of acid treatment duration and sulfuric acid molarity on purification of multi-walled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Mortazavi, Seyedeh; Novinrooz, Abdul; Reyhani, Ali; Mirershadi, Soghra

    2010-12-01

    Multi-walled carbon nanotubes were synthesized using a Fe-Ni bimetallic catalyst supported by MgO using thermal chemical vapor deposition. Purification processes to remove unwanted carbon structures and other metallic impurities were carried out by boiling in sulfuric acid solution. Various analytical techniques such as TGA/DSC, Raman spectroscopy, SEM, HRTEM and EDAX were employed to investigate the morphology, graphitization and quality of the carbon nanotubes. The obtained results reveal the molarity of sulfuric acid and immersed time of the carbon nanotubes in the acid solution is very effective at purifying multi-walled carbon nanotubes. It was also found that 5 M concentration of boiling sulfuric acid for a 3 h treatment duration led to the highest removal of the impurities with the least destructive effect. Moreover, it was observed that acid treatment results in decreasing of CNTs' diameter.

  18. 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.

  19. 40 CFR 721.7770 - Alkylphenoxypoly(oxyethylene) sulfuric acid ester, substituted amine salt.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... acid ester, substituted amine salt. 721.7770 Section 721.7770 Protection of Environment ENVIRONMENTAL... ester, substituted amine salt. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as alkyl phenoxypoly(oxyethylene) sulfuric acid ester,...

  20. 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.

  1. 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. PMID:26821256

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. Bimodal distribution of sulfuric acid aerosols in the upper haze of Venus

    NASA Astrophysics Data System (ADS)

    Gao, Peter; Zhang, Xi; Crisp, David; Bardeen, Charles G.; Yung, Yuk L.

    2014-03-01

    Observations by the SPICAV/SOIR instruments aboard Venus Express have revealed that the upper haze (UH) of Venus, between 70 and 90 km, is variable on the order of days and that it is populated by two particle modes. We use a one-dimensional microphysics and vertical transport model based on the Community Aerosol and Radiation Model for Atmospheres to evaluate whether interaction of upwelled cloud particles and sulfuric acid particles nucleated in situ on meteoric dust are able to generate the two observed modes, and whether their observed variability are due in part to the action of vertical transient winds at the cloud tops. Nucleation of photochemically produced sulfuric acid onto polysulfur condensation nuclei generates mode 1 cloud droplets, which then diffuse upwards into the UH. Droplets generated in the UH from nucleation of sulfuric acid onto meteoric dust coagulate with the upwelled cloud particles and therefore cannot reproduce the observed bimodal size distribution. By comparison, the mass transport enabled by transient winds at the cloud tops, possibly caused by sustained subsolar cloud top convection, are able to generate a bimodal size distribution in a time scale consistent with Venus Express observations. Below the altitude where the cloud particles are generated, sedimentation and vigorous convection causes the formation of large mode 2 and mode 3 particles in the middle and lower clouds. Evaporation of the particles below the clouds causes a local sulfuric acid vapor maximum that results in upwelling of sulfuric acid back into the clouds. In the case where the polysulfur condensation nuclei are small and their production rate is high, coagulation of small droplets onto larger droplets in the middle cloud may set up an oscillation in the size modes of the particles such that precipitation of sulfuric acid “rain” may be possible immediately below the clouds once every few Earth months. Reduction of the polysulfur condensation nuclei production

  7. 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.

  8. 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.

  9. 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.

  10. New Particle Formation and Growth from Methanesulfonic Acid, Amines, Water, and Organics

    NASA Astrophysics Data System (ADS)

    Arquero, K. D.; Ezell, M. J.; Finlayson-Pitts, B. J.

    2014-12-01

    Particles in the atmosphere can influence visibility, negatively impact human health, and affect climate. The largest uncertainty in determining global radiative forcing is attributed to atmospheric aerosols. While new particle formation in many locations is correlated with sulfuric acid in air, neither the gas-phase binary nucleation of H2SO4-H2O nor the gas-phase ternary nucleation of H2SO4-NH3-H2O alone can fully explain observations. An additional potential particle source, based on previous studies in this laboratory, is methanesulfonic acid (MSA) with amines and water vapor. However, organics are ubiquitous in the atmosphere, with secondary organic aerosol (SOA) being a major component of particles. Organics could be involved in the initial stages of particle formation by enhancing or inhibiting nucleation from sulfuric acid or MSA, in addition to contributing to their growth to form SOA. Experiments to measure the effects of a series of organics of varying structure on particle formation and growth from MSA, amines, and water were performed in a custom-built small volume aerosol flow tube reactor. Analytical instruments and techniques include a scanning mobility particle sizer to measure particle size distributions, sampling onto a weak cation exchange resin with analysis by ion chromatography to measure amine concentrations, and filter collection and analysis by ultra-high performance liquid chromatography tandem mass spectrometry to measure MSA concentrations. Organics were measured by atmospheric pressure chemical ionization tandem mass spectrometry. The impact of these organics on the initial particle formation as well as growth will be reported. The outcome is an improved understanding of fundamental chemistry of nucleation and growth to ultimately be incorporated into climate models to better predict how particles affect the global climate budget.

  11. 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.

  12. 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.

  13. 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.

  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. 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.

  16. 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.

  17. Configuring the thermochemical hydrogen sulfuric acid process step for the Tandem Mirror Reactor

    SciTech Connect

    Galloway, T.R.

    1981-05-01

    This paper identifies the sulfuric acid step as the critical part of the thermochemical cycle in dictating the thermal demands and temperature requirements of the heat source. The General Atomic Sulfur-Iodine Cycle is coupled to a Tandem Mirror. The sulfuric acid decomposition process step is focused on specifically since this step can use the high efficiency electrical power of the direct converter together with the other thermal-produced electricity to Joule-heat a non-catalytic SO/sub 3/ decomposer to approximately 1250/sup 0/K. This approach uses concepts originally suggested by Dick Werner and Oscar Krikorian. The blanket temperature can be lowered to about 900/sup 0/K, greatly alleviating materials problems, the level of technology required, safety problems, and costs. A moderate degree of heat has been integrated to keep the cycle efficiency around 48%, but the number of heat exchangers has been limited in order to keep hydrogen production costs within reasonable bounds.

  18. 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

    2016-01-01

    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. PMID:27438241

  19. 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. PMID:25353947

  20. 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.

  1. Improved process for the production of cellulose sulfate using sulfuric acid/ethanol solution.

    PubMed

    Chen, Guo; Zhang, Bin; Zhao, Jun; Chen, Hongwen

    2013-06-01

    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.

  2. 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.

  3. 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.

  4. New insights into sulfur amino acid function in gut health and disease

    Technology Transfer Automated Retrieval System (TEKTRAN)

    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...

  5. 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...

  6. 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. PMID:18588315

  7. 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

  8. 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.

  9. 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.

  10. 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.

  11. 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

  12. 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.

  13. 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.

  14. Reflex-mediated desquamation of bronchiolar epithelium in guinea pigs exposed acutely to sulfuric acid aerosol.

    PubMed Central

    Brownstein, D. G.

    1980-01-01

    Terminal conducting airways are known to be vulnerable to direct injury by a variety of noxious aerosols. Sulfuric acid aerosol, a by-product of fossil fuel combustion, produces desquamation of terminal bronchiolar epithelium in guinea pigs that is believed to result from direct deep lung irritation, an effect separable from reflex airway constriction induced by sulfuric acid. To characterize desquamation of bronchiolar epithelium, 20 guinea pigs were exposed to 32.6 mg/cu m sulfuric acid aerosol with a mass median aerodynamic diameter of 1.0 micron for 4 hours. The guinea pigs were killed upon termination of the exposure, or 24 hours later, and airway alterations were evaluated by light and transmission electron microscopy. To test whether the development of bronchiolar epithelial desquamation is independent of reflex airway constriction, 24 guinea pigs were exposed to an identical aerosol for 4 hours after pretreating half with 5 mg/kg atropine sulfate intraperitoneally to inhibit airway constriction. Sulfuric acid produced diffuse pulmonary hyperinflation with areas of consolidation and atelectasis. Epithelial desquamation occurred in airways supplying regions of developing atelectasis and was most extensive in terminal bronchioles. Parasympathetic effector blockade with atropine eliminated epithelial desquamation. These results indicate that sulfuric acid-produced desquamation of terminal bronchiolar epithelium is not separable from reflex airway constriction and that terminal conducting airways are vulnerable not only to direct injury by noxious aerosols but also to indirect, reflex-mediated injury. Images Figure 1 Figure 2 Figure 3 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 Figure 11 Figure 12 Figure 13 Figure 14 PMID:7361847

  15. Carbonylation of nitrobenzene in methanol on the sulfur-containing catalyst potassium ethylxanthate-rubeanic acid

    SciTech Connect

    Bordzilovskii, V.Ya.; Gerega, V.F.; Redoshkin, B.A.; Dergunov, Yu.I.

    1988-05-10

    The kinetics of nitrobenzene carbonylation with carbon monoxide in methanol over the two-component catalyst potassium ethylxanthate-rubeanic acid was studied from 383-423/sup 0/K and pressures of 11-32 MPa. It was established that at low (< 15%) conversion of nitrobenzene the investigated process is second order in sulfur-containing catalyst and first order in nitrobenzene. The apparent activation energy was (113 +/- 6) 10/sup 3/ J/mole. A scheme of carbonylation of nitrobenzene in methanol in the presence of sulfur-containing catalyst was proposed which includes formation of complexes of nitrobenzene and CO with catalyst.

  16. 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.

  17. 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.

  18. 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. PMID:27542478

  19. 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

  20. Corrosion of some chromium-nickel steels and alloys in sulfuric acid solutions of sodium sulfite

    SciTech Connect

    Kopeliovich, D.K.; Glagolenko, Yu.V.; Ermolinskii, S.P.

    1988-05-01

    Steels 12Kh18N1OT and 10Kh17N13M3T and alloys 06KhN28MDT and 46KhNM were studied in sulfuric acid solutions containing sodium sulfite and sulfur dioxide to determine the effects of different concentrations of the corrosive constituents on the anodic and cathodic active and passive corrosion behavior of the metals. Polarization curves were obtained with a P-5827 M potentiostat. Addition of sulfite facilitated both electrode processes and the region of the reactive state was broadened due to the shift of passivation potentials to more positive values. The activating effect of sulfite reduction products were confirmed by tests of alloys in spent solutions. This increased likelihood of activation and the decrease of the solutions's own corrosion potential were both attributed to retardation of the cathodic process by lower valence sulfur compounds.

  1. 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

  2. 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.

  3. 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. PMID:24595051

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. Effects of simulated sulfuric acid rain on crop plants

    SciTech Connect

    Cohen, C.J.; Grothaus, L.C.; Perrigan, S.C.

    1981-01-01

    Since relatively little is known about the effects of acid precipitation on growth and productivity of crop plants, a crop survey was initiated to study effects of H/sub 2/SO/sub 4/ rain simulants on growth, yield, and quality of selected crops which were chosen to represent diverse taxonomic groups and crop products. Plants were grown in pots in field-exposure chambers and subjected to three H/sub 2/SO/sub 4/ rain simulants (pH levels 4.0, 3.5, and 3.0) and to a control simulant (pH 5.6). Yield of approximately two-thirds of the crops surveyed was not affected by the H/sub 2/SO/sub 4/ rain treatments. Equal numbers of the remaining crops exhibited stimulatory and inhibitory yield responses at some H/sub 2/SO/sub 4/ rain simulant pH levels. These results did not suggest that acid rain treatment either generally inhibited or stimulated crop productivity. Crop response depended on crop species and crop product. For example, while forage yield of alfalfa and timothy was stimulated at some acid rain pH levels, yield of the remaining forage legume and grass species was not generally affected by acid rain treatment. However, root and fruit crop species exhibited generalized responses (yield inhibition and stimulation, respectively) which appeared to be more closely associated with crop product than occurred for other crop product groupings. Effects on crop quality were also important. For instance, although yield of some horticultural leaf and fruit crops was either unaffected or stimulated by H/sub 2/SO/sub 4/ rain treatment, marketability was adversely affected at low pH because of the presence of discoloration and/or lesions produced by H/sub 2/SO/sub 4/ rain treatment. This preliminary study demonstrates considerable variability in crop response to acid rain.

  9. Mixed-Metal-Organic Framework with Effective Lewis Acidic Sites for Sulfur Confinement in High-Performance Lithium-Sulfur Batteries.

    PubMed

    Wang, Ziqi; Wang, Buxue; Yang, Yu; Cui, Yuanjing; Wang, Zhiyu; Chen, Banglin; Qian, Guodong

    2015-09-23

    The mixed-metal-organic framework approach and a representative zirconium-metalloporphyrin framework (MOF-525) have been developed to create novel sulfur hosts and Li-S batteries. The different local environments at the centers of the porphyrin moieties in a series of MMOFs-MOF-525(2H), MOF-525(FeCl), and MOF-525(Cu)-have led to their different behaviors for the confinement of sulfur and thus Li-S batteries. The unique structure of MOF-525(Cu) has enabled each Cu(2+) site to offer two Lewis acidic sites, featuring it as a very powerful MOF host for the inclusion of sulfur and polysulfides. The S@MOF-525(Cu) cathode has demonstrated the best performance among all reported sulfur/MOFs composite cathode materials, with a reversible capacity of about 700 mAh/g at 0.5 C after 200 cycles. PMID:26323942

  10. 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... acid, mono-C9-11-alkyl esters, sodium salts (PMN P-01-149; CAS No. 84501-49-5) is subject to...

  11. 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... acid, mono-C9-11-alkyl esters, sodium salts (PMN P-01-149; CAS No. 84501-49-5) is subject to...

  12. 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... acid, mono-C9-11-alkyl esters, sodium salts (PMN P-01-149; CAS No. 84501-49-5) is subject to...

  13. 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... acid, mono-C9-11-alkyl esters, sodium salts (PMN P-01-149; CAS No. 84501-49-5) is subject to...

  14. 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... acid, mono-C9-11-alkyl esters, sodium salts (PMN P-01-149; CAS No. 84501-49-5) is subject to...

  15. 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

  16. 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. PMID:27357706

  17. 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.

  18. Stability of Supported Platinum Sulfuric Acid Decomposition Catalysts for use in Thermochemical Water Splitting Cycles

    SciTech Connect

    Daniel M. Ginosar; Lucia M. Petkovic; Anne W. Glenn; Kyle C. Burch

    2007-03-01

    The activity and stability of several metal oxide supported platinum catalysts were explored for the sulfuric acid decomposition reaction. The acid decomposition reaction is common to several sulfur based thermochemical water splitting cycles. Reactions were carried out using a feed of concentrated liquid sulfuric acid (96 wt%) at atmospheric pressure at temperatures between 800 and 850 °C and a weight hour space velocity of 52 g acid/g catalyst/hr. Reactions were run at these high space velocities such that variations in kinetics were not masked by surplus catalyst. The influence of exposure to reaction conditions was explored for three catalysts; 0.1-0.2 wt% Pt supported on alumina, zirconia and titania. The higher surface area Pt/Al2O3 and Pt/ZrO2 catalysts were found to have the highest activity but deactivated rapidly. A low surface area Pt/TiO2 catalyst was found to have good stability in short term tests, but slowly lost activity for over 200 hours of continuous operation.

  19. Resistance of biofilm-covered mortars to microbiologically influenced deterioration simulated by sulfuric acid exposure

    SciTech Connect

    Soleimani, Sahar Isgor, O. Burkan Ormeci, Banu

    2013-11-15

    Following the reported success of biofilm applications on metal surfaces to inhibit microbiologically influenced corrosion, effectiveness and sustainability of E. coli DH5α biofilm on mortar surface to prevent microbiologically influenced concrete deterioration (MICD) are investigated. Experiments simulating microbial attack were carried out by exposing incrementally biofilm-covered mortar specimens to sulfuric acid solutions with pH ranging from 3 to 6. Results showed that calcium concentration in control reactors without biofilm was 23–47% higher than the reactors with biofilm-covered mortar. Formation of amorphous silica gel as an indication of early stages of acid attack was observed only on the control mortar specimens without biofilm. During acidification, the biofilm continued to grow and its thickness almost doubled from ∼ 30 μm before acidification to ∼ 60 μm after acidification. These results demonstrated that E. coli DH5α biofilm was able to provide a protective and sustainable barrier on mortar surfaces against medium to strong sulfuric acid attack. -- Highlights: •Effectiveness of E.coli DH5α biofilm to prevent MICD was studied. •Conditions that lead to MICD were simulated by chemical acidification. •Biofilm-covered mortar specimens were exposed to sulfuric acid solutions. •The presence of biofilm helped reduce the chemically-induced mortar deterioration. •Biofilm remained alive and continued to grow during the acidification process.

  20. Optical constants of sulfuric Acid; application to the clouds of venus?

    PubMed

    Palmer, K F; Williams, D

    1975-01-01

    With the purpose of obtaining the real and imaginary parts of the complex refractive index N; = n + ik, we have made quantitative measurements of spectral transmission and reflection of sulfuric acid solutions in the visible and near infrared. On the basis of the results, we have obtained values for n throughout the entire region and values of k in the near infrared together with upper limits for k in the visible region. These optical constants can be used to interpret the results of polarization studies of solar radiation that has been scattered by the clouds of Venus. We have Kramers-Kronig phase-shift analysis to obtain values of n and k from reflection measurements in the intermediate infrared region (400-4000 cm(-1)). Our measurements were made at 300 K on sulfuric acid solutions having concentrations by weight of 95.6, 84.5, 75, 50, 38, and 25%. If the particles in the Venus clouds consist of liquid droplets of sulfuric acid at a temperature of 250 K, comparison of existing Venus data with our data suggests that the acid concentration is probably higher than 70%. Various possibilities are discussed.

  1. Particle size distributions in Arctic polar stratospheric clouds, growth and freezing of sulfuric acid droplets, and implications for cloud formation

    NASA Technical Reports Server (NTRS)

    Dye, James E.; Baumgardner, D.; Gandrud, B. W.; Kawa, S. R.; Kelly, K. K.; Loewenstein, M.; Ferry, G. V.; Chan, K. R.; Gary, B. L.

    1992-01-01

    The paper uses particle size and volume measurements obtained with the forward scattering spectrometer probe model 300 during January and February 1989 in the Airborne Arctic Stratospheric Experiment to investigate processes important in the formation and growth of polar stratospheric cloud (PSC) particles. It is suggested on the basis of comparisons of the observations with expected sulfuric acid droplet deliquescence that in the Arctic a major fraction of the sulfuric acid droplets remain liquid until temperatures at least as low as 193 K. It is proposed that homogeneous freezing of the sulfuric acid droplets might occur near 190 K and might play a role in the formation of PSCs.

  2. Electrochemistry of ferroelectric thin film lead zirconate titanate in sulfuric acid

    NASA Astrophysics Data System (ADS)

    Small, Leo J.

    Remote sensing applications in harsh environments require sensor materials appropriately matched to the environment. PbZr0.52Ti0.48O 3 (PZT) is a candidate for remote sensing applications, where it could be used as both a sensor and power source. In this light, the evolution of the PZT-H2SO4 interface is explored at low pHs. A robotic microdroplet cell is developed to differentiate the electrochemical response of the cracks and pores inherent to the PZT film from that of continuous PZT. Accelerated chemical attack is observed at the pores, while the continuous PZT displays electrochemical hysteresis; the ferroelectric-solution interface can be switched between two different charge states at a given potential. As time progresses, electrochemical impedance spectroscopy reveals a change in the structure of the PZT-H2SO4 interface. Development of equivalent circuits to model the competing processes of pore growth, interfacial layer formation, and uniform chemical attack are guided by the evolution of film structure and chemistry as observed ex-situ with scanning electron microscopy, x-ray photoelectron spectroscopy, and x-ray diffraction. The Point Defect Model for the passive state is used to explain the dissolution processes observed in the complex oxide. Application of this model to PbZrxTi1- xO3 for x = 0.25, 0.52, and 0.95 points to the role of titanium in the creation of an ionically insulating layer that impedes further chemical attack.

  3. 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. PMID:26797956

  4. IR spectroscopic study of the surface of TiO/sub 2/ anatase modified with sulfuric acid

    SciTech Connect

    Khadzhiivanov, K.I.; Davydov, A.A.

    1988-10-01

    The elevated activity of anatase modified with sulfuric acid, which is determined by the acidity of the catalyst, has been observed in reactions of acylation, esterification, and isomerization of cyclopropane. It was shown that the formation of surface sulfates in modification of anatase with sulfuric acid causes the appearance of Broensted acid centers which persist up to high dehydration temperatures and an increase in the strength of Lewis acid centers. The symmetry, structure, and sites of the surface sulfates were discussed. The Broensted acid centers are caused by mobile protons bound with sulfate ions.

  5. Co-oxidation of the sulfur-containing amino acids in an autoxidizing lipid system

    USGS Publications Warehouse

    Wedemeyer, G.A.; Dollar, A.M.

    1963-01-01

    Oxidation of the sulfur amino acids by autoxidizing lipids was studied in a model system consisting of an amino acid dispersed in cold-pressed, molecularly distilled menhaden oil (20–80% w/w). Under all conditions investigated, cysteine was oxidized completely to cystine. Preliminary results suggest that at 110°C the oxidation follows first-order kinetics for at least the first 8 hr. A specific reaction rate constant of 0.25 per hour was calculated. When fatty acids were added to the system, cystine was oxidized to its thiosulfinate ester. When the fatty acid-cystine ratio was 1:2, oxidation of cystine was a maximum. No oxidation of cystine occurred unless either a fatty acid, volatile organic acid, or ethanol was added. Under the conditions investigated, methionine was not oxidized to either its sulfoxide or its sulfone.

  6. Mineralogical Controls on Microbial Diversity in a Sulfuric Acid Karst System

    NASA Astrophysics Data System (ADS)

    Jones, A. A.; Bennett, P.

    2011-12-01

    The role mineralogy plays on microbial community distribution, composition, niche differentiation, and accumulation is a complex and nebulous association. Microbial phylogenetic diversity and bacterial composition of communities obtained from Lower Kane Cave (LKC), WY, USA, were studied using next generation bacterial 16S rRNA sequencing techniques. The microbial consortium found within LKC was found to be primarily composed of neutrophilic sulfur-oxidizing members of the gamma- and epsilon-proteobacteria . The microbial population within LKC has been instigated in previous studies to have a significant role in the processes of sulfuric acid speleogenesis. Using a LKC biomat as the inoculant in a series of 3 nutrient limited laboratory reactor experiments, and a pure culture of Thiothrix unzii (ATCC type strain 49747) in a parallel experiment, we found that both limestone and dolostone substratum consistently had higher biomass accumulation than silicate minerals in the same reactor. At the Class level, the carbonate substratum (Calcite, Limestone, and Dolostone) had ~84% - 88.7% of phylotypes in common. Aside from Basalt (Simpson's Index, D of 0.53), the carbonate substratum produced the least diverse phylotype distributions. Feldspar and quartz were colonized by the most diverse communities with Simpson's Index values of 0.16 and 0.31. Evaluation of metabolic guild distribution shows that potential neutrophilic sulfur-oxidizers have an affinity for acid neutralizing carbonate substrata over silicate substrata. These potential sulfur-oxidizing guilds compose ~28%-38% of the total microbial community. For feldspar and chert substratum, potential sulfur-oxidizing metabolic guilds composed merely ~5% of the total microbial community. The quartz substratum, in contrast, was uniquely populated by potential acidophilic sulfur-oxidizers Acidithiobacillus and Acidithiomicrobium; composing ~19% of the total community. A quartz substratum may offer these acidophiles a

  7. Uptake of formaldehyde by sulfuric acid solutions - Impact on stratospheric ozone

    NASA Technical Reports Server (NTRS)

    Tolbert, Margaret A.; Pfaff, Jeanne; Jayaweera, Indira; Prather, Michael J.

    1993-01-01

    The study investigates the uptake of CH2O by low temperature sulfuric acid solutions representative of global stratospheric particulate. It is argued that if similar uptake occurs under stratospheric pressures of CH2O, i.e., 1000 times lower than used in the present study, then the removal of CH2O from the gas phase can take away a significant source of odd hydrogen in the mid- and high-latitude lower stratosphere. It is shown that with the inclusion of this reaction, concentrations of OH and H2O are reduced by as much as 4 percent under background levels of aerosols and more than 15 percent under elevated (volcanic) conditions. The accumulation of CH2O in stratospheric aerosols over a season, reaching about 1 M solutions, will alter the composition and may even change the reactivity of these sulfuric acid-water mixtures.

  8. Design bases: Bauxite-sulfuric acid feed facilities 100-K Area

    SciTech Connect

    Etheridge, E.L.

    1993-06-10

    This document defines the objective, bases, and functional requirements governing the preparation of detail design of the bauxite-sulfuric acid feed facilities to be installed in the 183-KE and KW buildings. These facilities will produce the chemical coagulant used in the treatment of Columbia River water in the water plants; they will replace existing liquid alum feed systems. The treated water will be used as reactor coolant.

  9. The dynamics of sorption of sulfuric acid by weakly basic polyacrylic anion exchangers

    NASA Astrophysics Data System (ADS)

    Mamchenko, A. V.; Kushnir, T. V.

    2009-05-01

    The nonequilibrium dynamics of sorption of sulfuric acid by free base forms of Amberlite IRA-67 and Lewatite VP.OC.1072 weakly basic anion exchangers is studied. It is established that, in hydrodynamic regimes of filtration, which are typical of OH filters of the first stage of water-desalting plants, the limiting stage of sorption kinetics is inside diffusion. It is concluded that the process is correctly described by an asymptotic solution to the inside-diffusion model of sorption dynamics.

  10. Size Distribution Studies on Sulfuric Acid-Water Particles in a Photolytic Reactor

    NASA Astrophysics Data System (ADS)

    Abdullahi, H. U.; Kunz, J. C.; Hanson, D. R.; Thao, S.; Vences, J.

    2015-12-01

    The size distribution of particles composed of sulfuric acid and water were measured in a Photolytic cylindrical Flow Reactor (PhoFR, inner diameter 5 cm, length ~ 100 cm). In the reactor, nitrous acid, water and sulfur dioxide gases along with ultraviolet light produced sulfuric acid. The particles formed from these vapors were detected with a scanning mobility particle spectrometer equipped with a diethylene glycol condensation particle counter (Jiang et al. 2011). For a set of standard conditions, particles attained a log-normal distribution with a peak diameter of 6 nm, and a total number of about 3x105 cm-3. The distributions show that ~70 % of the particles are between 4 and 8 nm diameter (lnσ ~ 0.37). These standard conditions are: 296 K, 25% relative humidity, total flow = 3 sLpm, ~10 ppbv HONO, SO2 in excess. With variations of relative humidity, the total particle number varied strongly, with a power relationship of ~3.5, and the size distributions showed a slight increase in peak diameter with relative humidity, increasing about 1 nm from 8 to 33 % relative humidity. Variations of HONO at a constant light intensity (wavelength of ~ 360 nm) were performed and particle size and total number changed dramatically. Size distributions also changed drastically with variations of light intensity, accomplished by turning on/off some of the black light flourescent bulbs that illuminated the flow reactor. Comparisons of these size distributions to recently published nucleation experiments (e.g. Zollner et al., Glasoe et al.) as well as to simulations of PhoFR reveal important details about the levels of sulfuric acid present in PhoFR as well as possible base contaminants.

  11. Reexamination of London, England, mortality in relation to exposure to acidic aerosols during 1963-1972 winters.

    PubMed

    Thurston, G D; Ito, K; Lippmann, M; Hayes, C

    1989-02-01

    Air pollution epidemiology since the 1950s has been able to demonstrate that increases in daily mortality in London, England, were associated with elevated concentrations of index air pollutants, i.e., British Smoke (BS) and sulfur dioxide (SO2). In this work, we reanalyze that portion of the 1958-1972 winter mortality-pollution record for which daily direct acid aerosol measurements were made at a central site in London (St. Bartholomew's Medical College). The purposes of these exploratory analyses are to examine the dataset for indications of a relationship between acid aerosol pollution and human mortality and to compare any noted associations with those for other pollution variables. It is found that the log of acid aerosol concentrations is more strongly associated with raw total mortality in bivariate analyses than is BS or SO2, despite the fact that acid data are available from only one central site (versus seven disperse sites for BS and SO2). The logarithmic nature of the exposure side of the H2SO4-mortality relationship implies a saturation model of pollution effects, possibly due to multiday pollution harvesting influences on a susceptible subpopulation. Moreover, mortality-pollution cross-correlation analyses indicate that mortality effects usually follow pollution in time, supporting a causal relationship between the two. The apparent advantage of H2SO4 over BS in predicting total raw mortality is consistent with the hypothesis that it is the portion of particulate mass of greater health significance and may also allow the development of London mortality results which are more easily transferable to other environments than is the case for existing BS results.

  12. Reexamination of London, England, mortality in relation to exposure to acidic aerosols during 1963-1972 winters.

    PubMed Central

    Thurston, G D; Ito, K; Lippmann, M; Hayes, C

    1989-01-01

    Air pollution epidemiology since the 1950s has been able to demonstrate that increases in daily mortality in London, England, were associated with elevated concentrations of index air pollutants, i.e., British Smoke (BS) and sulfur dioxide (SO2). In this work, we reanalyze that portion of the 1958-1972 winter mortality-pollution record for which daily direct acid aerosol measurements were made at a central site in London (St. Bartholomew's Medical College). The purposes of these exploratory analyses are to examine the dataset for indications of a relationship between acid aerosol pollution and human mortality and to compare any noted associations with those for other pollution variables. It is found that the log of acid aerosol concentrations is more strongly associated with raw total mortality in bivariate analyses than is BS or SO2, despite the fact that acid data are available from only one central site (versus seven disperse sites for BS and SO2). The logarithmic nature of the exposure side of the H2SO4-mortality relationship implies a saturation model of pollution effects, possibly due to multiday pollution harvesting influences on a susceptible subpopulation. Moreover, mortality-pollution cross-correlation analyses indicate that mortality effects usually follow pollution in time, supporting a causal relationship between the two. The apparent advantage of H2SO4 over BS in predicting total raw mortality is consistent with the hypothesis that it is the portion of particulate mass of greater health significance and may also allow the development of London mortality results which are more easily transferable to other environments than is the case for existing BS results. PMID:2785034

  13. [Determination of organic acids in rice wine by ion-exclusion chromatography].

    PubMed

    Lin, Xiaojie; Wei, Wei; He, Zhigang; Lin, Xiaozi

    2014-03-01

    An ion-exclusion chromatographic method for the simultaneous determination of organic acids in rice wine was developed. An IC-Pak Ion Exclusion column (300 mm x 7.8 mm, 7 microm) was used at 50 degrees C. The mobile phases were H2SO4 (phase A) and acetonitrile (phase B) (98:2, v/v) at a flow rate of 0.5 mL/min. The gradient elution program was as follows: 0-40 min, 0.01 mol/L H2SO4 to 0.02 mol/L H2SO4; 40-50 min, 0.01 mol/L H2SO4. The injection volume was 10 microL. The detection wavelength was set at 210 nm. The results showed that oxalic acid, maleic acid, citric acid, tartaric acid, malic acid, ascorbic acid, succinic acid, lactic, fumaric acid, acetic acid, propionic acid, isobutyric acid and butyric acid were completely separated and determined in 30 min. The linear correlation coefficients were above 0.999 7 in the range of 0.001- 1.000 g/L. Under the optimized conditions, the recoveries of organic acids in rice wine were in the range of 93.4% - 103.8% with the relative standard deviations (RSDs, n = 5) of 0.1% - 1.5%. This method is feasible, convenient, fast, accurate and applicable for the quantitative analysis of the organic acids in rice wine.

  14. [Determination of organic acids in rice wine by ion-exclusion chromatography].

    PubMed

    Lin, Xiaojie; Wei, Wei; He, Zhigang; Lin, Xiaozi

    2014-03-01

    An ion-exclusion chromatographic method for the simultaneous determination of organic acids in rice wine was developed. An IC-Pak Ion Exclusion column (300 mm x 7.8 mm, 7 microm) was used at 50 degrees C. The mobile phases were H2SO4 (phase A) and acetonitrile (phase B) (98:2, v/v) at a flow rate of 0.5 mL/min. The gradient elution program was as follows: 0-40 min, 0.01 mol/L H2SO4 to 0.02 mol/L H2SO4; 40-50 min, 0.01 mol/L H2SO4. The injection volume was 10 microL. The detection wavelength was set at 210 nm. The results showed that oxalic acid, maleic acid, citric acid, tartaric acid, malic acid, ascorbic acid, succinic acid, lactic, fumaric acid, acetic acid, propionic acid, isobutyric acid and butyric acid were completely separated and determined in 30 min. The linear correlation coefficients were above 0.999 7 in the range of 0.001- 1.000 g/L. Under the optimized conditions, the recoveries of organic acids in rice wine were in the range of 93.4% - 103.8% with the relative standard deviations (RSDs, n = 5) of 0.1% - 1.5%. This method is feasible, convenient, fast, accurate and applicable for the quantitative analysis of the organic acids in rice wine. PMID:24984473

  15. Activated carbon cleanup of the acid gas feed to Claus sulfur plants

    SciTech Connect

    Harruff, L.G.; Bushkuhl, S.J.

    1996-12-31

    This paper presents the details of a recently developed novel process using activated carbon to remove hydrocarbon contaminants from the acid gas feed to Claus sulfur recovery units. Heavy hydrocarbons, particularly benzene, toluene and xylene (BTX) have been linked to coke formation and catalyst deactivation in Claus converters. This deactivation results in reduced sulfur recovery and increased sulfur emissions from these plants. This effect is especially evident in split flow Claus plants which bypass some of the acid gas feed stream around the initial combustion step because of a low hydrogen sulfide concentration. This new clean-up process was proven to be capable of removing 95% of the BTX and other C{sub 6}{sup +} hydrocarbons from acid gas over a wide range of actual plant conditions. Following the adsorption step, the activated carbon was easily regenerated using low pressure steam. A post regeneration drying step using plant fuel gas also proved beneficial. This technology was extensively pilot tested in Saudi Aramco`s facilities in Saudi Arabia. Full scale commercial units are planned for two plants in the near future with the first coming on-line in 1997. The process described here represents the first application of activated carbon in this service, and a patent has been applied for. The paper will discuss the pilot plant results and the issues involved in scale-up to commercial size.

  16. A hybrid Li-air battery with buckypaper air cathode and sulfuric acid electrolyte

    SciTech Connect

    Li, YF; Huang, K; Xing, YC

    2012-10-30

    We demonstrate a type of carbon nanotube based buckypaper cathode in a hybrid electrolyte Li-air battery (HyLAB) that showed outstanding discharging performances. The HyLAB has sulfuric acid as the catholyte and a large active electrode area (10 cm(2)). The active cathode layer was made from a buckypaper with 5 wt.% Pt supported on carbon nanotubes (Pt/CNTs) for oxygen reduction and evolution. A similar cathode was constructed with a catalyst of 5 wt.% Pt supported on carbon black (Pt/CB). It is demonstrated that sulfuric acid can achieve high discharging current densities while maintaining relatively high cell potentials. The cell with Pt/CNTs showed a much better performance than with Pt/CB at high current densities. The HyLAB with Pt/CNTs achieved a discharging capacity of 306 mAh/g and a cell voltage of 3.15 V at 0.2 mA/cm(2). The corresponding specific energy is 1067 Wh/kg based on the total weight of the sulfuric acid. Slow decrease in performance was observed, but it can be recovered by refilling the cell with new electrolyte after continuous discharging of more than 75 h. A charge-discharge experiment at 0.2 mA/cm(2) showed that the cell was rechargeable with a capacity of more than 300 mAh/g. (c) 2012 Elsevier Ltd. All rights reserved.

  17. Molecular understanding of atmospheric particle formation from sulfuric acid and large oxidized organic molecules.

    PubMed

    Schobesberger, Siegfried; Junninen, Heikki; Bianchi, Federico; Lönn, Gustaf; Ehn, Mikael; Lehtipalo, Katrianne; Dommen, Josef; Ehrhart, Sebastian; Ortega, Ismael K; Franchin, Alessandro; Nieminen, Tuomo; Riccobono, Francesco; Hutterli, Manuel; Duplissy, Jonathan; Almeida, João; Amorim, Antonio; Breitenlechner, Martin; Downard, Andrew J; Dunne, Eimear M; Flagan, Richard C; Kajos, Maija; Keskinen, Helmi; Kirkby, Jasper; Kupc, Agnieszka; Kürten, Andreas; Kurtén, Theo; Laaksonen, Ari; Mathot, Serge; Onnela, Antti; Praplan, Arnaud P; Rondo, Linda; Santos, Filipe D; Schallhart, Simon; Schnitzhofer, Ralf; Sipilä, Mikko; Tomé, António; Tsagkogeorgas, Georgios; Vehkamäki, Hanna; Wimmer, Daniela; Baltensperger, Urs; Carslaw, Kenneth S; Curtius, Joachim; Hansel, Armin; Petäjä, Tuukka; Kulmala, Markku; Donahue, Neil M; Worsnop, Douglas R

    2013-10-22

    Atmospheric aerosols formed by nucleation of vapors affect radiative forcing and therefore climate. However, the underlying mechanisms of nucleation remain unclear, particularly the involvement of organic compounds. Here, we present high-resolution mass spectra of ion clusters observed during new particle formation experiments performed at the Cosmics Leaving Outdoor Droplets chamber at the European Organization for Nuclear Research. The experiments involved sulfuric