The effect of NaCl/g/ on the Na2SO4-induced hot corrosion of NiAl

NASA Technical Reports Server (NTRS)

Smeggil, J. G.; Bornstein, N. S.; Decrescente, M. A.

1977-01-01

Studies have been performed to examine the effect of NaCl vapor on the Na2SO4-induced hot corrosion of the alumina former NiAl. In the incubation period associated with such hot corrosion, NaCl(g) has been shown to be effective in removing aluminum from below the protective alumina scale and redepositing it as Al2O3 whiskers on the surface of the Na2SO4-coated sample. Similar effects seen in simple oxidation are associated with isothermal rupturing of the protective alumina scale.

The ternary system K2SO4MgSO4CaSO4

USGS Publications Warehouse

Rowe, J.J.; Morey, G.W.; Silber, C.C.

1967-01-01

Melting and subsolidus relations in the system K2SO4MgSO4CaSO4 were studied using heating-cooling curves, differential thermal analysis, optics, X-ray diffraction at room and high temperatures and by quenching techniques. Previous investigators were unable to study the binary MgSO4CaSO4 system and the adjacent area in the ternary system because of the decomposition of MgSO4 and CaSO4 at high temperatures. This problem was partly overcome by a novel sealed-tube quenching method, by hydrothermal synthesis, and by long-time heating in the solidus. As a result of this study, we found: (1) a new compound, CaSO4??3MgSO4 (m.p. 1201??C) with a field extending into the ternary system; (2) a high temperature form of MgSO4 with a sluggishly reversible inversion. An X-ray diffraction pattern for this polymorphic form is given; (3) the inversion of ??-CaSO4 (anhydrite) to ??-CaSO4 at 1195??C, in agreement with grahmann; (1) (4) the melting point of MgSO4 is 1136??C and that of CaSO4 is 1462??C (using sealed tube methods to prevent decomposition of the sulphates); (5) calcium langbeinite (K2SO4??2CaSO4) is the only compound in the K2SO4CaSO4 binary system. This resolved discrepancies in the results of previous investigators; (6) a continuous solid solution series between congruently melting K2SOP4??2MgSO4 (langbeinite) and incongruently melting K2SO4??2CaSO4 (calcium langbeinite); (7) the liquidus in the ternary system consists of primary phase fields of K2SO4, MgSO4, CaSO4, langbeinite-calcium langbeinite solid solution, and CaSO4??3MgSO4. The CaSO4 field extends over a large portion of the system. Previously reported fields for the compounds (K2SO4??MgSO4??nCaSO4), K2SO4??3CaSO4 and K2SO4??CaSO4 were not found; (8) a minimum in the ternary system at: 740??C, 25% MgSO4, 6% CaSO4, 69% K2SO4; and ternary eutectics at 882??C, 49% MgSO4, 19% CaSO4, 32% K2SO4; and 880??, 67??5% MgSO4, 5% CaSO4, 27??5% K2SO4. ?? 1967.

Hot-corrosion of AISI 1020 steel in a molten NaCl/Na2SO4 eutectic at 700°C

NASA Astrophysics Data System (ADS)

Badaruddin, Mohammad; Risano, Ahmad Yudi Eka; Wardono, Herry; Asmi, Dwi

2017-01-01

Hot-corrosion behavior and morphological development of AISI 1020 steel with 2 mg cm-2 mixtures of various NaCl/Na2SO4 ratios at 700°C were investigated by means of weight gain measurements, Optical Microscope (OM), X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDS). The weight gain kinetics of the steel with mixtures of salt deposits display a rapid growth rates, compared with the weight gain kinetics of AISI 1020 steel without salt deposit in dry air oxidation, and follow a steady-state parabolic law for 49 h. Chloridation and sulfidation produced by a molten NaCl/Na2SO4 on the steel induced hot-corrosion mechanism attack, and are responsible for the formation of thicker scale. The most severe corrosion takes place with the 70 wt.% NaCl mixtures in Na2SO4. The typical Fe2O3 whisker growth in outer part scale was attributed to the FeCl3 volatilization. The formation of FeS in the innermost scale is more pronounced as the content of Na2SO4 in the mixture is increased.

Sodium relations in desert plants: 8. Differential effects of NaCl and Na/sub 2/SO/sub 4/ on growth and composition of Atriplex hymenelytra (desert holly)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Soufi, S.M.; Wallace, A.

1982-07-01

Maximum growth over a period of 3 months of Atriplex hymenelytra (Torr.) Wats. (desert holly) in solution culture was obtained when the nutrient solution contained 5 x 10/sup -2/ N NaCl. Sodium concentratons in leaves at maximum yield was 7.88% and that of Cl was also 7.88%. In the presence of 10/sup -2/ N Na/sub 2/SO/sub 4/, there was much less growth than with 10/sup -2/ N NaCl. The highest NaCl level depressed levels of K, Ca, and Mg in leaves, stems, and roots. The highest NaCl level also decreased levels of micronutrients in many of the plants.

Kinetics Study on the Effect of NaCl on the CaSO4 Dissolution Behavior

NASA Astrophysics Data System (ADS)

Song, Jingyao; Shi, Peiyang; Wang, Yeguang; Jiang, Maofa

2018-01-01

The study of the dissolution kinetics of CaSO4 is essential for the control of the dissolution and recrystallization behavior of CaSO4. In this work, the kinetic behavior of CaSO4 dissolved in NaCl solution was investigated by means of conductivity meter. The results show that with the increase of concentration of NaCl, the temperature rise and the time prolonged, the dissolution rate of dihydrate CaSO4 gradually increases, and the dissolved apparent activation energy is gradually decreased. When the NaCl concentration is 1.8%, the dissolution kinetic equation is 1-(1-α) 1/3=5.46*10-4exp (-9147/RT) t; When the NaCl concentration is 3.0%, the dissolution kinetic equation is 1-(1-α) 1/3=2.81×10-4 exp (-6753/RT)t; When the NaCl concentration is 3.6%, the dissolution kinetic equation is 1-(1-α) 1/3=3.07×l0-4exp(-6103/RT)t.

Treatment for GaSb surfaces using a sulphur blended (NH4)2S/(NH4)2SO4 solution

NASA Astrophysics Data System (ADS)

Murape, D. M.; Eassa, N.; Neethling, J. H.; Betz, R.; Coetsee, E.; Swart, H. C.; Botha, J. R.; Venter, A.

2012-07-01

A sulphur based chemical, [(NH4)2S/(NH4)2SO4] to which S has been added, not previously reported for the treatment of (1 0 0) n-GaSb surfaces, is introduced and benchmarked against the commonly used passivants Na2S·9H2O and (NH4)2S. The surfaces of the treated material were studied by scanning electron microscopy (SEM), Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS). It has been found that the native oxides present on the GaSb surface are more effectively removed when treated with ([(NH4)2S/(NH4)2SO4] + S) than with (NH4)2S or Na2S·9H2O, as evidenced by the ratio of the O506 eV to Sb457 eV AES peaks. XPS results reveal that Sb2S3/Sb2S5 "replaces" Sb2O3/Sb2O5, suggesting that sulphur atoms substitute oxygen atoms in Sb2O3/Sb2O5 to form Sbsbnd S. It seems sulphurization only partially removes Ga2O3. Treatment with ([(NH4)2S/(NH4)2SO4] + S) also results in a noteworthy improvement in the current-voltage (I-V) characteristics of Au/n-GaSb Schottky contacts compared to those fabricated on as-received material.

Mechanism of Na2SO4 Promoting Nickel Extraction from Sulfide Concentrates by Sulfation Roasting-Water Leaching

NASA Astrophysics Data System (ADS)

Li, Guangshi; Cheng, Hongwei; Chen, Sha; Lu, Xionggang; Xu, Qian; Lu, Changyuan

2018-04-01

As a more environmentally friendly and energy-efficient route, the sulfation roasting-water leaching technique has been developed for highly effective extraction of non-ferrous metals from nickel sulfide concentrate in the presence of a Na2SO4 additive. The effects of several important roasting parameters—the roasting temperature, the addition of Na2SO4, the holding time, and the heating rate in particular—have been investigated. The results suggest that about 90 pct Ni, 92 pct Co, 95 pct Cu, and < 1 pct Fe can be leached from the calcine roasted under the optimum conditions. Furthermore, the behavior and mechanism of the Na2SO4 additive in the roasting process have been well addressed by detailed characterization of the roasted product and leaching residue using quantitative phase analysis (QPA) and energy dispersive spectroscopy (EDS) mapping. The Na2SO4 additive was observed to play a noticeable role in promoting the sulfation degree of valuable metals by forming liquid phases [Na2Me(SO4)2] at the outermost layer, which can create a suitable dynamic environment for sulfation. Thus, addition of Na2SO4 might be conducive to an alternative metallurgical process involving complex sulfide ores.

Mechanism of Na2SO4 Promoting Nickel Extraction from Sulfide Concentrates by Sulfation Roasting-Water Leaching

NASA Astrophysics Data System (ADS)

Li, Guangshi; Cheng, Hongwei; Chen, Sha; Lu, Xionggang; Xu, Qian; Lu, Changyuan

2018-06-01

As a more environmentally friendly and energy-efficient route, the sulfation roasting-water leaching technique has been developed for highly effective extraction of non-ferrous metals from nickel sulfide concentrate in the presence of a Na2SO4 additive. The effects of several important roasting parameters—the roasting temperature, the addition of Na2SO4, the holding time, and the heating rate in particular—have been investigated. The results suggest that about 90 pct Ni, 92 pct Co, 95 pct Cu, and < 1 pct Fe can be leached from the calcine roasted under the optimum conditions. Furthermore, the behavior and mechanism of the Na2SO4 additive in the roasting process have been well addressed by detailed characterization of the roasted product and leaching residue using quantitative phase analysis (QPA) and energy dispersive spectroscopy (EDS) mapping. The Na2SO4 additive was observed to play a noticeable role in promoting the sulfation degree of valuable metals by forming liquid phases [Na2Me(SO4)2] at the outermost layer, which can create a suitable dynamic environment for sulfation. Thus, addition of Na2SO4 might be conducive to an alternative metallurgical process involving complex sulfide ores.

The influence of pressure on the activity coefficients of the solutes and on the solubility of minerals in the system Na-Ca-Cl-SO 4-H 2O to 200°C and 1 kbar and to high NaCl concentration

NASA Astrophysics Data System (ADS)

Monnin, Christophe

1990-12-01

A model is presented which is used to calculate the effect of pressure on activity coefficients of aqueous solutes in the system Na-Ca-Cl-SO 4-H 2O to 200°C. Literature data for the density and compressibility of aqueous binary solutions of Na 2SO 4 and CaCl 2 to 200°C are used to calculate the first and second pressure derivatives of Pitzer's ion interaction model parameters, as well as the standard molal compressibility and volume of these two salts. Empirical correlations between the apparent molal volume and compressibility of the aqueous electrolytes are used to guide the choice of the temperature dependent expressions used for the numerical representation of the derivatives of Pitzer's parameters with respect to pressure. For sodium sulfate solutions, such correlations are used to extrapolate compressibilities to 200°C. The change in the thermodynamic properties of the-CaSO 04 ion pair with pressure is taken into account by the variation of its dissociation constant. The volumetric properties (partial molal volumes and compressibilities) of multicomponent solutions in the Na-Ca-Cl-SO 4-H 2O system can be predicted from the information generated here and the volumetric equations of ROGERS and PITZER (1982) for NaCl. This model is then combined with the high temperature model of MOLLER (1988) of the same system in order to calculate activity coefficients at high pressures to 200°C. The resulting model is validated by comparing calculated and measured solubilities of anhydrite and gypsum in pure water and in NaCl solutions up to 6 M. The agreement between the calculated and measured solubilities of the calcium sulfates is typically better than 10% up to 200°C and 1 kbar. The relevance of temperature and pressure corrections to the activity coefficients of aqueous solutes is discussed in regard to the assumed accuracy with which geochemical models are able to calculate mineral solubilities.

Formation of Na2SO4 and K2SO4 in flames doped with sulfur and alkali chlorides and carbonates

NASA Technical Reports Server (NTRS)

Fryburg, G. C.; Miller, R. A.; Stearns, C. A.; Kohl, F. J.

1977-01-01

High pressure, free-jet expansion, mass spectrometric sampling was used to identify directly and to measure reaction products formed in doped methane-oxygen flames. Flames were doped with SO2 or CH3SH and sodium or potassium chlorides or carbonates. Gaseous NA2SO4 or K2S04 molecules were formed in residence times on the order of msec for each combination of dopants used. Composition profiles of combustion products were measured and compared with equilibrium thermodynamic calculations of product composition.

Mechanistic and Kinetic Analysis of Na2SO4-Modified Laterite Decomposition by Thermogravimetry Coupled with Mass Spectrometry

PubMed Central

Yang, Song; Du, Wenguang; Shi, Pengzheng; Shangguan, Ju; Liu, Shoujun; Zhou, Changhai; Chen, Peng; Zhang, Qian; Fan, Huiling

2016-01-01

Nickel laterites cannot be effectively used in physical methods because of their poor crystallinity and fine grain size. Na2SO4 is the most efficient additive for grade enrichment and Ni recovery. However, how Na2SO4 affects the selective reduction of laterite ores has not been clearly investigated. This study investigated the decomposition of laterite with and without the addition of Na2SO4 in an argon atmosphere using thermogravimetry coupled with mass spectrometry (TG-MS). Approximately 25 mg of samples with 20 wt% Na2SO4 was pyrolyzed under a 100 ml/min Ar flow at a heating rate of 10°C/min from room temperature to 1300°C. The kinetic study was based on derivative thermogravimetric (DTG) curves. The evolution of the pyrolysis gas composition was detected by mass spectrometry, and the decomposition products were analyzed by X-ray diffraction (XRD). The decomposition behavior of laterite with the addition of Na2SO4 was similar to that of pure laterite below 800°C during the first three stages. However, in the fourth stage, the dolomite decomposed at 897°C, which is approximately 200°C lower than the decomposition of pure laterite. In the last stage, the laterite decomposed and emitted SO2 in the presence of Na2SO4 with an activation energy of 91.37 kJ/mol. The decomposition of laterite with and without the addition of Na2SO4 can be described by one first-order reaction. Moreover, the use of Na2SO4 as the modification agent can reduce the activation energy of laterite decomposition; thus, the reaction rate can be accelerated, and the reaction temperature can be markedly reduced. PMID:27333072

Effect of the amount of Na2SO4 on the high temperature corrosion of Udimet-700

NASA Technical Reports Server (NTRS)

Misra, A. K.; Kohl, F. J.

1983-01-01

The corrosion of Udimet-700, coated with different doses of Na2SO4, was studied in an isothermal thermogravimetric test in the temperature range 900 to 950 C. The weight gain curve is characterized by five distinct stages: an initial period of linear corrosion; an induction period; a period of accelerated corrosion; a period of decelerating corrosion; and a period of parabolic oxidation. The time required for the failure of the alloy increases with an increase in the amount of Na2SO4, reaches a peak and then decreases with further increase in the amount of Na2SO4. For low and intermediate doses (0.3 to 2.0 mg/sq cm), the catastrophic failure of the material occurs by the formation of Na2MoO4 and interaction of the liquid Na2MoO4 with the alloy. For heavy doses, the degradation of the material is due to the formation of large amounts of sulfides.

The binary system K2SO4CaSO4

USGS Publications Warehouse

Rowe, J.J.; Morey, G.W.; Hansen, I.D.

1965-01-01

The binary system K2SO4CaSO4 was studied by means of heating-cooling curves, differential thermal analysis, high-temperature quenching technique and by means of a heating stage mounted on an X-ray diffractometer. Compositions and quench products were identified optically and by X-ray. Limited solid solution of CaSO4 in K2SO4 was found. There is a eutectic at 875??C and 34 wt. per cent CaSO4. Calcium langbeinite melts incongruently at 1011??C. The melting-point of CaSO4 (1462??C) was determined by the quenching technique using sealed platinum tubes. The only intermediate crystalline phase found in the system is K2SO4??2CaSO4 (calcium langbeinite). ?? 1965.

The system K2Mg2(SO4)3 (langbeinite)-K2Ca2(SO4)3 (calcium-langbeinite)

USGS Publications Warehouse

Morey, G.W.; Rowe, J.J.; Fournier, R.O.

1964-01-01

The join between the compositions K2Mg2(SO4)3 and K2Ca2(SO4)3 was studied by means of high-temperature equilibrium quenching techniques and by means of a heating stage mounted on an X-ray diffractometer. Complete solid solution exists in the system, but at 25??C members of the solid solution series are isometric only in the composition range 0-73??5 wt. per cent K2Ca2(SO4)3. At compositions richer in K2Ca2(SO4)3 than 73??5 wt. per cent, members of the series are optically biaxial. At higher temperatures members of the solid solution series are isometric at successively more calcium-rich compositions and pure K2Ca2(SO4)3 is isometric above about 200 ?? 2??C. The system is not binary, as mixtures richer in K2Ca2(SO4)3 than 42 wt. per cent decompose with the formation of liquid and CaSO4. ?? 1964.

Deposition of Na2SO4 from salt-seeded combustion gases of a high velocity burner rig

NASA Technical Reports Server (NTRS)

Santoro, G. J.; Kohl, F. J.; Stearns, C. A.; Gokoglu, S. A.; Rosner, D. A.

1985-01-01

With a view to developing simulation criteria for the laboratory testing of high-temperature materials for gas turbine engines, the deposition rates of sodium sulfate from sodium salt-seeded combustion gases were determined experimentally using a well instrumented high-velocity burner. In the experiments, Na2SO4, NaCl, NaNO3, and simulated sea salt solutions were injected into the combustor of the Mach 0.3 burner rig operating at constant fuel/air ratios. The deposits formed on an inert rotating collector were then weighed and analyzed. The experimental results are compared to Rosner's vapor diffusion theory. Some additional test results, including droplet size distribution of an atomized salt spray, are used in interpreting the deposition rate data.

Kinetics of heterogeneous reactions of HO2 radical at ambient concentration levels with (NH4)2SO4 and NaCl aerosol particles.

PubMed

Taketani, Fumikazu; Kanaya, Yugo; Akimoto, Hajime

2008-03-20

The HO2 uptake coefficient (gamma) for inorganic submicrometer wet and dry aerosol particles ((NH4)2SO4 and NaCl) under ambient conditions (760 Torr and 296 +/- 2 K) was measured using an aerosol flow tube (AFT) coupled with a chemical conversion/laser-induced fluorescence (CC/LIF) technique. The CC/LIF technique enabled experiments to be performed at almost the same HO2 radical concentration as that in the atmosphere. HO2 radicals were injected into the AFT through a vertically movable Pyrex tube. Injector position-dependent profiles of LIF intensity were measured as a function of aerosol concentration. Measured gamma values for dry aerosols of (NH4)2SO4 were 0.04 +/- 0.02 and 0.05 +/- 0.02 at 20% and 45% relative humidity (RH), respectively, while those of NaCl were <0.01 and 0.02 +/- 0.01 at 20% and 53% RH, respectively. For wet (NH4)2SO4 aerosols, measured gamma values were 0.11 +/- 0.03, 0.15 +/- 0.03, 0.17 +/- 0.04, and 0.19 +/- 0.04, at 45%, 55%, 65%, and 75% RH, respectively, whereas for wet NaCl aerosols the values were 0.11 +/- 0.03, 0.09 +/- 0.02, and 0.10 +/- 0.02 for 53%, 63%, and 75% RH, respectively. Wet (NH4)2SO4 and NaCl aerosols doped with CuSO4 showed gamma values of 0.53 +/- 0.12 and 0.65 +/- 0.17, respectively. These results suggest that compositions, RH, and phase for aerosol particles are significant to HO2 uptake. Potential HO2 loss processes and their atmospheric contributions are discussed.

Effects of Na2SO4 on iron and nickel reduction in a high-iron and low-nickel laterite ore

NASA Astrophysics Data System (ADS)

Wang, Xiao-ping; Sun, Ti-chang; Chen, Chao; Kou, Jue

2018-04-01

This study investigates the reactions of Na2SO4 and its effects on iron and nickel reduction in the roasting of a high-iron and low-nickel laterite ore through gas composition, X-ray diffraction, and scanning electron microscope analyses. Results showed that a reduction reaction of Na2SO4 to SO2 was performed with roasting up to 600°C. However, no clear influence on iron and nickel reductions appeared, because only a small amount of Na2SO4 reacted to produce SO2. Na2SO4 reacted completely at 1000°C, mainly producing troilite and nepheline, which remarkably improves selective reduction of nickel. Furthermore, the production of low-melting-point minerals, including troilite and nepheline, accelerated nickel reduction and delayed iron reduction, which is attributed to the concurrent production of magnesium magnetite, whose structure is more stable than the structure of magnetite. Reduction reactions of Na2SO4 resulted in weakening of the reduction atmosphere, and the main product of Na2SO4 changed and delayed the reduction of iron. Eventually, iron metallization was effectively controlled during laterite ore reduction roasting, leading to iron mainly being found in wustite and high iron-containing olivine.

Effects of Partial Substitutions of NaCl with KCl, CaSO4 and MgSO4 on the Quality and Sensorial Properties of Pork Patties.

PubMed

Davaatseren, Munkhtugs; Chun, Ji-Yeon; Cho, Hyung-Yong; Min, Sang-Gi; Choi, Mi-Jung

2014-01-01

This study investigated the effects of NaCl replacers (KCl, CaSO4, and MgSO4) on the quality and sensorial properties of pork patty. In the characteristics of spray-dried salt particles, KCl showed the largest particle size with low viscosity in solution. Meanwhile CaSO4 treatment resulted in the smallest particle size and the highest viscosity (p<0.05). In comparison of the qualities of pork patties manufactured by varying level of Na replacers, MgSO4 treatment exhibited low cooking loss comparing to control (p<0.05). Textural properties of KCl and MgSO4 treatments showed similar pattern, i.e., low level of the replacers caused harder and less adhesive texture than those of control (p<0.05), whereas the hardness of these products was not different with control when the replacers were added more than 1.0%. The addition of CaSO4 also manifested harder and less adhesive than control (p<0.05), but the textural properties of CaSO4 treatment was not affected by level of Ca-salt. Eventually, sensorial properties indicated that KCl and CaSO4 influenced negative effects on pork patties. In contrast, MgSO4 showed better sensorial properties in juiciness intensity, tenderness intensity as well as overall acceptability than control, reflecting that MgSO4 was an effective Na-replacer in meat product formulation.

Empirical electronic polarizabilities: deviations from the additivity rule. I. M2+SO4·nH2O, blödite Na2M2+(SO4)2·4H2O, and kieserite-related minerals with sterically strained structures

NASA Astrophysics Data System (ADS)

Gagné, Olivier; Hawthorne, Frank; Shannon, Robert D.; Fischer, Reinhard X.

2017-09-01

Empirical electronic polarizabilities allow the prediction of total mineral polarizabilities and mean refractive indices of the vast majority of minerals and synthetic oxides. However, deviations from the valence-sum rule at cations in some minerals are associated with large deviations of observed from calculated total polarizabilities. We have identified several groups of minerals and compounds where deviations from the valence-sum rule at cations lead to polarizability deviations of 2-5%: M(SO4)·nH2O, n = 1-6, blödite-group minerals [Na2M2+(SO4)2·4H2O], and the kieserite-related minerals: isokite, panasqueiraite and tilasite. In these minerals, the environment of the M ions contains both O and H2O: Mg[O4(H2O)2] in kieserite, szmikite, and szomolnokite; Mg[O2(H2O)4] in starkeyite, ilesite, and rozenite, and Mg[(H2O)6] in hexahydrite. In compounds where the ligands are only H2O, deviations from the valence-sum rule at the M(H2O)6 groups are not accompanied by significant polarizability deviations. This is the case for epsomite, MgSO4·7H2O; bieberite, CoSO4·7H2O; goslarite, ZnSO4·7H2O, six silicofluorides, MSiF6·6H2O; eighteen Tutton's salts, M2M'(SO4)2·6H2O, where M = K, Rb, Cs and M' = Mg, Mn, Fe, Co, Ni, Cu, and Zn; and eleven MM'(SO4)2·12H2O alums, where M = Na, K, Rb and Cs, and M' = Al, Cr, Ga and In. This is also the case for the sulfates alunogen, Al2(SO4)3·17H2O and halotrichite, FeAl2(SO4)4·22H2O; three hydrated nitrates; one phosphate; three antimonates and two hydrated perchlorates. A possible explanation for this different behavior is that the bond-valence model treats O and H separately, whereas polarizability calculations treat the polarizability of the entire H2O molecule.

The Corrosion Behavior of Pure Iron under Solid Na2SO4 Deposit in Wet Oxygen Flow at 500 °C

PubMed Central

Tang, Yanbing; Liu, Li; Fan, Lei; Li, Ying; Wang, Fuhui

2014-01-01

The corrosion behavior of pure Fe under a Na2SO4 deposit in an atmosphere of O2 + H2O was investigated at 500 °C by thermo gravimetric, and electrochemical measurements, viz. potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and surface characterization methods viz. X-ray diffraction (XRD), and scanning electron microscope (SEM)/energy dispersive spectroscopy(EDS). The results showed that a synergistic effect occurred between Na2SO4 and O2 + H2O, which significantly accelerated the corrosion rate of the pure Fe. Briefly, NaFeO2 was formed in addition to the customary Fe oxides; at the same time, H2SO4 gas was produced by introduction of water vapor. Subsequently, an electrochemical corrosion reaction occurred due to the existence of Na2SO4, NaFeO2, and H2O. When this coupled to the chemical corrosion reaction, the progress of the chemical corrosion reaction was promoted and eventually resulted in the acceleration of the corrosion of the pure Fe. PMID:28788182

Möhnite, (NH4)K2Na(SO4)2, a new guano mineral from Pabellón de Pica, Chile

NASA Astrophysics Data System (ADS)

Chukanov, Nikita V.; Aksenov, Sergey M.; Rastsvetaeva, Ramiza K.; Pekov, Igor V.; Belakovskiy, Dmitry I.; Britvin, Sergey N.

2015-10-01

The new mineral möhnite, ideally (NH4)K2Na(SO4)2, the ammonium analogue of aphthitalite, is found in a guano deposit on the Pabellón de Pica mountain, near Chanabaya, Iquique Province, Tarapacá Region, Chile. It is associated with salammoniac, halite, joanneumite, natroxalate, nitratine, chanabayaite, and a clay mineral. Möhnite occurs as random aggregates and clusters of brown imperfect bipyramidal or spindle-shaped crystals. The mineral is brittle, with Mohs' hardness of 3; Dmeas is 2.4(1) g/cm3 and Dcalc is 2.461 g/cm3. The IR spectrum shows the presence of NH4 + cations (the bands at 1431, 3076 and 3240 cm-1). Möhnite is almost isotropic, optically neutral; ɛ = ω = 1.505(2). The chemical composition (electron-microprobe data, N determined by gas chromatography of products of ignition, H calculated by stoichiometry, wt%) is: (NH4)2O 7.99, Na2O 9.49, K2O 32.34, SO3 51.32, total 101.14. The empirical formula is (NH4)0.95Na0.95 K2.14S1.99O8. The crystal structure was solved and refined to R = 0.049 based on 241 unique reflections with I > 2σ( I). Möhnite is trigonal, space group P m1, a = 5.7402(3) Å, c = 7.435(1) Å, V = 212.16(4) Å3, Z = 1. The strongest reflections of the powder X-ray diffraction pattern [ d, Å ( I,%) ( hkl)] are: 4.955 (27) (100), 4.122 (37) (101, 011), 3.708 (29) (002), 2.969 (74) (102, 012), 2.861 (100) (110), 2.474 (20) (003), 2.060 (33) (022). The mineral is named in honour of the German amateur mineralogist Gerhard Möhn (born 1959).

Role of molybdenum in the Na sub 2SO sub 4 induced corrosion of superalloys at high temperatures

NASA Technical Reports Server (NTRS)

Misra, A. K.

1986-01-01

Sodium sulfate induced corrosion of a molybdenum containing nickel-base superalloy, Udimet 700, was studied in laboratory furnace tests and in a high velocity (Mach 0.3) burner rig. The effect of SO2 content in the atmosphere on the corrosion behavior in the laboratory furnace tests was determined. Catastrophic corrosion occurs only when the melt contains MoO3 in addition to Na2SO4 and Na2MoO4. The conditions under which catastrophic corrosion occurs are identified and a mechanism is described to explain the catastrophic corrosion.

Physiological responses to salt stress of salt-adapted and directly salt (NaCl and NaCl+Na2SO4 mixture)-stressed cyanobacterium Anabaena fertilissima.

PubMed

Swapnil, Prashant; Rai, Ashwani K

2018-05-01

Soil salinity in nature is generally mixed type; however, most of the studies on salt toxicity are performed with NaCl and little is known about sulfur type of salinity (Na 2 SO 4 ). Present study discerns the physiologic mechanisms responsible for salt tolerance in salt-adapted Anabaena fertilissima, and responses of directly stressed parent cells to NaCl and NaCl+Na 2 SO 4 mixture. NaCl at 500 mM was lethal to the cyanobacterium, whereas salt-adapted cells grew luxuriantly. Salinity impaired gross photosynthesis, electron transport activities, and respiration in parent cells, but not in the salt-adapted cells, except a marginal increase in PSI activity. Despite higher Na + concentration in the salt mixture, equimolar NaCl appeared more inhibitive to growth. Sucrose and trehalose content and antioxidant activities were maximal in 250 mM NaCl-treated cells, followed by salt mixture and was almost identical in salt-adapted (exposed to 500 mm NaCl) and control cells, except a marginal increase in ascorbate peroxidase activity and an additional fourth superoxide dismutase isoform. Catalase isoform of 63 kDa was induced only in salt-stressed cells. Salinity increased the uptake of intracellular Na + and Ca 2+ and leakage of K + in parent cells, while cation level in salt-adapted cells was comparable to control. Though there was differential increase in intracellular Ca 2+ under different salt treatments, ratio of Ca 2+ /Na + remained the same. It is inferred that stepwise increment in the salt concentration enabled the cyanobacterium to undergo priming effect and acquire robust and efficient defense system involving the least energy.

Investigation into the dehydration of selenate doped Na2M(SO4)2·2H2O (M = Mn, Fe, Co and Ni): Stabilisation of the high Na content alluaudite phases Na3M1.5(SO4)3-1.5x(SeO4)1.5x (M = Mn, Co and Ni) through selenate incorporation

NASA Astrophysics Data System (ADS)

Driscoll, L. L.; Kendrick, E.; Knight, K. S.; Wright, A. J.; Slater, P. R.

2018-02-01

In this paper we report an investigation into the phases formed on dehydration of Na2M(SO4)2-x(SeO4)x·2H2O (0 ≤ x ≤ 1; M = Mn, Fe, Co and Ni). For the Fe series, all attempts to dehydrate the samples doped with selenate resulted in amorphous products, and it is suspected that a side redox reaction involving the Fe and selenate may be occurring leading to phase decomposition and hence the lack of a crystalline product on dehydration. For M = Mn, Co, Ni, the structure observed was shown to depend upon the transition metal cation and level of selenate doping. An alluaudite phase, Na3M1.5(SO4)3-1.5x(SeO4)1.5x, was observed for the selenate doped compositions, with this phase forming as a single phase for x ≥ 0.5 M = Co, and x = 1.0 M = Ni. For M = Mn, the alluaudite structure is obtained across the series, albeit with small impurities for lower selenate content samples. Although the alluaudite-type phases Na2+2y(Mn/Co)2-y(SO4)3 have recently been reported [1,2], doping with selenate appears to increase the maximum sodium content within the structure. Moreover, the selenate doped Ni based samples reported here are the first examples of a Ni sulfate/selenate containing system exhibiting the alluaudite structure.

Investigation into the effect on structure of oxoanion doping in Na{sub 2}M(SO{sub 4}){sub 2}·2H{sub 2}O

DOE Office of Scientific and Technical Information (OSTI.GOV)

Driscoll, L.L.; Kendrick, E.; Sharp Laboratories Europe, Oxford Science Park, Edmund Halley Road, Oxford OX4 4GB

2016-10-15

In this paper an investigation into the effect of transition metal ion and selenate/fluorophosphate doping on the structures of Na{sub 2}M(SO{sub 4}){sub 2}·2H{sub 2}O (M=transition metal) materials is reported. In agreement with previous reports, the monoclinic (Kröhnkite) structure is adopted for M=Mn, Fe, Co, Cu, while for the smallest first row divalent transition metal ion, M=Ni, the triclinic (Fairfieldite structure) is adopted. On selenate doping there is a changeover in structure from monoclinic to triclinic for M=Fe, Co, Cu, with the larger Fe{sup 2+} system requiring the highest level of selenate to complete the changeover. Thus the results suggest thatmore » the relative stability of the two structure types is influenced by the relative size of the transition metal: oxoanion group, with the triclinic structure favoured for small transition metals/large oxoanions. The successful synthesis of fluorophosphate doped samples, Na{sub 2}M(SO{sub 4}){sub 2−x}(PO{sub 3}F){sub x}·2H{sub 2}O was also obtained for M=Fe, Co, Cu, with the results showing a changeover in structure from monoclinic to triclinic for M=Co, Cu for very low levels (x=0.1) of fluorophosphate. In the case of M=Fe, the successful synthesis of fluorophosphates samples was achieved for x≤0.3, although no change in cell symmetry was observed. Rather in this particular case, the X-ray diffraction patterns showed evidence for selective peak broadening, attributed to local disorder as a result of the fluorophosphate group disrupting the H-bonding network. Overall the work highlights how isovalent doping can be exploited to alter the structures of Na{sub 2}M(SO{sub 4}){sub 2}·2H{sub 2}O systems. - Graphical abstract: Partial substitution of sulfate in Na{sub 2}M(SO{sub 4}){sub 2}0.2H{sub 2}O (M=Co, Cu) by selenate or fluorophosphate leads to a structural change from the monoclinic Kröhnkite to the triclinic Fairfieldite structure. - Highlights: • The successful synthesis of Na{sub 2}M(SO

Densities and apparent molar volumes of atmospherically important electrolyte solutions. 2. The systems H(+)-HSO4(-)-SO4(2-)-H2O from 0 to 3 mol kg(-1) as a function of temperature and H(+)-NH4(+)-HSO4(-)-SO4)2-)-H2O from 0 to 6 mol kg(-1) at 25 °C using a Pitzer ion interaction model, and NH4HSO4-H2O and (NH4)3H(SO4)2-H2O over the entire concentration range.

PubMed

Clegg, S L; Wexler, A S

2011-04-21

A Pitzer ion interaction model has been applied to the systems H(2)SO(4)-H(2)O (0-3 mol kg(-1), 0-55 °C) and H(2)SO(4)-(NH(4))(2)SO(4)-H(2)O (0-6 mol kg(-1), 25 °C) for the calculation of apparent molar volume and density. The dissociation reaction HSO(4)(-)((aq)) ↔ H(+)((aq)) + SO(4)(2-)((aq)) is treated explicitly. Apparent molar volumes of the SO(4)(2-) ion at infinite dilution were obtained from part 1 of this work, (1) and the value for the bisulfate ion was determined in this study from 0 to 55 °C. In dilute solutions of both systems, the change in the degree of dissociation of the HSO(4)(-) ion with concentration results in much larger variations of the apparent molar volumes of the solutes than for conventional strong (fully dissociated) electrolytes. Densities and apparent molar volumes are tabulated. Apparent molar volumes calculated using the model are combined with other data for the solutes NH(4)HSO(4) and (NH(4))(3)H(SO(4))(2) at 25 °C to obtain apparent molar volumes and densities over the entire concentration range (including solutions supersaturated with respect to the salts).

Crystal structures of NiSO4·9H2O and NiSO4·8H2O: magnetic properties, stability with respect to morenosite (NiSO4·7H2O), the solid-solution series (Mg x Ni1-x )SO4·9H2O

NASA Astrophysics Data System (ADS)

Fortes, A. D.; Knight, K. S.; Gibbs, A. S.; Wood, I. G.

2018-02-01

Since being discovered initially in mixed-cation systems, a method of forming end-member NiSO4·9H2O and NiSO4·8H2O has been found. We have obtained powder diffraction data from protonated analogues (with X-rays) and deuterated analogues (using neutrons) of these compounds over a range of temperatures, allowing us to determine their crystal structures—including all H-atoms—and to characterise the transitions on warming from 220 to 278 K; glass → 9-hydrate → 8-hydrate + ice → 7-hydrate + ice → partial melt (7-hydrate + liquid). NiSO4·8D2O is triclinic, space-group P\\bar {1} , Z = 2, with unit cell parameters at 150 K, a = 6.12463(8) Å, b = 6.8401(1) Å, c = 12.5339(2) Å, α = 92.846(1)°, β = 97.822(1)°, γ = 96.627(1)° and V = 515.58(1) Å3. The structure consists of two symmetry-inequivalent Ni(D2O)6 octahedra on sites of \\bar {1} symmetry. These are directly joined by a water-water H-bond to form chains of octahedra parallel with the c-axis at x = 0. Two interstitial water molecules serve both to bridge the Ni(D2O)6 octahedral chains in the b-c plane and also to connect with the SO4 2- tetrahedral oxyanion. These tetrahedra are linked by the two interstitial water molecules in a reticular motif to form sheets perpendicular to c. NiSO4·9D2O is monoclinic, space-group P21/c, Z = 4, with unit-cell parameters at 150 K, a = 6.69739(6) Å, b = 11.8628(1) Å, c = 14.5667(1) Å, β = 94.9739(8)° and V = 1152.96(1) Å3. The structure is isotypic with the Mg analogue described elsewhere (Fortes et al., Acta Cryst B 73:47‒64, 2017b). It shares the motif of H-bonded octahedral chains with NiSO4·8D2O, although in the enneahydrate these run parallel with the b-axis at x = 0. Three interstitial water molecules bridge the Ni(D2O)6 octahedra to the SO4 2- tetrahedral oxyanion. The tetrahedra sit at x ≈ 0.5 and are linked by two of the three interstitial water molecules in a pentagonal motif to form ribbons parallel with b. A solid-solution series

The effectiveness of sodium hydroxide (NaOH) and sodium carbonate (Na2CO3) on the impurities removal of saturated salt solution

NASA Astrophysics Data System (ADS)

Pujiastuti, C.; Ngatilah, Y.; Sumada, K.; Muljani, S.

2018-01-01

Increasing the quality of salt can be done through various methods such as washing (hydro-extraction), re-crystallization, ion exchange methods and others. In the process of salt quality improvement by re-crystallization method where salt product diluted with water to form saturated solution and re-crystallized through heating process. The quality of the salt produced is influenced by the quality of the dissolved salt and the crystallization mechanism applied. In this research is proposed a concept that before the saturated salt solution is recrystallized added a chemical for removal of the impurities such as magnesium ion (Mg), calcium (Ca), potassium (K) and sulfate (SO4) is contained in a saturated salt solution. The chemical reagents that used are sodium hydroxide (NaOH) 2 N and sodium carbonate (Na2CO3) 2 N. This research aims to study effectiveness of sodium hydroxide and sodium carbonate on the impurities removal of magnesium (Mg), calcium (Ca), potassium (K) and sulfate (SO4). The results showed that the addition of sodium hydroxide solution can be decreased the impurity ions of magnesium (Mg) 95.2%, calcium ion (Ca) 45%, while the addition of sodium carbonate solution can decreased magnesium ion (Mg) 66.67% and calcium ion (Ca) 77.5%, but both types of materials are not degradable sulfate ions (SO4). The sodium hydroxide solution more effective to decrease magnesium ion than sodium carbonate solution, and the sodium carbonate solution more effective to decrease calcium ion than sodium hydroxide solution.

K3Na(SO4)2 : Eu nanoparticles for high dose of ionizing radiation

NASA Astrophysics Data System (ADS)

Sahare, P. D.; Ranjan, Ranju; Salah, Numan; Lochab, S. P.

2007-02-01

K3Na(SO4)2 : Eu nanocrystalline powder was synthesized by the chemical co-precipitation method. The x-ray diffraction pattern of the nanomaterials shows a hexagonal structure for its crystals having grain size of ~28 nm. Transmission electron microscopy revealed that the K3Na(SO4)2 : Eu nanoparticles are single crystals with almost a uniform shape and size. Thermoluminescence (TL) was taken after irradiating the samples at various exposures of γ-rays from a 60Co source. A prominent TL glow peak is observed at 423 K along with three small peaks/shoulders at around 382, 460 and 509 K. The observed TL sensitivity of the prepared nanocrystalline powder is around 4 times more than that of LiF : Mg,Ti (TLD-100) phosphor. The 423 K peak of the nanomaterial phosphor eventually shows a near linear response with exposures increasing up to very high values (as high as 70 kGy), where all the other TLD phosphors saturate. This property along with its other desired properties such as high sensitivity, relatively simple glow curve structure and low fading makes the nanocrystalline phosphor a suitable dosimeter to estimate low as well as high exposures of γ-rays. TL analysis using the glow curve deconvolution technique was also done for determining different trapping parameters.

(NH4)2SO4 heterogeneous nucleation and glycerol evaporation of (NH4)2SO4-glycerol system in its dynamic efflorescence process

NASA Astrophysics Data System (ADS)

Cai, Chen; Luan, Ye-mei; Shi, Xiao-min; Zhang, Yun-hong

2017-02-01

Using the FTIR-ATR technique, we investigated the heterogeneous nucleation process of aqueous (NH4)2SO4 binary droplets and (NH4)2SO4/glycerol ternary droplets. From the red shift of δ-NH4+ with a linearly declining relative humidity (RH), the ERHs of pure (NH4)2SO4 droplets and mixed (NH4)2SO4/glycerol droplets with different organic-inorganic ratio (OIR) of 1:4, 1:2 and 1:1 ranges from ∼51.9 to ∼34.9%, ∼49.8 to ∼33.0%, ∼48.0 to ∼30.6% and ∼43.7 to ∼25.2%, respectively. From the changing absorbance of δ-NH4+ band, we determined the heterogeneous nucleation rates of crystalline (NH4)2SO4 in the pure and mixed droplets. The interfacial tension between an (NH4)2SO4 critical nucleus and surrounding (NH4)2SO4 solution was determined using classical nucleation theory and experimental data to be 0.031 ± 0.002 J m-2. Evaporation of glycerol in (NH4)2SO4/glycerol ternary droplets are also studied to be restrained by participation of (NH4)2SO4. Determined vapour pressure of glycerol is on the same magnitude with results from previous studies.

A thermodynamic model for the prediction of phase equilibria and speciation in the H 2O-CO 2-NaCl-CaCO 3-CaSO 4 system from 0 to 250 °C, 1 to 1000 bar with NaCl concentrations up to halite saturation

NASA Astrophysics Data System (ADS)

Li, Jun; Duan, Zhenhao

2011-08-01

A thermodynamic model is developed for the calculation of both phase and speciation equilibrium in the H 2O-CO 2-NaCl-CaCO 3-CaSO 4 system from 0 to 250 °C, and from 1 to 1000 bar with NaCl concentrations up to the saturation of halite. The vapor-liquid-solid (calcite, gypsum, anhydrite and halite) equilibrium together with the chemical equilibrium of H+,Na+,Ca, CaHCO3+,Ca(OH)+,OH-,Cl-, HCO3-,HSO4-,SO42-, CO32-,CO,CaCO and CaSO 4(aq) in the aqueous liquid phase as a function of temperature, pressure and salt concentrations can be calculated with accuracy close to the experimental results. Based on this model validated from experimental data, it can be seen that temperature, pressure and salinity all have significant effects on pH, alkalinity and speciations of aqueous solutions and on the solubility of calcite, halite, anhydrite and gypsum. The solubility of anhydrite and gypsum will decrease as temperature increases (e.g. the solubility will decrease by 90% from 360 K to 460 K). The increase of pressure may increase the solubility of sulphate minerals (e.g. gypsum solubility increases by about 20-40% from vapor pressure to 600 bar). Addition of NaCl to the solution may increase mineral solubility up to about 3 molality of NaCl, adding more NaCl beyond that may slightly decrease its solubility. Dissolved CO 2 in solution may decrease the solubility of minerals. The influence of dissolved calcite on the solubility of gypsum and anhydrite can be ignored, but dissolved gypsum or anhydrite has a big influence on the calcite solubility. Online calculation is made available on www.geochem-model.org/model.

The prediction of mineral solubilities in natural waters: A chemical equilibrium model for the Na-Ca-Cl-SO 4-H 2O system, to high temperature and concentration

NASA Astrophysics Data System (ADS)

Møller, Nancy

1988-04-01

This paper describes a chemical equilibrium model for the Na-Ca-Cl-SO 4-H 2O system which calculates solubilities from 25°C to 250°C and from zero to high concentration ( I ~ 18. m) within experimental uncertainty. The concentration and temperature dependence of the model were established by fitting available activity (solubility, osmotic and emf) data. A single ion complex, CaSO 04, which increases in strength with temperature, is included explicitly in the model. The validation of model accuracy by comparison to laboratory and field solubility data is included. Applications of the model are also given. Phase diagrams constructed for the Na-Ca-Cl-SO 4-H 2O system and predicted solubilities of anhydrite and hemihydrate in concentrated seawater at high temperature are in very good agreement with the data. Calculations of the temperature of gypsum-anhydrite coexistence as a function of water activity are compared to reported values, and are used to estimate the composition-temperature relation for gypsum-anhydrite transition in a natural brine evaporation. A preliminary model for barite solubility in sodium chloride solutions at high temperature (100°C to 250°C), based on this parameterization of the CaSO 4-NaCl-H 2O system, gives good agreement with the data.

Effect of Na poisoning catalyst (V2O5-WO3/TiO2) on denitration process and SO3 formation

NASA Astrophysics Data System (ADS)

Xiao, Haiping; Chen, Yu; Qi, Cong; Ru, Yu

2018-03-01

This paper aims to study the effect of alkali metal sodium (Na) poisoning on the performance of the Selective Catalytic Reduction (SCR) catalyst. The result showed that Na2SO4 poisoning leads to a reduced denitration rate of the SCR catalyst and an increase in the SO3 generation rate. Na2O poisoning leads to a significant reduction in the denitration rate of the SCR catalyst and marginally improves the formation of SO3. The maximum of the SO3 generation rate for a Na2SO4-poisoned catalyst reached 1.35%, whereas it was only 0.85% for the SCR catalyst. When the SO2 was contained in flue gas, the denitration rate for the Na2O-poisoned catalyst clearly increased by more than 28%. However, the effect of SO2 on the Na2SO4-poisoned catalyst was very slight. The denitration rate of the SCR catalyst decreased with an increase in the Na content. The BET and XRD results showed that Na poisoning of the catalyst decreased the number of acid sites, the reducibility of the catalyst, the surface area, and pore volume. The H2-TPR and NH3-TPD results show that Na decreases the number of acid sites and the reducibility of the catalyst. The FT-IR and XPS results showed that Na2O poisoning led to the decrease of V5+dbnd O bonds and the consumptions of oxygen atoms. Na2SO4 poisoning can improve surface adsorbed oxygen, which was beneficial for the SO2-SO3 conversion reaction.

An improved model for the calculation of CO2 solubility in aqueous solutions containing Na+, K+, Ca2+, Mg2+, Cl-, and SO42-

USGS Publications Warehouse

Duan, Zhenhao; Sun, R.; Zhu, Chen; Chou, I.-Ming

2006-01-01

An improved model is presented for the calculation of the solubility of carbon dioxide in aqueous solutions containing Na+, K+, Ca2+, Mg2+, Cl-, and SO42- in a wide temperature-pressure-ionic strength range (from 273 to 533 K, from 0 to 2000 bar, and from 0 to 4.5 molality of salts) with experimental accuracy. The improvements over the previous model [Duan, Z. and Sun, R., 2003. An improved model calculating CO2 solubility in pure water and aqueous NaCl solutions from 273 to 533K and from 0 to 2000 bar. Chemical Geology, 193: 257-271] include: (1) By developing a non-iterative equation to replace the original equation of state in the calculation of CO 2 fugacity coefficients, the new model is at least twenty times computationally faster and can be easily adapted to numerical reaction-flow simulator for such applications as CO2 sequestration and (2) By fitting to the new solubility data, the new model improved the accuracy below 288 K from 6% to about 3% of uncertainty but still retains the high accuracy of the original model above 288 K. We comprehensively evaluate all experimental CO2 solubility data. Compared with these data, this model not only reproduces all the reliable data used for the parameterization but also predicts the data that were not used in the parameterization. In order to facilitate the application to CO2 sequestration, we also predicted CO2 solubility in seawater at two-phase coexistence (vapor-liquid or liquid-liquid) and at three-phase coexistence (CO2 hydrate-liquid water-vapor CO2 [or liquid CO2]). The improved model is programmed and can be downloaded from the website http://www.geochem-model.org/programs.htm. ?? 2005 Elsevier B.V. All rights reserved.

Temperature-dependent solubility transition of Na₂SO₄ in water and the effect of NaCl therein: solution structures and salt water dynamics.

PubMed

Bharmoria, Pankaj; Gehlot, Praveen Singh; Gupta, Hariom; Kumar, Arvind

2014-11-06

Dual, aqueous solubility behavior of Na2SO4 as a function of temperatures is still a natural enigma lying unresolved in the literature. The solubility of Na2SO4 increases up to 32.38 °C and decreases slightly thereafter at higher temperatures. We have thrown light on this phenomenon by analyzing the Na2SO4-water clusters (growth and stability) detected from temperature-dependent dynamic light scattering experiments, solution compressibility changes derived from the density and speed of sound measurements, and water structural changes/Na2SO4 (ion pair)-water interactions observed from the FT-IR and 2D DOSY (1)H NMR spectroscopic investigations. It has been observed that Na2SO4-water clusters grow with an increase in Na2SO4 concentration (until the solubility transition temperature) and then start decreasing afterward. An unusual decrease in cluster size and solution compressibility has been observed with the rise in temperature for the Na2SO4 saturated solutions below the solubility transition temperature, whereas an inverse pattern is followed thereafter. DOSY experiments have indicated different types of water cluster species in saturated solutions at different temperatures with varying self-diffusion coefficients. The effect of NaCl (5-15 wt %) on the solubility behavior of Na2SO4 at different temperatures has also been examined. The studies are important from both fundamental and industrial application points of view, for example, toward the clean separation of NaCl and Na2SO4 from the effluent streams of textile and tannery industries.

Raman Spectroscopic Observations of the Ion Association between Mg(2+) and SO4(2-) in MgSO4-Saturated Droplets at Temperatures of ≤380 °C.

PubMed

Wan, Ye; Wang, Xiaolin; Hu, Wenxuan; Chou, I-Ming

2015-08-27

Liquid–liquid phase separation was observed in aqueous MgSO4 solutions with excess H2SO4 at elevated temperatures; the aqueous MgSO4/H2SO4 solutions separated into MgSO4-rich droplets (fluid F1) and a MgSO4-poor phase (fluid F2) during heating. The phase separation temperature increases with SO4(2–)/Mg2+ ratio at a constant MgSO4 concentration. At a MgSO4/H2SO4 ratio of 5, the liquid–liquid phase separation temperature decreases with an increase in MgSO4 concentration up to ∼1.0 mol/kg and then increases at higher concentrations, showing a typical macroscale property of polymer solutions with a lower critical solution temperature (LCST) of ∼271.4 °C. In situ Raman spectroscopic analyses show that the MgSO4 concentration in fluid F1 increases with an increase in temperature, whereas that in fluid F2 decreases with an increase in temperature. In addition, HSO4(–), which does not readily form complexes with Mg(2+), tends to accumulate in fluid F2. Analyses of the v1(SO4(2–)) bands confirmed the presence of four-sulfate species of unassociated SO4(2–) (∼980 cm(–1)), contact ion pairs (CIPs; ∼995 cm(–1)), and triple ion pairs (TIPs; ∼1005 cm(–1)) in aqueous solution, and more complex ion pair chain structure (∼1020 cm(–1)) in fluid F1. Comparison of the sulfate species in fluids F1 and F2 at 280 °C suggests that SO4(2–) in fluid F2 is less associated with Mg(2+). On the basis of in situ visual and Raman spectroscopic observations, we suggest that the formation of the complex Mg(2+)–SO4(2–) ion association might be responsible for the liquid–liquid phase separation. In addition, Raman spectroscopic analyses of the OH stretching bands indicate that the hydrogen bonding in fluid F1 is stronger than that in fluid F2, which might be ascribed to the increasing probability of collision of H2O with Mg(2+) and SO4(2–) in fluid F1.

Characterisation of Ba(OH){sub 2}–Na{sub 2}SO{sub 4}–blast furnace slag cement-like composites for the immobilisation of sulfate bearing nuclear wastes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mobasher, Neda; Bernal, Susan A.; Hussain, Oday H.

2014-12-15

Soluble sulfate ions in nuclear waste can have detrimental effects on cementitious wasteforms and disposal facilities based on Portland cement. As an alternative, Ba(OH){sub 2}–Na{sub 2}SO{sub 4}–blast furnace slag composites are studied for immobilisation of sulfate-bearing nuclear wastes. Calcium aluminosilicate hydrate (C–A–S–H) with some barium substitution is the main binder phase, with barium also present in the low solubility salts BaSO{sub 4} and BaCO{sub 3}, along with Ba-substituted calcium sulfoaluminate hydrates, and a hydrotalcite-type layered double hydroxide. This reaction product assemblage indicates that Ba(OH){sub 2} and Na{sub 2}SO{sub 4} act as alkaline activators and control the reaction of the slagmore » in addition to forming insoluble BaSO{sub 4}, and this restricts sulfate availability for further reaction as long as sufficient Ba(OH){sub 2} is added. An increased content of Ba(OH){sub 2} promotes a higher degree of reaction, and the formation of a highly cross-linked C–A–S–H gel. These Ba(OH){sub 2}–Na{sub 2}SO{sub 4}–blast furnace slag composite binders could be effective in the immobilisation of sulfate-bearing nuclear wastes.« less

The Scale Formation of Barite (BaSO4) from Laminar Flowing Water in The Presence of Tartaric Acid and Ba2+ Concentration Variation of Solution

NASA Astrophysics Data System (ADS)

Fatra, F.; Ivanto, G.; Dera, N. S.; Muryanto, S.; Bayuseno, A. P.

2017-05-01

The barite (BaSO4) scale is a mineral deposit that can be precipitated during the process of drilling oil and gas in the offshore. Deposite scale in pipes can cause a narrowing of the diameter of pipes, and can reduce water flowing in the pipe. The aim of this study is to investigation the effect of the tartaric acid additive and Ba2+ concentration on the growth o the scale formation of barite in the laminar flow of the piping system. Solution forming barite crystal was prepared by mixing equimolar solutions of barium chloride (BaCl2) and sodium sulfate (Na2SO4) with concentration variations of Ba2+ of 3000, 3500, 4000, 4500, and 5000 ppm. The flow rate of solution is 40 ml/min at temperature of 50 °C. Various concentrations of tartaric acid (C4H6O6) of 0 ppm, 5 ppm and 10 ppm were added to the solutions. The formation of barite from the solution was observed by ion conductivity measurement. The obtained barite crystals before and after adding tartaric acid were dried and characterized by using SEM/EDX for morphology and elemental analysis, and XRD for phase identification. The SEM results show that the morphology of the crystals are star-like particles, while XRD analysis confirmed that the barite crystals were produced during the experiments are high purity. Moreover, the tartaric acid can inhibit the crystal growth of barite.

Theoretical and experimental studies of the deposition of Na2So4 from seeded combustion gases

NASA Technical Reports Server (NTRS)

Kohl, F. J.; Santoro, G. J.; Stearns, C. A.; Fryburg, G. C.; Rosner, D. E.

1977-01-01

Flames in a Mach 0.3 atmospheric pressure laboratory burner rig were doped with sea salt, NaS04, and NaCl, respectively, in an effort to validate theoretical dew point predictions made by a local thermochemical equilibrium (LTCE) method of predicting condensation temperatures of sodium sulfate in flame environments. Deposits were collected on cylindrical platinum targets placed in the combustion products, and the deposition was studied as a function of collector temperature. Experimental deposition onset temperatures checked within experimental error with LTCE-predicted temperatures. A multicomponent mass transfer equation was developed to predict the rate of deposition of Na2SO4(c) via vapor transport at temperatures below the deposition onset temperature. Agreement between maximum deposition rates predicted by this chemically frozen boundary layer (CFBL) theory and those obtained in the seeded laboratory burner experiments is good.

Structural and impurity phase transitions of LiNaSO4:RE probed using cathodo-thermoluminescence

NASA Astrophysics Data System (ADS)

Maghrabi, M.; Finch, A. A.; Townsend, P. D.

2008-11-01

Spectrally resolved cathodo-thermoluminescence spectra of rare earth (RE) doped LiNaSO4 measured from 20 to 673 K reveal several anomalies in the RE emission lines and intensities. The low (20-300 K) temperature data show a discontinuous change in intensity at ~170 K that is either a marked intensity enhancement or a drop truncating the entire spectrum. Such an effect on the host luminescence has previously been assigned to a transition between cubic and hexagonal polymorphs of ice nanoparticle inclusions. Similar, but less profound anomalies are seen above room temperature (300-673 K) where the changes take the form of either a discontinuity in intensity at ~480 K or reduced intensity in the range 430-530 K. There are changes in the relative intensities of different emission lines of the same dopant in this temperature range. Such high temperature variations are ascribed to structural phase changes within the LiNaSO4 crystals. The behaviours may result from Li-poor surfaces or twin boundaries behaving like Na2SO4. This phase change is suggested in the open literature for LiNaSO4 but not yet fully documented, perhaps because the effects span a wide range of temperatures or due to experimental features inherent in most luminescence facilities.

An isopiestic study of aqueous NaBr and KBr at 50 °C: Chemical equilibrium model of solution behavior and solubility in the NaBr-H 2O, KBr-H 2O and Na-K-Br-H 2O systems to high concentration and temperature

NASA Astrophysics Data System (ADS)

Christov, Christomir

2007-07-01

The isopiestic method has been used to determine the osmotic coefficients of the binary solutions NaBr-H 2O (from 0.745 to 5.953 mol kg -1) and KBr-H 2O (from 0.741 to 5.683 mol kg -1) at the temperature t = 50 °C. Sodium chloride solutions have been used as isopiestic reference standards. The isopiestic results obtained have been combined with all other experimental thermodynamic quantities available in literature (osmotic coefficients, water activities, bromide mineral's solubilities) to construct a chemical model that calculates solute and solvent activities and solid-liquid equilibria in the NaBr-H 2O, KBr-H 2O and Na-K-Br-H 2O systems from dilute to high solution concentration within the 0-300 °C temperature range. The Harvie and Weare [Harvie C., and Weare J. (1980) The prediction of mineral solubilities in naturalwaters: the Na-K-Mg-Ca-Cl-SO 4-H 2O system from zero to high concentration at 25 °C. Geochim. Cosmochim. Acta44, 981-997] solubility modeling approach, incorporating their implementation of the concentration-dependent specific interaction equations of Pitzer [Pitzer K. (1973) Thermodynamics of electrolytes. I. Theoretical basis and general equations. J. Phys. Chem.77, 268-277] is employed. The model for binary systems is validated by comparing activity coefficient predictions with those given in literature, and not used in the parameterization process. Limitations of the mixed solutions model due to data insufficiencies are discussed. This model expands the variable temperature sodium-potassium model of Greenberg and Moller [Greenberg J., and Moller N. (1989) The prediction of mineral solubilities in natural waters: a chemical equilibrium model for the Na-K-Ca-Cl-SO 4-H 2O system to high concentration from 0 to 250 °C. Geochim. Cosmochim. Acta53, 2503-2518] by evaluating Br - pure electrolyte and mixing solution parameters and the chemical potentials of three bromide solid phases: NaBr-2H 2O (cr), NaBr (cr) and KBr (cr).

RNA adducts with Na 2SeO 4 and Na 2SeO 3 - Stability and structural features

NASA Astrophysics Data System (ADS)

Nafisi, Shohreh; Manouchehri, Firouzeh; Montazeri, Maryam

2011-12-01

Selenium compounds are widely available in dietary supplements and have been extensively studied for their antioxidant and anticancer properties. Low blood Se levels were found to be associated with an increased incidence and mortality from various types of cancers. Although many in vivo and clinical trials have been conducted using these compounds, their biochemical and chemical mechanisms of efficacy are the focus of much current research. This study was designed to examine the interaction of Na 2SeO 4 and Na 2SeO 3 with RNA in aqueous solution at physiological conditions, using a constant RNA concentration (6.25 mM) and various sodium selenate and sodium selenite/polynucleotide (phosphate) ratios of 1/80, 1/40, 1/20, 1/10, 1/5, 1/2 and 1/1. Fourier transform infrared, UV-Visible spectroscopic methods were used to determine the drug binding modes, the binding constants, and the stability of Na 2SeO 4 and Na 2SeO 3-RNA complexes in aqueous solution. Spectroscopic evidence showed that Na 2SeO 4 and Na 2SeO 3 bind to the major and minor grooves of RNA ( via G, A and U bases) with some degree of the Se-phosphate (PO 2) interaction for both compounds with overall binding constants of K(Na 2SeO 4-RNA) = 8.34 × 10 3 and K(Na 2SeO 3-RNA) = 4.57 × 10 3 M -1. The order of selenium salts-biopolymer stability was Na 2SeO 4-RNA > Na 2SeO 3-RNA. RNA aggregations occurred at higher selenium concentrations. No biopolymer conformational changes were observed upon Na 2SeO 4 and Na 2SeO 3 interactions, while RNA remains in the A-family structure.

Carbonate mineral solubility at low temperatures in the Na-K-Mg-Ca-H-Cl-SO 4-OH-HCO 3-CO 3-CO 2-H 2O system

NASA Astrophysics Data System (ADS)

Marion, Giles M.

2001-06-01

Carbonate minerals have played an important role in the geochemical evolution of Earth, and may have also played an important role in the geochemical evolution of Mars and Europa. Several models have been published in recent years that describe chloride and sulfate mineral solubilities in concentrated brines using the Pitzer equations. Few of these models are parameterized for subzero temperatures, and those that are do not include carbonate chemistry. The objectives of this work are to estimate Pitzer-equation bicarbonate-carbonate parameters and carbonate mineral solubility products and to incorporate them into the FREZCHEM model to predict carbonate mineral solubilities in the Na-K-Mg-Ca-H-Cl-SO 4-OH-HCO 3-CO 3-CO 2-H 2O system at low temperatures (≤25°C) with a special focus on subzero temperatures. Most of the Pitzer-equation parameters and equilibrium constants are taken from the literature and extrapolated into the subzero temperature range. Solubility products for 14 sodium, potassium, magnesium, and calcium bicarbonate and carbonate minerals are included in the model. Most of the experimental data are at temperatures ≥ -8°C; only for the NaHCO 3-NaCl-H 2O and Na 2CO 3-NaCl-H 2O systems are there bicarbonate and carbonate data to temperatures as low as -21.6°C. In general, the fit of the model to the experimental data is good. For example, calculated eutectic temperatures and compositions for NaHCO 3, Na 2CO 3, and their mixtures with NaCl and Na 2SO 4 salts are in good agreement with experimental data to temperatures as low as -21.6°C. Application of the model to eight saline, alkaline carbonate waters give predicted pHs ranging from 9.2 to 10.2, in comparison with measured pHs that range from 8.7 to 10.2. The model suggests that the CaCO 3 mineral that precipitates during seawater freezing is probably calcite and not ikaite. The model demonstrates that a proposed salt assemblage for the icy surface of Europa consisting of highly hydrated MgSO 4

The relative viscosity of NaNO 3 and NaNO 2 aqueous solutions

DOE PAGES

Reynolds, Jacob G.; Mauss, Billie M.; Daniel, Richard C.

2018-05-09

In aqueous solution, both nitrate and nitrite are planar, monovalent, and have the same elements but different sizes and charge densities. Comparing the viscosity of NaNO 2 and NaNO 3 aqueous solutions provides an opportunity to determine the relative importance of anion size versus strength of anion interaction with water. The viscosity of aqueous NaNO 2 and NaNO 3 were measured over a temperature and concentration range relevant to nuclear waste processing. The viscosity of NaNO 2 solutions was consistently larger than NaNO 3 under all conditions, even though nitrate is larger than nitrite. This was interpreted in terms ofmore » quantum mechanical charge field molecular dynamics calculations that indicate that nitrite forms more and stronger hydrogen bonds with water per oxygen atom than nitrate. Furthermore, these hydrogen bonds inhibit rotational motion required for fluid flow, thus increasing the nitrite solution viscosity relative to that of an equivalent nitrate solution.« less

The relative viscosity of NaNO 3 and NaNO 2 aqueous solutions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reynolds, Jacob G.; Mauss, Billie M.; Daniel, Richard C.

In aqueous solution, both nitrate and nitrite are planar, monovalent, and have the same elements but different sizes and charge densities. Comparing the viscosity of NaNO 2 and NaNO 3 aqueous solutions provides an opportunity to determine the relative importance of anion size versus strength of anion interaction with water. The viscosity of aqueous NaNO 2 and NaNO 3 were measured over a temperature and concentration range relevant to nuclear waste processing. The viscosity of NaNO 2 solutions was consistently larger than NaNO 3 under all conditions, even though nitrate is larger than nitrite. This was interpreted in terms ofmore » quantum mechanical charge field molecular dynamics calculations that indicate that nitrite forms more and stronger hydrogen bonds with water per oxygen atom than nitrate. Furthermore, these hydrogen bonds inhibit rotational motion required for fluid flow, thus increasing the nitrite solution viscosity relative to that of an equivalent nitrate solution.« less

A comparison of amorphous calcium carbonate crystallization in aqueous solutions of MgCl2 and MgSO4: implications for paleo-ocean chemistry

NASA Astrophysics Data System (ADS)

Han, Mei; Zhao, Yanyang; Zhao, Hui; Han, Zuozhen; Yan, Huaxiao; Sun, Bin; Meng, Ruirui; Zhuang, Dingxiang; Li, Dan; Liu, Binwei

2018-04-01

Based on the terminology of "aragonite seas" and "calcite seas", whether different Mg sources could affect the mineralogy of carbonate sediments at the same Mg/Ca ratio was explored, which was expected to provide a qualitative assessment of the chemistry of the paleo-ocean. In this work, amorphous calcium carbonate (ACC) was prepared by direct precipitation in anhydrous ethanol and used as a precursor to study crystallization processes in MgSO4 and MgCl2 solutions having different concentrations at 60 °C (reaction times 240 and 2880 min). Based on the morphology of the aragonite crystals, as well as mineral saturation indices and kinetic analysis of geochemical processes, it was found that these crystals formed with a spherulitic texture in 4 steps. First, ACC crystallized into columnar Mg calcite by nearly oriented attachment. Second, the Mg calcite changed from columnar shapes into smooth dumbbell forms. Third, the Mg calcite transformed into rough dumbbell or cauliflower-shaped aragonite forms by local dissolution and precipitation. Finally, the aragonite transformed further into spherulitic radial and irregular aggregate forms. The increase in Ca2+ in the MgSO4 solutions compared with the MgCl2 solutions indicates the fast dissolution and slow precipitation of ACC in the former solutions. The phase transition was more complete in the 0.005 M MgCl2 solution, whereas Mg calcite crystallized from the 0.005 M MgSO4 solution, indicating that Mg calcite could be formed more easily in an MgSO4 solution. Based on these findings, aragonite and Mg calcite relative to ACC could be used to provide a qualitative assessment of the chemistry of the paleo-ocean. Therefore, calcite seas relative to high-Mg calcite could reflect a low concentration MgSO4 paleo-ocean, while aragonite seas could be related to an MgCl2 or high concentration of MgSO4 paleo-ocean.

Ultrasonic-assisted solution combustion synthesis of porous Na3V2(PO4)3/C: formation mechanism and sodium storage performance

NASA Astrophysics Data System (ADS)

Chen, Qiuyun; Liu, Qing; Chu, Xiangcheng; Zhang, Yiling; Yan, Youwei; Xue, Lihong; Zhang, Wuxing

2017-04-01

Solution combustion synthesis (SCS) is an effective and rapid method for synthesizing nanocrystalline materials. However, the control over size, morphology, and microstructure are rather limited in SCS. Here, we develop a novel ultrasonic-assisted solution combustion route to synthesize the porous and nano-sized Na3V2(PO4)3/C composites, and reveal the effects of ultrasound on the structural evolution of NVP/C. Due to the cavitation effects generated from ultrasonic irradiation, the ultrasonic-assisted SCS can produce honeycomb precursor, which can be further transformed into porous Na3V2(PO4)3/C with reticular and hollow structures after thermal treatment. When used as cathode material for Na-ion batteries, the porous Na3V2(PO4)3/C delivers an initial discharge capacity of 118 mAh g-1 at 0.1 C and an initial coulombic efficiency of 85%. It can retain 93.8% of the initial capacity after 120 cycles at 0.2 C. The results demonstrate that ultrasonic-assisted SCS can be a new strategy to design crystalline nanomaterials with tunable microstructures.

Aqueous two-phase (PEG4000/Na2SO4) extraction and characterization of an acid invertase from potato tuber (Solanum tuberosum).

PubMed

Yuzugullu, Yonca; Duman, Yonca Avcı

2015-01-01

Invertases are key metabolic enzymes that catalyze irreversible hydrolysis of sucrose into fructose and glucose. Plant invertases have essential roles in carbohydrate metabolism, plant development, and stress responses. To study their isolation and purification from potato, an attractive system useful for the separation of biological molecules, an aqueous two-phase system, was used. The influence of various system parameters such as type of phase-forming salts, polyethylene glycol (PEG) molecular mass, salt, and polymer concentration was investigated to obtain the highest recovery of enzyme. The PEG4000 (12.5%, w/w)/Na2SO4(15%, w/w) system was found to be ideal for partitioning invertase into the bottom salt-rich phase. The addition of 3% MnSO4 (w/w) at pH 5.0 increased the purity by 5.11-fold with the recovered activity of 197%. The Km and Vmax on sucrose were 3.95 mM and 0.143 U mL(-1) min(-1), respectively. Our data confirmed that the PEG4000/Na2SO4 aqueous two-phase system combined with the presence of MnSO4 offers a low-cost purification of invertase from readily available potato tuber in a single step. The biochemical characteristics of temperature and pH stability for potato invertase prepared from an ATPS make the enzyme a good candidate for its potential use in many research and industrial applications.

[{(Mo)Mo5O21(H2O)3(SO4)}12(VO)30(H2O)20]36-: a molecular quantum spin icosidodecahedron.

PubMed

Botar, Bogdan; Kögerler, Paul; Hill, Craig L

2005-07-07

Self-assembly of aqueous solutions of molybdate and vanadate under reducing, mildly acidic conditions results in a polyoxomolybdate-based {Mo72V30} cluster compound Na8K16(VO)(H2O)5[K10 subset{(Mo)Mo5O21(H2O)3(SO4)}12(VO)30(H2O)20].150H2O, 1, a quantum spin-based Keplerate structure.

Structural phase transitions in the Ag{sub 2}Nb{sub 4}O{sub 11}-Na{sub 2}Nb{sub 4}O{sub 11} solid solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Woodward, David I., E-mail: d.i.woodward@warwick.ac.uk; Lees, Martin R.; Thomas, Pam A.

2012-08-15

The phase transitions between various structural modifications of the natrotantite-structured system xAg{sub 2}Nb{sub 4}O{sub 11}-(1-x)Na{sub 2}Nb{sub 4}O{sub 11} have been investigated and a phase diagram constructed as a function of temperature and composition. This shows three separate phase transition types: (1) paraelectric-ferroelectric, (2) rhombohedral-monoclinic and (3) a phase transition within the ferroelectric rhombohedral zone between space groups R3c and R3. The parent structure for the entire series has space group R3{sup Macron }c. Compositions with x>0.75 are rhombohedral at all temperatures whereas compositions with x<0.75 are all monoclinic at room temperature and below. At x=0.75, rhombohedral and monoclinic phases coexistmore » with the phase boundary below room temperature being virtually temperature-independent. The ferroelectric phase boundary extends into the monoclinic phase field. No evidence was found for the R3-R3c phase boundary extending into the monoclinic phase field and it is concluded that a triple point is formed. - Graphical abstract: Phase diagram for xAg{sub 2}Nb{sub 4}O{sub 11}-(1-x)Na{sub 2}Nb{sub 4}O{sub 11} solid solution showing changes in crystal symmetry as a function of temperature and composition. The crystal structure is depicted. Highlights: Black-Right-Pointing-Triangle Ferroelectric, rhombohedral Ag{sub 2}Nb{sub 4}O{sub 11} in solid solution with monoclinic Na{sub 2}Nb{sub 4}O{sub 11}. Black-Right-Pointing-Triangle Three phase boundaries were studied as a function of composition and temperature. Black-Right-Pointing-Triangle Both rhombohedral and monoclinic variants exhibit ferroelectricity. The parent phase of the series has space group R3{sup Macron }c.« less

The erosion and abrasion-inhibiting effect of TiF(4) and NaF varnishes and solutions on enamel in vitro.

PubMed

Levy, Flávia Mauad; Magalhães, Ana Carolina; Gomes, Marina Franciscon; Comar, Livia Picchi; Rios, Daniela; Buzalaf, Marília Afonso Rabelo

2012-01-01

OBJECTIVE. Previous in vitro study has shown that TiF(4) varnish might reduce enamel erosion. No data regarding the effect of this experimental varnish on enamel erosion plus abrasion, however, are available so far. Thus, this in vitro study aimed to analyse the effect of TiF(4) compared with NaF varnishes and solutions, to protect against enamel erosion with or without abrasion. METHODS. Enamel specimens were pre-treated with experimental-TiF(4) (2.45% F), experimental-NaF (2.45% F), NaF-Duraphat (2.26% F), and placebo varnishes; NaF (2.26% F) and TiF(4) (2.45% F) solutions. Controls remained untreated. The erosive challenge was performed using a soft drink (pH 2.6) 4 × 90 s/day (ERO) and the toothbrushing abrasion (ERO+ABR) 2 × 10 s/day, for 5 days. Between the challenges, the specimens were exposed to artificial saliva. Enamel loss was measured profilometrically (μm). RESULTS. Kruskal-Wallis/Dunn tests showed that all fluoridated varnishes (TiF(4) -ERO:0.53 ± 0.20, ERO+ABR:0.65 ± 0.19/NaF-ERO:0.94 ± 0.18, ERO+ABR:1.74 ± 0.37/Duraphat-ERO:1.00 ± 0.37, ERO+ABR:1.72 ± 0.58) were able to significantly reduce enamel loss when compared with placebo varnish (ERO:3.45 ± 0.41/ERO+ABR:3.20 ± 0.66) (P < 0.0001). Placebo varnish, control (ERO:2.68 ± 0.53/ERO+ABR:3.01 ± 0.34), and fluoridated (NaF-ERO:2.84 ± 0.09/ERO+ABR:2.40 ± 0.21/TiF(4) -ERO:3.55 ± 0.59/ERO+ABR:4.10 ± 0.38) solutions did not significantly differ from each other. CONCLUSION. Based on the results, it can be concluded that the TiF(4) varnish seems to be a promising treatment to reduce enamel loss under mild erosive and abrasive conditions in vitro. © 2011 The Authors. International Journal of Paediatric Dentistry © 2011 BSPD, IAPD and Blackwell Publishing Ltd.

Structural, electrical conductivity and dielectric behavior of Na2SO4-LDT composite solid electrolyte.

PubMed

Iqbal, Mohd Z; Rafiuddin

2016-01-01

A series of composite materials of general molecular formula (1 - x) Na2SO4 - (x) LDT was prepared by solid state reaction method. The phase structure and functionalization of these materials were defined by X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FT-IR) respectively. Differential thermal analysis (DTA) revealed that the hump of phase transition at 250 °C has decreased while its thermal stability was enhanced. Scanning electron microscopy signifies the presence of improved rigid surfaces and interphases that are accountable for the high ionic conduction due to dispersion of LDT particles in the composite systems. Arrhenius plots of the conductance show the maximum conductivity, σ = 4.56 × 10(-4) S cm(-1) at 500 °C for the x = 0.4 composition with the lowest activation energy 0.34 eV in the temperature range of 573-773 K. The value of dielectric constant was decreased with increasing frequency and follows the usual trend.

Removal of Calcium from Scheelite Leaching Solution by Addition of CaSO4 Inoculating Crystals

NASA Astrophysics Data System (ADS)

Liu, Wenting; Li, Yongli; Zeng, Dewen; Li, Jiangtao; Zhao, Zhongwei

2018-04-01

In this work, the solubility behaviors of gypsum and anhydrite in the H2SO4-H3PO4-H2O system were investigated over the temperature range T = 30-80°C, and the results showed that the solubility of anhydrite was considerably lower than that of gypsum. On the basis of the differential solubilities of gypsum and anhydrite, a method was developed to remove calcium from the scheelite leaching solution by adding anhydrite as an inoculating crystal. The effects of the reaction time, concentration of the CaSO4 inoculating crystals, and temperature were investigated. With an addition of CaSO4 inoculating crystals at a concentration of 60 g/L, the Ca2+ concentration of the scheelite leaching solution decreased to a low level of approximately 0.76 g/L after 10 h at 70°C.

Low temperature heat capacity and thermodynamic functions of anion bearing sodalites Na 8Al 6Si 6O 24X 2 (X = SO 4, ReO 4, Cl, I)

DOE PAGES

Schliesser, Jacob; Lilova, Kristina; Pierce, Eric M.; ...

2017-06-01

Heat capacities of sulfate, perrhenate, chloride, and iodide sodalites with the ideal formula Na 8Al 6Si 6O 24X 2 (X = SO 4, ReO 4, Cl, I) were measured from 2 K to 300 K using a Quantum Design Physical Property Measurement System (PPMS). From the heat capacity data, the standard thermodynamic functions were determined. All four sodalites undergo a phase transition below room temperature for which thermodynamic parameters were determined. Additionally, the heat capacity of one of the constituent compounds (NaReO 4) was measured.

Growth morphology of epsomite (MgSO 4·7H 2O)

NASA Astrophysics Data System (ADS)

Rubbo, Marco; Aquilano, Dino; Franchini-Angela, Marinella; Sgualdino, Giulio

1985-06-01

A first approach to the study of the growth properties of epsomite (MgSO 4·7H 2O) is presented. Particular attention is payed to the growth forms and to epitaxy relations between epsomite and some known habit modifiers. The starting point of the study is the Hartman and Perdok PBC analysis. It proves to be essential for knowing the actual surface profiles. Successively the theoretical growth morphology is given taking into account: the broken-bond model of Wolff and Broder, the energies associated to the hydrogen bonds only, and finally the attachment energies calculated on the basis of the Coulomb potential. Furthermore an analysis of 2D coincidence lattices leads us to the conclusion that a 2D epitaxy of both Na 2B 4O 7·lOH 2O and/or Na 2SO 4·lOH 2O on {111} and/or ? forms of epsomite explains the effect of borax and Glauber's salt as habit modifiers.

Electrochemical Behavior Assessment of Micro- and Nano-Grained Commercial Pure Titanium in H2SO4 Solutions

NASA Astrophysics Data System (ADS)

Fattah-alhosseini, Arash; Ansari, Ali Reza; Mazaheri, Yousef; Karimi, Mohsen

2017-02-01

In this study, the electrochemical behavior of commercial pure titanium with both coarse-grained (annealed sample with the average grain size of about 45 µm) and nano-grained microstructure was compared by potentiodynamic polarization, electrochemical impedance spectroscopy (EIS), and Mott-Schottky analysis. Nano-grained Ti, which typically has a grain size of about 90 nm, is successfully made by six-cycle accumulative roll-bonding process at room temperature. Potentiodynamic polarization plots and impedance measurements revealed that as a result of grain refinement, the passive behavior of the nano-grained sample was improved compared to that of annealed pure Ti in H2SO4 solutions. Mott-Schottky analysis indicated that the passive films behaved as n-type semiconductors in H2SO4 solutions and grain refinement did not change the semiconductor type of passive films. Also, Mott-Schottky analysis showed that the donor densities decreased as the grain size of the samples reduced. Finally, all electrochemical tests showed that the electrochemical behavior of the nano-grained sample was improved compared to that of annealed pure Ti, mainly due to the formation of thicker and less defective oxide film.

Phase Changes of Monosulfoaluminate in NaCl Aqueous Solution

DOE PAGES

Yoon, Seyoon; Ha, Juyoung; Chae, Sejung Rosie; ...

2016-05-21

Monosulfoaluminate (Ca 4Al 2(SO 4)(OH) 12∙6H 2O) plays an important role in anion binding in Portland cement by exchanging its original interlayer ions (SO 4 2- and OH -) with chloride ions. In this study, scanning transmission X-ray microscope (STXM), X-ray absorption near edge structure (XANES) spectroscopy, and X-ray diffraction (XRD) were used to investigate the phase change of monosulfoaluminate due to its interaction with chloride ions. Pure monosulfoaluminate was synthesized and its powder samples were suspended in 0, 0.1, 1, 3, and 5 M NaCl solutions for seven days. At low chloride concentrations, a partial dissolution of monosulfoaluminate formedmore » ettringite, while, with increasing chloride content, the dissolution process was suppressed. As the NaCl concentration increased, the dominant mechanism of the phase change became ion exchange, resulting in direct phase transformation from monosulfoaluminate to Kuzel’s salt or Friedel’s salt. The phase assemblages of the NaCl-reacted samples were explored using thermodynamic calculations and least-square linear combination (LC) fitting of measured XANES spectra. A comprehensive description of the phase change and its dominant mechanism are discussed.« less

A Study of Electrochemical Machining of Ti-6Al-4V in NaNO3 solution

NASA Astrophysics Data System (ADS)

Li, Hansong; Gao, Chuanping; Wang, Guoqian; Qu, Ningsong; Zhu, Di

2016-10-01

The titanium alloy Ti-6Al-4V is used in many industries including aviation, automobile manufacturing, and medical equipment, because of its low density, extraordinary corrosion resistance and high specific strength. Electrochemical machining (ECM) is a non-traditional machining method that allows applications to all kinds of metallic materials in regardless of their mechanical properties. It is widely applied to the machining of Ti-6Al-4V components, which usually takes place in a multicomponent electrolyte solution. In this study, a 10% NaNO3 solution was used to make multiple holes in Ti-6Al-4V sheets by through-mask electrochemical machining (TMECM). The polarization curve and current efficiency curve of this alloy were measured to understand the electrical properties of Ti-6Al-4V in a 10% NaNO3 solution. The measurements show that in a 10% NaNO3 solution, when the current density was above 6.56 A·cm-2, the current efficiency exceeded 100%. According to polarization curve and current efficiency curve, an orthogonal TMECM experiment was conducted on Ti-6Al-4V. The experimental results suggest that with appropriate process parameters, high-quality holes can be obtained in a 10% NaNO3 solution. Using the optimized process parameters, an array of micro-holes with an aperture of 2.52 mm to 2.57 mm and maximum roundness of 9 μm were produced using TMECM.

ZrB 2-HfB 2 solid solutions as electrode materials for hydrogen reaction in acidic and basic solutions

DOE PAGES

Sitler, Steven J.; Raja, Krishnan S.; Charit, Indrajit

2016-11-09

Spark plasma sintered transition metal diborides such as HfB 2, ZrB 2 and their solid solutions were investigated as electrode materials for electrochemical hydrogen evolutions reactions (HER) in 1 M H 2SO 4 and 1 M NaOH electrolytes. HfB 2 and ZrB 2 formed complete solid solutions when mixed in 1:1, 1:4, and 4:1 ratios and they were stable in both electrolytes. The HER kinetics of the diborides were slower in the basic solution than in the acidic solutions. The Tafel slopes in 1 M H 2SO 4 were in the range of 0.15 - 0.18 V/decade except for puremore » HfB 2 which showed a Tafel slope of 0.38 V/decade. In 1 M NaOH the Tafel slopes were in the range of 0.12 - 0.27 V/decade. The composition of Hf xZr 1-xB 2 solid solutions with x = 0.2 - 0.8, influenced the exchange current densities, overpotentials and Tafel slopes of the HER. As a result, the EIS data were fitted with a porous film equivalent circuit model in order to better understand the HER behavior. In addition, modeling calculations, using density functional theory approach, were carried out to estimate the density of states and band structure of the boride solid solutions.« less

Thermodynamics of concentrated electrolyte mixtures and the prediction of mineral solubilities to high temperatures for mixtures in the system Na-K-Mg-Cl-SO 4-OH-H 2O

NASA Astrophysics Data System (ADS)

Pabalan, Roberto T.; Pitzer, Kenneth S.

1987-09-01

Mineral solubilities in binary and ternary electrolyte mixtures in the system Na-K-Mg-Cl-SO 4-OH-H 2O are calculated to high temperatures using available thermodynamic data for solids and for aqueous electrolyte solutions. Activity and osmotic coefficients are derived from the ion-interaction model of Pitzer (1973, 1979) and co-workers, the parameters of which are evaluated from experimentally determined solution properties or from solubility data in binary and ternary mixtures. Excellent to good agreement with experimental solubilities for binary and ternary mixtures indicate that the model can be successfully used to predict mineral-solution equilibria to high temperatures. Although there are currently no theoretical forms for the temperature dependencies of the various model parameters, the solubility data in ternary mixtures can be adequately represented by constant values of the mixing term θ ij and values of ψ ijk which are either constant or have a simple temperature dependence. Since no additional parameters are needed to describe the thermodynamic properties of more complex electrolyte mixtures, the calculations can be extended to equilibrium studies relevant to natural systems. Examples of predicted solubilities are given for the quaternary system NaCl-KCl-MgCl 2-H 2O.

A New Parameterization of H2SO4/H2O Aerosol Composition: Atmospheric Implications

NASA Technical Reports Server (NTRS)

Tabazadeh, Azadeh; Toon, Owen B.; Clegg, Simon L.; Hamill, Patrick

1997-01-01

Recent results from a thermodynamic model of aqueous sulfuric acid are used to derive a new parameterization for the variation of sulfuric acid aerosol composition with temperature and relative humidity. This formulation is valid for relative humidities above 1 % in the temperature range of 185 to 260 K. An expression for calculating the vapor pressure of supercooled liquid water, consistent with the sulfuric acid model, is also presented. We show that the Steele and Hamill [1981] formulation underestimates the water partial pressure over aqueous H2SOI solutions by up to 12% at low temperatures. This difference results in a corresponding underestimate of the H2SO4 concentration in the aerosol by about 6 % of the weight percent at approximately 190 K. In addition, the relation commonly used for estimating the vapor pressure of H2O over supercooled liquid water differs by up to 10 % from our derived expression. The combined error can result in a 20 % underestimation of water activity over a H2SO4 solution droplet in the stratosphere, which has implications for the parameterization of heterogeneous reaction rates in stratospheric sulfuric acid aerosols. The influence of aerosol composition on the rate of homogeneous ice nucleation from a H2SO4 solution droplet is also discussed. This parameterization can also be used for homogeneous gas phase nucleation calculations of H2SO4 solution droplets under various environmental conditions such as in aircraft exhaust or in volcanic plumes.

Carbon dioxide sequestration using NaHSO4 and NaOH: A dissolution and carbonation optimisation study.

PubMed

Sanna, Aimaro; Steel, Luc; Maroto-Valer, M Mercedes

2017-03-15

The use of NaHSO 4 to leach out Mg fromlizardite-rich serpentinite (in form of MgSO 4 ) and the carbonation of CO 2 (captured in form of Na 2 CO 3 using NaOH) to form MgCO 3 and Na 2 SO 4 was investigated. Unlike ammonium sulphate, sodium sulphate can be separated via precipitation during the recycling step avoiding energy intensive evaporation process required in NH 4 -based processes. To determine the effectiveness of the NaHSO 4 /NaOH process when applied to lizardite, the optimisation of the dissolution and carbonation steps were performed using a UK lizardite-rich serpentine. Temperature, solid/liquid ratio, particle size, concentration and molar ratio were evaluated. An optimal dissolution efficiency of 69.6% was achieved over 3 h at 100 °C using 1.4 M sodium bisulphate and 50 g/l serpentine with particle size 75-150 μm. An optimal carbonation efficiency of 95.4% was achieved over 30 min at 90 °C and 1:1 magnesium:sodium carbonate molar ratio using non-synthesised solution. The CO 2 sequestration capacity was 223.6 g carbon dioxide/kg serpentine (66.4% in terms of Mg bonded to hydromagnesite), which is comparable with those obtained using ammonium based processes. Therefore, lizardite-rich serpentinites represent a valuable resource for the NaHSO 4 /NaOH based pH swing mineralisation process. Copyright © 2016 Elsevier Ltd. All rights reserved.

Polymorphism in Bi2(SO4)3

NASA Astrophysics Data System (ADS)

Subban, Chinmayee V.; Rousse, Gwenaëlle; Courty, Matthieu; Barboux, Philippe; Tarascon, Jean-Marie

2014-12-01

A new polymorph of Bi2(SO4)3 was prepared by reaction of LiBiO2 with H2SO4 and its crystal structure was solved from X-ray powder diffraction. This new polymorph crystallizes in C2/c space group with lattice parameters a = 17.3383(3) Å, b = 6.77803(12) Å, c = 8.30978(13) Å, β = 101.4300(12)°. Bi2(SO4)3 presents a layered structure made of SO4 sulfate groups and signs of stereochemically active Bi3+ lone pairs. The new Bi2(SO4)3 absorbs water to form Bi2(H2O)2(SO4)2(OH)2 through an intermediate Bi2O(OH)2SO4 phase, and the transition is reversible when heated under vacuum.

Effect of NaF and TiF(4) varnish and solution on bovine dentin erosion plus abrasion in vitro.

PubMed

Magalhães, Ana Carolina; Levy, Flávia Mauad; Rizzante, Fábio A; Rios, Daniela; Buzalaf, Marília Afonso Rabelo

2012-03-01

This in vitro study aimed to analyze the effect of TiF(4) compared to NaF varnishes and solutions, to protect against dentin erosion associated with abrasion. Bovine dentin specimens were pre-treated with NaF-Duraphat (2.26% F), NaF/CaF(2)-Duofluorid (5.63% F), experimental-NaF (2.45% F), experimental-TiF(4) (2.45% F) and placebo varnishes; NaF (2.26% F) and TiF(4) (2.45% F) solutions. Controls remained untreated. The erosive pH cycling was performed using a soft drink (pH 2.6) 4 × 90 s/day and the toothbrushing-abrasion 2 × 10 s/day, in vitro for 5 days. Between the challenges, the specimens were exposed to artificial saliva. Dentin tissue loss was measured profilometrically (μm). ANOVA/Tukey's test showed that all fluoridated varnishes (Duraphat, 7.5 ± 1.1; Duofluorid, 6.8 ± 1.1; NaF, 7.2 ± 1.9; TiF(4), 6.5 ± 1.0) were able to significantly reduce dentin tissue loss (40.7% reduction compared to control) when compared to placebo varnish (11.2 ± 1.3), control (11.8 ± 1.7) and fluoridated (NaF, 9.9 ± 1.8; TiF(4), 10.3 ± 2.1) solutions (p < 0.0001), which in turn did not significantly differ from each other. All fluoridated varnishes, but not the solutions, had a similar performance and a good potential to reduce dentin tissue loss under mild erosive and abrasive conditions in vitro. Risk patients for erosion and abrasion, especially those with exposed dentin, should benefit from this clinical preventive measure. Further research has to confirm this promising result in the clinical situation.

Interpreting activity in H(2)O-H(2)SO(4) binary nucleation.

PubMed

Bein, Keith J; Wexler, Anthony S

2007-09-28

Sulfuric acid-water nucleation is thought to be a key atmospheric mechanism for forming new condensation nuclei. In earlier literature, measurements of sulfuric acid activity were interpreted as the total (monomer plus hydrate) concentration above solution. Due to recent reinterpretations, most literature values for H(2)SO(4) activity are thought to represent the number density of monomers. Based on this reinterpretation, the current work uses the most recent models of H(2)O-H(2)SO(4) binary nucleation along with perturbation analyses to predict a decrease in critical cluster mole fraction, increase in critical cluster diameter, and orders of magnitude decrease in nucleation rate. Nucleation rate parameterizations available in the literature, however, give opposite trends. To resolve these discrepancies, nucleation rates were calculated for both interpretations of H(2)SO(4) activity and directly compared to the available parameterizations as well as the perturbation analysis. Results were in excellent agreement with older parameterizations that assumed H(2)SO(4) activity represents the total concentration and duplicated the predicted trends from the perturbation analysis, but differed by orders of magnitude from more recent parameterizations that assume H(2)SO(4) activity represents only the monomer. Comparison with experimental measurements available in the literature revealed that the calculations of the current work assuming a(a) represents the total concentration are most frequently in agreement with observations.

Room temperature electrical properties of solution derived p-type Cu{sub 2}ZnSnS{sub 4} thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gupta, Goutam Kumar; Dixit, Ambesh, E-mail: ambesh@iitj.ac.in

2016-05-06

Electrical properties of solution processed Cu{sub 2}ZnSnS{sub 4} (CZTS) compound semiconductor thin film structures on molybdenum (Mo) coated glass substrates are investigated using Mott-Schottky and Impedance spectroscopy measurements at room temperature. These measurements are carried out in sodium sulfate (Na{sub 2}SO{sub 4}) electrolytic medium at pH ~ 9.5. The inversion/depletion/accumulation regions are clearly observed in CZTS semiconductor −Na{sub 2}SO{sub 4} electrolyte interface and measured flat band potential is ~ −0.27 V for CZTS thin film electrode. The positive slope of the depletion region confirms the intrinsic p-type characteristics of CZTS thinfilms with ~ 2.5× 10{sup 19} holes/m{sup 3}. The high frequencymore » impedance measurements showed ~ 30 Ohm electrolyte resistance for the investigated configuration.« less

Beyond Chloride Brines: Variable Metabolomic Responses in the Anaerobic Organism Yersinia intermedia MASE-LG-1 to NaCl and MgSO4 at Identical Water Activity

PubMed Central

Schwendner, Petra; Bohmeier, Maria; Rettberg, Petra; Beblo-Vranesevic, Kristina; Gaboyer, Frédéric; Moissl-Eichinger, Christine; Perras, Alexandra K.; Vannier, Pauline; Marteinsson, Viggó T.; Garcia-Descalzo, Laura; Gómez, Felipe; Malki, Moustafa; Amils, Ricardo; Westall, Frances; Riedo, Andreas; Monaghan, Euan P.; Ehrenfreund, Pascale; Cabezas, Patricia; Walter, Nicolas; Cockell, Charles

2018-01-01

Growth in sodium chloride (NaCl) is known to induce stress in non-halophilic microorganisms leading to effects on the microbial metabolism and cell structure. Microorganisms have evolved a number of adaptations, both structural and metabolic, to counteract osmotic stress. These strategies are well-understood for organisms in NaCl-rich brines such as the accumulation of certain organic solutes (known as either compatible solutes or osmolytes). Less well studied are responses to ionic environments such as sulfate-rich brines which are prevalent on Earth but can also be found on Mars. In this paper, we investigated the global metabolic response of the anaerobic bacterium Yersinia intermedia MASE-LG-1 to osmotic salt stress induced by either magnesium sulfate (MgSO4) or NaCl at the same water activity (0.975). Using a non-targeted mass spectrometry approach, the intensity of hundreds of metabolites was measured. The compatible solutes L-asparagine and sucrose were found to be increased in both MgSO4 and NaCl compared to the control sample, suggesting a similar osmotic response to different ionic environments. We were able to demonstrate that Yersinia intermedia MASE-LG-1 accumulated a range of other compatible solutes. However, we also found the global metabolic responses, especially with regard to amino acid metabolism and carbohydrate metabolism, to be salt-specific, thus, suggesting ion-specific regulation of specific metabolic pathways. PMID:29535699

Water activities of NaClO4, Ca(ClO4)2, and Mg(ClO4)2 brines from experimental heat capacities: Water activity >0.6 below 200 K

NASA Astrophysics Data System (ADS)

Toner, J. D.; Catling, D. C.

2016-05-01

Perchlorate salts found on Mars are extremely hygroscopic and form low eutectic temperature aqueous solutions, which could allow liquid water to exist on Mars despite cold and dry conditions. The formation, dynamics, and potential habitability of perchlorate salt solutions can be broadly understood in terms of water activity. Water activity controls condensation and evaporation of water vapor in brines, deliquescence and efflorescence of crystalline salts, and ice formation during freezing. Furthermore, water activity is a basic parameter defining the habitability of aqueous solutions. Despite the importance of water activity, its value in perchlorate solutions has only been measured at 298.15 K and at the freezing point of water. To address this lack of data, we have determined water activities in NaClO4, Ca(ClO4)2, and Mg(ClO4)2 solutions using experimental heat capacities measured by Differential Scanning Calorimetry. Our results include concentrations up to near-saturation and temperatures ranging from 298.15 to 178 K. We find that water activities in NaClO4 solutions increase with decreasing temperature, by as much as 0.25 aw from 298.15 to 178 K. Consequently, aw reaches ∼0.6-0.7 even for concentrations up to 15 molal NaClO4 below 200 K. In contrast, water activities in Ca(ClO4)2 and Mg(ClO4)2 solutions generally decrease with decreasing temperature. The temperature dependence of water activity indicates that low-temperature NaClO4 solutions will evaporate and deliquesce at higher relative humidity, crystallize ice at higher temperature, and potentially be more habitable for life (at least in terms of water activity) compared to solutions at 298.15 K. The opposite effects occur in Ca(ClO4)2 and Mg(ClO4)2 solutions.

Thermal decomposition of europium sulfates Eu2(SO4)3·8H2O and EuSO4

NASA Astrophysics Data System (ADS)

Denisenko, Yu. G.; Khritokhin, N. A.; Andreev, O. V.; Basova, S. A.; Sal'nikova, E. I.; Polkovnikov, A. A.

2017-11-01

Reactions of europium sulfates Eu2(SO4)3·8H2O and EuSO4 complete decomposition were studied by Simultaneous Thermal Analysis. It was revealed that one-step dehydratation of Eu2(SO4)3·8H2O crystallohydrate is accompanied by the formation of amorphous anhydrous europium sulfate Eu2(SO4)3. Crystallization of amorphous europium (III) sulfate occurs at 381.1 °C (in argon) and 391.3 °C (in air). The average enthalpy values for dehydratation reaction of Eu2(SO4)3·8H2O (ΔH° = 141.1 kJ/mol), decomposition reactions of Eu2(SO4)3 (ΔH = 463.1 kJ/mol), Eu2O2SO4 (ΔH = 378.4 kJ/mol) and EuSO4 (ΔH = 124.1 kJ/mol) were determined. The step process mechanisms of thermal decomposition of europium (III) sulfate in air and europium (II) sulfate in inert atmosphere were established and justified. The kinetic parameters of complete thermal decomposition of europium (III) sulfate octahydrate were calculated by Kissinger model. The standard enthalpies of compound formation were calculated using thermal effects and formation enthalpy data for binary compounds.

THE INTERSECTION OF STABLE AND NON-EQUILIBRIUM TETRAHEDRA IN A MUTUAL 7- COMPONENT SYSTEM OF Li, Na, Rb, T1/Br, C1, NO$sub 3$, SO$sub 4$ (in Russian)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dombrovskaya, N.S.; Khakhlova, N.V.; Alekseeva, E.A.

1961-04-21

The most stable configuration of the mixture of the 16 salts formed from Li, Na, Rb, Tl/Br, Cl, NO/sub 3/, and S0/sub 4/ con ture which however interact, resulting in a stable mixture. On the basis of exchange reactions the following equation has been derived: LiBr + NaNO/sub 3/ + RbCl + 1/2Tl/sub 2/SO/sub 4/ = 1/ 2LiSO/sub 4/ + NaCl + RbNO/sub 3/ + TlBr. In addition, several binary complexes are also formed, such as Li/sub 2/SO/sub 4/ - Rb/sub 2/SO/sub 4/, 4Li/sub 2/SO/ sub 4/ - RbSO /sub 4/, RbCl - 2Li/sub 2/SO/sub 4/ and possible others. Inmore » view of the great interest, the intersection of stable and non-equilibrium tetrahedra consisting of components of both, was experimentally studied by thermai analysis. On the basis of cooling curves the following deflection points have been observed: 453 deg C, precipitation of the first Li/sub 2/SO/sub 4/ crystals; 409 deg , coprecipitation of Li/sub 2/SO/sub 4/ and NaCl; 391 deg , coprecipitation of Li/sub 2/SO/sub 4/, NaCl snd TlBr; and finally at 107 deg , formation of the quaternary eutectic with the previously mentioned salts + RbNO/sub 3/. The microstructures of the stable and non-equilibrium phases are quite similar. (TTT)« less

Effect of a single application of TiF(4) and NaF varnishes and solutions on dentin erosion in vitro.

PubMed

Magalhães, Ana Carolina; Levy, Flávia Mauad; Rios, Daniela; Buzalaf, Marília Afonso Rabelo

2010-02-01

This in vitro study aimed to analyse the effect of a single application of TiF(4) and NaF varnishes and solutions to protect against dentin erosion. Bovine root dentin samples were pre-treated with NaF-Duraphat varnish (2.26%F, pH 4.5), NaF/CaF(2)-Duofluorid varnish (5.63%F, pH 8.0), NaF-experimental varnish (2.45%F, pH 4.5), TiF(4)-experimental varnish (2.45%F, pH 1.2), NaF solution (2.26%F, pH 4.5), TiF(4) solution (2.45%F, pH 1.2) and placebo varnish (pH 5.0, no-F varnish control). Controls remained untreated. Ten samples in each group were then subjected to an erosive demineralisation (Sprite Zero, 4x 90s/day) and remineralisation (artificial saliva, between the erosive cycles) cycling for 5 days. Dentin loss was measured profilometrically after pre-treatment and after 1, 3 and 5 days of de-remineralisation cycling. The data were statistically analysed by two-way ANOVA and Bonferroni's post hoc test (p<0.05). After pre-treatment, TiF(4) solution significantly induced surface loss (1.08+/-0.53 microm). Only Duraphat reduced the dentin loss overtime, but it did not significantly differ from placebo varnish (at 3rd and 5th days) and TiF(4) varnish (at 3rd day). Duraphat varnish seems to be the best option to partially reduce dentin erosion. However, the maintenance of the effects of this treatment after successive erosive challenges is limited. Copyright 2009 Elsevier Ltd. All rights reserved.

The role of SO{sub 4}{sup 2−} surface distribution in arsenic removal by iron oxy-hydroxides

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tresintsi, S.; Simeonidis, K., E-mail: ksime@physics.auth.gr; Department of Mechanical Engineering, University of Thessaly, 38334 Volos

2014-05-01

This study investigates the contribution of chemisorbed SO{sub 4}{sup 2−} in improving arsenic removal properties of iron oxy-hydroxides through an ion-exchange mechanism. An analytical methodology was developed for the accurate quantification of sulfate ion (SO{sub 4}{sup 2−}) distribution onto the surface and structural compartments of iron oxy-hydroxides synthesized by FeSO{sub 4} precipitation. The procedure is based on the sequential determination of SO{sub 4}{sup 2−} presence in the diffuse and Stern layers, and the structure of these materials as defined by the sulfate-rich environments during the reaction and the variation in acidity (pH 3–12). Physically sorbed SO{sub 4}{sup 2−}, extracted inmore » distilled water, and physically/chemically adsorbed ions on the oxy-hydroxide's surface leached by a 5 mM NaOH solution, were determined using ion chromatography. Total sulfate content was gravimetrically measured by precipitation as BaSO{sub 4}. To validate the suggested method, results were verified by X-ray photoelectron and Fourier-transformed infrared spectroscopy. Results showed that low precipitation pH-values favor the incorporation of sulfate ions into the structure and the inner double layer, while under alkaline conditions ions shift to the diffuse layer. - Graphical abstract: An analytical methodology for the accurate quantification of sulfate ions (SO{sub 4}{sup 2−}) distribution onto the diffuse layer, the Stern layer and the structure of iron oxy-hydroxides used as arsenic removal agents. - Highlights: • Quantification of sulfate ions presence in FeOOH surface compartments. • Preparation pH defines the distribution of sulfates. • XPS and FTIR verify the presence of SO{sub 4}{sup 2−} in the structure, the Stern layer the diffuse layer of FeOOH. • Chemically adsorbed sulfates control the arsenic removal efficiency of iron oxyhydroxides.« less

Front and Back Face Gum Yields from 2,4-D and H2SO4 Treatments on Slash Pine

Treesearch

Ralph W. Clements

1970-01-01

A 2-percent water soluble solution of 2,4-D was as effective as 50-percent H2SO4 for stimulating gum flow from slash pine in stands of natural reproduction. In the 4-year study reported here, there was no appreciable difference in gum yields for zny one year of work, for either front or back faces, and for the...

Room-temperature NaI/H2O compression icing: solute-solute interactions.

PubMed

Zeng, Qingxin; Yao, Chuang; Wang, Kai; Sun, Chang Q; Zou, Bo

2017-10-11

In situ Raman spectroscopy revealed that transiting the concentrated NaI/H 2 O solutions to an ice VI phase and then into an ice VII phase at 298 K proceeds in a way different from that activated by the solute type. Unlike the solute type that raises both the critical pressures P C1 and P C2 , for the liquid-VI, the VI-VII transition simultaneously occurs in the Hofmeister series order: I > Br > Cl > F ∼ 0; concentration increase raises the P C1 faster than the P C2 that remains almost constant at higher NaI/H 2 O molecular number ratios. Concentration increase moves the P C1 along the liquid-VI phase boundary and it finally merges with P C2 at the triple-phase junction featured at 350 K and 3.05 GPa. The highly-deformed H-O bond is less sensitive to the concentration because of the involvement of anion-anion repulsion that weakens the electric field in the hydration shells. Observations confirm that the salt solvation lengthens the O:H nonbond and softens its phonon but relaxes the H-O bond contrastingly. Compression, however, has the opposite effect from that of salt solvation. Therefore, compression recovers the polarization-deformed O:H-O bond first and then proceeds to the phase transitions. The anion-anion interaction discriminates the effect of NaI/H 2 O concentration from that of the solute type at an identical concentration on the phase transitions.

Absorption and desorption of SO2 in aqueous solutions of diamine-based molten salts.

PubMed

Lim, Seung Rok; Hwang, Junhyeok; Kim, Chang Soo; Park, Ho Seok; Cheong, Minserk; Kim, Hoon Sik; Lee, Hyunjoo

2015-05-30

SO2 absorption and desorption behaviors were investigated in aqueous solutions of diamine-derived molten salts with a tertiary amine group on the cation and a chloride anion, including butyl-(2-dimethylaminoethyl)-dimethylammonium chloride ([BTMEDA]Cl, pKb=8.2), 1-butyl-1,4-dimethylpiperazinium chloride ([BDMP]Cl, pKb=9.8), and 1-butyl-4-aza-1-azoniabicyclo[2,2,2]octane chloride ([BDABCO]Cl, pKb=11.1). The SO2 absorption and desorption performance of the molten salt were greatly affected by the basicity of the molten salt. Spectroscopic, X-ray crystallographic, and computational results for the interactions of SO2 with molten salts suggest that two types of SO2-containg species could be generated depending on the basicity of the unquaternized amino group: a dicationic species comprising two different anions, HSO3(-) and Cl(-), and a monocationic species bearing Cl(-) interacting with neutral H2SO3. Copyright © 2015 Elsevier B.V. All rights reserved.

Insight to the Thermal Decomposition and Hydrogen Desorption Behaviors of NaNH2-NaBH4 Hydrogen Storage Composite.

PubMed

Pei, Ziwei; Bai, Ying; Wang, Yue; Wu, Feng; Wu, Chuan

2017-09-20

The lightweight compound material NaNH 2 -NaBH 4 is regarded as a promising hydrogen storage composite due to the high hydrogen density. Mechanical ball milling was employed to synthesize the composite NaNH 2 -NaBH 4 (2/1 molar ratio), and the samples were investigated utilizing thermogravimetric-differential thermal analysis-mass spectroscopy (TG-DTA-MS), X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR) analyses. The full-spectrum test (range of the ratio of mass to charge: 0-200) shows that the released gaseous species contain H 2 , NH 3 , B 2 H 6 , and N 2 in the heating process from room temperature to 400 °C, and possibly the impurity gas B 6 H 12 also exists. The TG/DTA analyses show that the composite NaNH 2 -NaBH 4 (2/1 molar ratio) is conductive to generate hydrogen so that the dehydrogenation process can be finished before 400 °C. Moreover, the thermal decomposition process from 200 to 400 °C involves two-step dehydrogenation reactions: (1) Na 3 (NH 2 ) 2 BH 4 hydride decomposes into Na 3 BN 2 and H 2 (200-350 °C); (2) remaining Na 3 (NH 2 ) 2 BH 4 reacts with NaBH 4 and Na 3 BN 2 , generating Na, BN, NH 3 , N 2 , and H 2 (350-400 °C). The better mechanism understanding of the thermal decomposition pathway lays a foundation for tailoring the hydrogen storage performance of the composite complex hydrides system.

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.

[Isolation and purification of alpha-glycerophosphate oxidase in a polyethylene glycol/(NH4 )2SO4 aqueous two-phase system].

PubMed

Meng, Yao; Jin, Jiagui; Liu, Shuangfeng; Yang, Min; Zhang, Qinglian; Wan, Li; Tang, Kun

2014-02-01

Alpha-glycerophosphate oxidase (alpha-GPO) from Enterococcus casseli flavus was successfully isolated and purified by using polyethylene glycol (PEG)/(NH4)2SO4 aqueous two-phase system (ATPS). The results showed that the chosen PEG/(NH4)2SO4 ATPS could be affected by PEG molecular weight, pH, concentration of PEG and (NH4)2SO4, and inorganic salt as well as additional amount of crude enzyme. After evaluating these influencing factors, the final optimum purification strategy was formed by 16.5% (m/m) PEG2000, 13.2% (m/m) (NH4)2SO4, pH 7.5 and 30% (m/m) additive crude enzyme, respectively. The NaCl was a negative influencing factor which would lead to lower purification fold and activity recovery. These conditions eventually resulted in the activity recovery of 89% (m/m), distribution coefficient of 1.2 and purification fold of 7.0.

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.

Neutron diffraction studies of the Na-ion battery electrode materials NaCoCr{sub 2}(PO{sub 4}){sub 3}, NaNiCr{sub 2}(PO{sub 4}){sub 3}, and Na{sub 2}Ni{sub 2}Cr(PO{sub 4}){sub 3}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yahia, H. Ben; Essehli, R., E-mail: ressehli@qf.org.qa; Avdeev, M.

The new compounds NaCoCr{sub 2}(PO{sub 4}){sub 3}, NaNiCr{sub 2}(PO{sub 4}){sub 3}, and Na{sub 2}Ni{sub 2}Cr(PO{sub 4}){sub 3} were synthesized by sol-gel method and their crystal structures were determined by using neutron powder diffraction data. These compounds were characterized by galvanometric cycling and cyclic voltammetry. NaCoCr{sub 2}(PO{sub 4}){sub 3}, NaNiCr{sub 2}(PO{sub 4}){sub 3}, and Na{sub 2}Ni{sub 2}Cr(PO{sub 4}){sub 3} crystallize with a stuffed α-CrPO{sub 4}-type structure. The structure consists of a 3D-framework made of octahedra and tetrahedra that are sharing corners and/or edges generating channels along [100] and [010], in which the sodium atoms are located. Of significance, in the structuresmore » of NaNiCr{sub 2}(PO{sub 4}){sub 3}, and Na{sub 2}Ni{sub 2}Cr(PO{sub 4}){sub 3} a statistical disorder Ni{sup 2+}/Cr{sup 3+} was observed on both the 8g and 4a atomic positions, whereas in NaCoCr{sub 2}(PO{sub 4}){sub 3} the statistical disorder Co{sup 2+}/Cr{sup 3+} was only observed on the 8g atomic position. When tested as negative electrode materials, NaCoCr{sub 2}(PO{sub 4}){sub 3}, NaNiCr{sub 2}(PO{sub 4}){sub 3}, and Na{sub 2}Ni{sub 2}Cr(PO{sub 4}){sub 3} delivered specific capacities of 352, 385, and 368 mA h g{sup −1}, respectively, which attests to the electrochemical activity of sodium in these compounds. - Highlights: • NaCoCr{sub 2}(PO{sub 4}){sub 3}, NaNiCr{sub 2}(PO{sub 4}){sub 3}, and Na{sub 2}Ni{sub 2}Cr(PO{sub 4}){sub 3} were synthesized by sol-gel method. • The crystal structures were determined by using neutron powder diffraction data. • The three compounds crystallize with a stuffed α-CrPO{sub 4}-type structure. • The three compounds were tested as anodes in sodium-ion batteries. • Relatively high specific capacities were obtained for these compounds.« less

Thermal decomposition behavior of the rare-earth ammonium sulfate R{sub 2}(SO{sub 4}){sub 3}.(NH{sub 4}){sub 2}SO{sub 4}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nagai, Tsukasa; Japan Society for the Promotion of Science, 1-8 Chiyoda-ku, Tokyo 102-8472; Tamura, Shinji

2010-07-15

Rare-earth ammonium sulfate octahydrates of R{sub 2}(SO{sub 4}){sub 3}.(NH{sub 4}){sub 2}SO{sub 4}.8H{sub 2}O (R=Pr, Nd, Sm, and Eu) were synthesized by a wet process, and the stable temperature region for the anhydrous R{sub 2}(SO{sub 4}){sub 3}.(NH{sub 4}){sub 2}SO{sub 4} form was clarified by thermogravimetry/differential thermal analysis, infrared, Raman, and electrical conductivity measurements. Detailed characterization of these double salts demonstrated that the thermal stability of anhydrous R{sub 2}(SO{sub 4}){sub 3}.(NH{sub 4}){sub 2}SO{sub 4} is different between the Pr, Nd salts and the Sm, Eu salts, and the thermal decomposition behavior of these salts was quite different from the previous reports. -more » Graphical abstract: Stable temperature range of anhydrous rare-earth ammonium sulfate R{sub 2}(SO{sub 4}){sub 3}.(NH{sub 4}){sub 2}SO{sub 4} was clarified by thermogravimetry/differential thermal analysis, infrared, Raman, and electrical conductivity measurements. Since the previous reports were based only on thermal analysis, the present work has more accurately determined the exact thermal stability of rare-earth ammonium sulfate solids.« less

Simultaneous absorption of NO and SO2 into hexamminecobalt(II)/iodide solution.

PubMed

Long, Xiang-Li; Xiao, Wen-De; Yuan, Wei-kang

2005-05-01

An innovative catalyst system has been developed to simultaneously remove NO and SO2 from combustion flue gas. Such catalyst system may be introduced to the scrubbing solution using ammonia solution to accomplish sequential absorption and catalytic oxidation of both NO and SO2 in the same reactor. When the catalyst system is utilized for removing NO and SO2 from the flue gas, Co(NH3)(6)2+ ions act as the catalyst and I- as the co-catalyst. Dissolved oxygen, in equilibrium with the residual oxygen in the flue gas, is the oxidant. The overall removal process is further enhanced by UV irradiation at 365 nm. More than 95% of NO is removed at a feed concentration of 250-900 ppm, and nearly 100% of SO2 is removed at a feed concentration of 800-2500 ppm. The sulfur dioxide co-existing in the flue gas is beneficial to NO absorption into hexamminecobalt(II)/iodide solution. NO and SO2 can be converted to ammonium sulfate and ammonium nitrate that can be used as fertilizer materials. The process described here demonstrates the feasibility of removing SO2 and NO simultaneously only by retrofitting the existing wet ammonia flue-gas-desulfurization (FGD) scrubbers.

Ionic strength dependence of the oxidation of SO2 by H2O2 in sodium chloride particles

NASA Astrophysics Data System (ADS)

Ali, H. M.; Iedema, M.; Yu, X.-Y.; Cowin, J. P.

2014-06-01

The reaction of sulfur dioxide and hydrogen peroxide in the presence of deliquesced (>75% RH) sodium chloride (brine) particles was studied by utilizing a cross flow mini-reactor. The reaction kinetics were followed by observing chloride depletion in particles by computer-controlled scanning electron microscope with energy dispersive X-ray analysis, namely CCSEM/EDX. The reactions take place in concentrated mixed salt brine aerosols, for which no complete kinetic equilibrium data previously existed. We measured the Henry's law solubility of H2O2 in brine solutions to close that gap. We also calculated the reaction rate as the particle transforms continuously from concentrated NaCl brine to, eventually, a mixed NaHSO4 plus H2SO4 brine solution. The reaction rate of the SO2 oxidation by H2O2 was found to be influenced by the change in ionic strength as the particle undergoes compositional transformation, following closely the dependence of the third order rate constant on ionic strength as predicted using established rate equations. This is the first study that has measured the ionic strength dependence of sulfate formation (in non-aqueous media) from oxidation of mixed salt brine aerosols in the presence of H2O2. It also gives the first report of the dependence of the Henry's law constant of H2O2 on ionic strength.

Recombination luminescence of CaSO4:Tb3+ and CaSO4:Gd3+phosphors

NASA Astrophysics Data System (ADS)

Kudryavtseva, Irina; Lushchik, Aleksandr; Maaroos, Aarne; Azmaganbetova, Zhannur; Nurakhmetov, Turlybek; Salikhoja, Zhussupbek

2012-08-01

A comparative study of the excitation of luminescence by VUV radiation as well as of thermally and photostimulated luminescence has been carried out for CaSO4:Tb3+ and CaSO4:Gd3+ phosphors, where Na+ or F- ions are used for charge compensation. The distinction in hole processes for the phosphors with Na+ or F- compensators is determined by the differing thermal stability of the holes localized at/near Tb3+Na+ and Gd3+Na+ (up to 100-160 K) or at/near Tb3+F- V Ca and Gd3+F- V Ca centers involving also a cation vacancy (up to 400-550 K). Tunnel luminescence in the pairs of localized electrons and holes nearby Tb3+ or Gd3+ has been detected. The mechanisms of electron-hole, hole-electron and tunnel recombination luminescence as well as a subsequent released energy transfer to RE3+ ions are considered.

Electrodeposition of Fe{sub 3}O{sub 4} layer from solution of Fe{sub 2}(SO{sub 4}){sub 3} with addition ethylene glycol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dahlan, Dahyunir, E-mail: dahyunir@yahoo.com; Asrar, Allan

2016-03-11

The electrodeposition of Fe{sub 3}O{sub 4} layer from the solution Fe{sub 2}(SO{sub 4}){sub 3} with the addition of ethylene glycol on Indium Tin Oxide (ITO) substrate has been performed. The electrodeposition was carried out using a voltage of 5 volts for 120 seconds, with and without the addition of 2% wt ethylene glycol. Significant effects of temperature on the resulting the samples is observed when they are heated at 400 °C. Structural characterization using X-ray diffraction (XRD) shows that all samples produce a layer of Fe{sub 3}O{sub 4} with particle size less than 50 nanometers. The addition of ethylene glycolmore » and the heating of the sample causes a shrinkage in particle size. The scanning electron microscopy (SEM) characterization shows that Fe{sub 3}O{sub 4} layer resulting from the process of electrodeposition of Fe{sub 2}(SO{sub 4}){sub 3} without ethylene glycol, independent of whether the sample is heated or not, is uneven and buildup. Layer produced by the addition of ethylene glycol without heating produces spherical particles. On contrary, when the layer is heated the spherical particles transform to irregularly-shaped particles with smaller size.« less

Insights into water-mediated ion clustering in aqueous CaSO4 solutions: pre-nucleation cluster characteristics studied by ab initio calculations and molecular dynamics simulations.

PubMed

Li, Hui-Ji; Yan, Dan; Cai, Hou-Qin; Yi, Hai-Bo; Min, Xiao-Bo; Xia, Fei-Fei

2017-05-10

The molecular structure of growth units building crystals is a fundamental issue in the crystallization processes from aqueous solutions. In this work, a systematic investigation of pre-nucleation clusters and their hydration characteristics in aqueous CaSO 4 solutions was performed using ab initio calculations and molecular dynamics (MD) simulations. The results of ab initio calculations and MD simulations indicate that the dominant species in aqueous CaSO 4 solutions are monodentate ion-associated structures. Compared with charged ion clusters, neutral clusters are more likely to be present in an aqueous CaSO 4 solution. Neutral (CaSO 4 ) m clusters are probably the growth units involved in the pre-nucleation or crystallization processes. Meanwhile, hydration behavior around ion associated species in aqueous CaSO 4 solutions plays an important role in related phase/polymorphism selections. Upon ion clustering, the residence of some water molecules around Ca 2+ in ion-associated species is weakened while that of some bridging waters is enhanced due to dual interaction by Ca 2+ and SO 4 2- . Some phase/polymorphism selections can be achieved in aqueous CaSO 4 solutions by controlling the hydration around pre-nucleation clusters. Moreover, the association trend between calcium and sulfate is found to be relatively strong, which hints at the low solubility of calcium sulfate in water.

ATR-FTIR spectroscopy for the determination of Na4EDTA in detergent aqueous solutions.

PubMed

Suárez, Leticia; García, Roberto; Riera, Francisco A; Diez, María A

2013-10-15

Fourier transform infrared spectroscopy in the attenuated total reflectance mode (ATR-FTIR) combined with partial last square (PLS) algorithms was used to design calibration and prediction models for a wide range of tetrasodium ethylenediaminetetraacetate (Na4EDTA) concentrations (0.1 to 28% w/w) in aqueous solutions. The spectra obtained using air and water as a background medium were tested for the best fit. The PLS models designed afforded a sufficient level of precision and accuracy to allow even very small amounts of Na4EDTA to be determined. A root mean square error of nearly 0.37 for the validation set was obtained. Over a concentration range below 5% w/w, the values estimated from a combination of ATR-FTIR spectroscopy and a PLS algorithm model were similar to those obtained from an HPLC analysis of NaFeEDTA complexes and subsequent detection by UV absorbance. However, the lowest detection limit for Na4EDTA concentrations afforded by this spectroscopic/chemometric method was 0.3% w/w. The PLS model was successfully used as a rapid and simple method to quantify Na4EDTA in aqueous solutions of industrial detergents as an alternative to HPLC-UV analysis which involves time-consuming dilution and complexation processes. © 2013 Elsevier B.V. All rights reserved.

Hydrogen production by sodium borohydride in NaOH aqueous solution

NASA Astrophysics Data System (ADS)

Wang, Q.; Zhang, L. F.; Zhao, Z. G.

2018-01-01

The kinetics of hydrolysis reaction of NaBH4 in NaOH aqueous solution is studied. The influence of pH of the NaOH aqueous solution on the rate of hydrogen production and the hydrogen production efficiency are studied for the hydrolysis reaction of NaBH4. The results show that the activation energy of hydrolysis reaction of NaBH4 increased with the increase of the initial pH of NaOH aqueous solution.With the increasing of the initial pH of NaOH aqueous solution, the rate of hydrogen production and hydrogen production efficiency of NaBH4 hydrolysis decrease.

The influence of Na + and Ca 2+ ions on the SiO 2-AlPO 4 materials structure — IR and Raman studies

NASA Astrophysics Data System (ADS)

Rokita, M.; Mozgawa, W.; Handke, M.

2001-09-01

The series of samples containing 0-20 mol% of NaCaPO4 and 20-0 mol% of AlPO4, respectively, with the constant amount of SiO2 (80 mol%) have been selected. The materials were prepared using both sol-gel as well as aerosil pseudo-aqua solution method. The AlPO4·SiO2 and NaCaPO4·SiO2 (80 mol% of SiO2) samples have been prepared. IR and Raman spectra of these samples are presented. The spectra of materials from NaCaPO4-AlPO4-SiO2 system are compared to those of NaCaPO4·SiO2 and AlPO4·SiO2 sample (samples without Al3+ or Na+ and Ca2+ cations, respectively). The studies have enabled us to identify the bands arising from the internal and lattice vibrations. The slight differences between the spectra of sol-gel and aerosil pseudo-aqua solution materials are pointed out and discussed. The influence of Na+ and Ca2+ ions on the AlPO4-SiO2 materials structure is analysed.

Synthesis of cationic iridium(I) complexes of water-soluble phosphine ligands, [Ir(CO)(TPPMS){sub 3}]CF{sub 3}SO{sub 3}, [Ir(CO)(H{sub 2}O)(TPPTS){sub 2}]CF{sub 3}SO{sub 3}, and [Ir(CO){sub 2}(TPPMS){sub 3}]ClO{sub 4} (TPPMS = PPh{sub 2}(m-C{sub 6}H{sub 4}SO{sub 3}K), TPPTS = P(m-C{sub 6}H{sub 4}SO{sub 3}Na){sub 3})

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paterniti, D.P.; Francisco, L.W.; Atwood, J.D.

Several new water-soluble iridium(I) complexes were synthesized and their reactivities with small molecules (H{sub 2} or CO) in polar solvents (DMSO or H{sub 2}O) examined. Reaction of H{sub 2} with [Ir(CO)(TPPMS){sub 3}]CF{sub 3}SO{sub 3} (TPPMS = P(C{sub 6}H{sub 5}){sub 2}(m-C{sub 6}H{sub 4}SO{sub 3}K)) in DMSO or H{sub 2}O produces [cis,mer-Ir(CO)(H){sub 2}(TPPMS){sub 3}]CF{sub 3}SO{sub 3}, while the reaction of CO with [Ir(CO)(TPPMS){sub 3}]-CF{sub 3}SO{sub 3} in water yields [Ir(CO){sub 2}(TPPMS){sub 3}]CF{sub 3}SO{sub 3}. Carbonylation of [Ir(CO){sub 2}(TPPMS){sub 3}]ClO{sub 4} in DMSO produces [Ir(CO){sub 3}(TPPMS){sub 2}]ClO{sub 4} and TPPMS; no reaction is observed in H{sub 2}O. Hydrogenation of [Ir(CO){sub 2}(TPPMS){sub 3}]ClO{sub 4}more » in DMSO or H{sub 2}O yields [cis,mer-Ir(CO)(H){sub 2}(TPPMS){sub 3}]ClO{sub 4}, while reaction of H{sub 2} with an aqueous solution of [Ir(CO)(H{sub 2}O)(TPPTS){sub 2}]CF{sub 3}SO{sub 3} produces [Ir(CO)(H{sub 2}O)(H){sub 2}(TPPTS){sub 2}]CF{sub 3}SO{sub 3}. Reaction of trans-Ir(CO)ClL{sub 2} (L = TPPMS or TPPTS) with excess L in H{sub 2}O produces [Ir(CO)L{sub 3}]Cl, while no reaction occurs in DMSO, [Ir(CO){sub 3}(TPPMS){sub 2}]Cl reacts irreversibly with TPPMS in H{sub 2}O to produce [Ir(CO){sub 2}-(TPPMS){sub 3}]Cl.« less

Thermal Measurement during Electrolysis of Pd-Ni Thin-film -Cathodes in Li2SO4/H2O Solution

NASA Astrophysics Data System (ADS)

Castano, C. H.; Lipson, A. G.; S-O, Kim; Miley, G. H.

2002-03-01

Using LENR - open type calorimeters, measurements of excess heat production were carried out during electrolysis in Li_2SO_4/H_2O solution with a Pt-anode and Pd-Ni thin film cathodes (2000-8000 Åthick) sputtered on the different dielectric substrates. In order to accurately evaluate actual performance during electrolysis runs in the open-type calorimeter used, considering effects of heat convection, bubbling and possible H_2+O2 recombination, smooth Pt sheets were used as cathodes. Pt provides a reference since it does not produce excess heat in the light water electrolyte. To increase the accuracy of measurements the water dissociation potential was determined for each cathode taking into account its individual over-voltage value. It is found that this design for the Pd-Ni cathodes resulted in the excess heat production of ~ 20-25 % of input power, equivalent to ~300 mW. In cases of the Pd/Ni- film fracture (or detachment from substrate) no excess heat was detected, providing an added reference point. These experiments plus use of optimized films will be presented.

Phosphoinnelite, Ba4Na3Ti3Si4O14(PO4,SO4)2(O,F)3, a new mineral species from peralkaline pegmatite of the Kovdor pluton, Kola Peninsula

NASA Astrophysics Data System (ADS)

Pekov, I. V.; Chukanov, N. V.; Kulikova, I. M.; Belakovsky, D. I.

2007-12-01

Phosphoinnelite, an analogue of innelite with P > S, has been found in a peralkaline pegmatite vein crosscutting calcite carbonatite at the phlogopite deposit, Kovdor pluton, Kola Peninsula. Cancrinite (partly replaced with thomsonite-Ca), orthoclase, aegirine-augite, pectolite, magnesioarfvedsonite, golyshevite, and fluorapatite are associated minerals. Phosphoinnelite occurs as lath-shaped crystals up to 0.2 × 1 × 6 mm in size, which are combined typically in bunch-, sheaf-, and rosettelike segregations. The color is yellow-brown, with vitreous luster on crystal faces and greasy luster on broken surfaces. The mineral is transparent. The streak is pale yellowish. Phosphoinnelite is brittle, with perfect cleavage parallel to the {010} and good cleavage parallel to the {100}; the fracture is stepped. The Mohs hardness is 4.5 to 5. Density is 3.82 g/cm3 (meas.) and 3.92 g/cm3 (calc.). Phosphoinnelite is biaxial (+), α = 1.730, β = 1.745, and γ = 1.764, 2V (meas.) is close to 90°. Optical orientation is Z^c ˜ 5°. Chemical composition determined by electron microprobe is as follows (wt %): 6.06 Na2O, 0.04 K2O, 0.15 CaO, 0.99 SrO, 41.60 BaO, 0.64 MgO, 1.07 MnO, 1.55 Fe2O3, 0.27 Al2O3, 17.83 SiO2, 16.88 TiO2, 0.74 Nb2O5, 5.93 P2O5, 5.29 SO3, 0.14 F, -O=F2 = -0.06, total is 99.12. The empirical formula calculated on the basis of (Si,Al)4O14 is (Ba3.59Sr0.13K0.01)Σ3.73(Na2.59Mg0.21Ca0.04)Σ3.04(Ti2.80Fe{0.26/3+}Nb0.07)Σ3.13[(Si3.93Al0.07)Σ4O14(P1.11S0.87)Σ1.98O7.96](O2.975F0.10)Σ3.075. The simplified formula is Ba4Na3Ti3Si4O14(PO4,SO4)2(O,F)3. The mineral is triclinic, space group P overline 1 or P1. The unit cell dimensions are a = 5.38, b = 7.10, c = 14.76 Å; α = 99.00°, β = 94.94°, γ = 90.14°; and V = 555 Å3, Z = 1. The strongest lines of the X-ray powder pattern [ d, Å in ( I)( hkl)] are: 14.5(100)(001), 3.455(40)(103), 3.382(35)(0overline 2 2), 2.921(35)(005), 2.810(40)(1overline 1 4), 2.683(90)(200, overline 2 01), 2.133(80)(overline 2 overline

Osmolality- and Na+ -dependent effects of hyperosmotic NaCl solution on contractile activity and Ca2+ cycling in rat ventricular myocytes.

PubMed

Ricardo, Rafael A; Bassani, Rosana A; Bassani, José W M

2008-01-01

Hypertonic NaCl solutions have been used for small-volume resuscitation from hypovolemic shock. We sought to identify osmolality- and Na(+)-dependent components of the effects of the hyperosmotic NaCl solution (85 mOsm/kg increment) on contraction and cytosolic Ca(2+) concentration ([Ca(2+)](i)) in isolated rat ventricular myocytes. The biphasic change in contraction and Ca(2+) transient amplitude (decrease followed by recovery) was accompanied by qualitatively similar changes in sarcoplasmic reticulum (SR) Ca(2+) content and fractional release and was mimicked by isosmotic, equimolar increase in extracellular [Na(+)] ([Na(+)](o)). Raising osmolality with sucrose, however, augmented systolic [Ca(2+)](i) monotonically without change in SR parameters and markedly decreased contraction amplitude and diastolic cell length. Functional SR inhibition with thapsigargin abolished hyperosmolality effects on [Ca(2+)](i). After 15-min perfusion, both hyperosmotic solutions slowed mechanical relaxation during twitches and [Ca(2+)](i) decline during caffeine-evoked transients, raised diastolic and systolic [Ca(2+)](i), and depressed systolic contractile activity. These effects were greater with sucrose solution, and were not observed after isosmotic [Na(+)](o) increase. We conclude that under the present experimental conditions, transmembrane Na(+) redistribution apparently plays an important role in determining changes in SR Ca(2+) mobilization, which markedly affect contractile response to hyperosmotic NaCl solutions and attenuate the osmotically induced depression of contractile activity.

Electrochemical Behavior of Al-B4C Metal Matrix Composites in NaCl Solution

PubMed Central

Han, Yu-Mei; Chen, X.-Grant

2015-01-01

Aluminum based metal matrix composites (MMCs) have received considerable attention in the automotive, aerospace and nuclear industries. One of the main challenges using Al-based MMCs is the influence of the reinforcement particles on the corrosion resistance. In the present study, the corrosion behavior of Al-B4C MMCs in a 3.5 wt.% NaCl solution were investigated using potentiodynamic polarization (PDP) and electrochemical impedance spectroscopy (EIS) techniques. Results indicated that the corrosion resistance of the composites decreased when increasing the B4C volume fraction. Al-B4C composite was susceptible to pitting corrosion and two types of pits were observed on the composite surface. The corrosion mechanism of the composite in the NaCl solution was primarily controlled by oxygen diffusion in the solution. In addition, the galvanic couples that formed between Al matrix and B4C particles could also be responsible for the lower corrosion resistance of the composites. PMID:28793574

Cyclic oxidation behavior of some plasma-sprayed coatings in Na2SO4-60%V2O5 environment

NASA Astrophysics Data System (ADS)

Singh, Harpreet; Prakash, Satya; Puri, Devendra; Phase, D. M.

2006-12-01

Cyclic oxidation behavior of plasma-sprayed NiCrAlY, Ni-20Cr, Ni3Al, and Stellite-6 coatings was investigated in an aggressive environment of Na2SO4-60%V2O5 by thermogravimetric techniques for 50 cycles. These coatings were deposited on a Ni-base superalloy, namely Superni 600; 10Fe-15.5Cr-0.5Mn-0.2C-Bal Ni (wt.%). X-ray diffraction, scanning electron microscopy/energy dispersive x-ray (SEM/EDX), and electron probe microanalyzer (EPMA) techniques were used to analyze the oxidation products. The uncoated superalloy suffered accelerated oxidation in the form of intense spallation of its oxide scale. After deposition of the NiCrAlY coating, the superalloy showed a minimum mass gain, whereas after application of the Stellite-6 coating, a maximum mass gain was observed among the coatings studied. All of the coatings were found to be useful in reducing the spallation of the substrate superalloy. Moreover, the coatings were successful in maintaining continuous surface contact with the base superalloy during the cyclic oxidation. The phases revealed for the oxidized coatings were mainly the oxides of chromium and/or aluminum and the spinels containing nickel-chromium/cobalt-chromium/nickel-aluminum mixed oxides, which are reported to be protective against high-temperature oxidation/hot corrosion.

Mineral solubilities in the Na-K-Mg-Ca-Cl-SO 4-H 2O system: a re-evaluation of the sulfate chemistry in the Spencer-Møller-Weare model

NASA Astrophysics Data System (ADS)

Marion, Giles M.; Farren, Ronald E.

1999-05-01

The Spencer-Møller-Weare (SMW) (1990) model is parameterized for the Na-K-Mg-Ca-Cl-SO 4-H 2O system over the temperature range from -60° to 25°C. This model is one of the few complex chemical equilibrium models for aqueous solutions parameterized for subzero temperatures. The primary focus of the SMW model parameterization and validation deals with chloride systems. There are problems with the sulfate parameterization of the SMW model, most notably with sodium sulfate and magnesium sulfate. The primary objective of this article is to re-estimate the Pitzer-equation parameters governing interactions among sodium, potassium, magnesium, and calcium with sulfate in the SMW model. A mathematical algorithm is developed to estimate 22 temperature-dependent Pitzer-equation parameters. The sodium sulfate reparameterization reduces the overall standard error (SE) from 0.393 with the SMW Pitzer-equation parameters to 0.155. Similarly, the magnesium sulfate reparameterization reduces the SE from 0.335 to 0.124. In addition to the sulfate reparameterization, five additional sulfate minerals are included in the model, which allows a more complete treatment of sulfate chemistry in the Na-K-Mg-Ca-Cl-SO 4-H 2O system. Application of the model to seawater evaporation predicts gypsum precipitation at a seawater concentration factor (SCF) of 3.37 and halite precipitation at an SCF of 10.56, which are in good agreement with previous experimental and theoretical estimates. Application of the model to seawater freezing helps explain the two pathways for seawater freezing. Along the thermodynamically stable "Gitterman pathway," calcium precipitates as gypsum and the seawater eutectic is -36.2°C. Along the metastable "Ringer-Nelson-Thompson pathway," calcium precipitates as antarcticite and the seawater eutectic is -53.8°C.

Long-term stability of FeSO4 and H2SO4 treated chromite ore processing residue (COPR): Importance of H+ and SO42.

PubMed

Wang, Xin; Zhang, Jingdong; Wang, Linling; Chen, Jing; Hou, Huijie; Yang, Jiakuan; Lu, Xiaohua

2017-01-05

In this study, the long-term stability of Cr(VI) in the FeSO 4 and H 2 SO 4 (FeSO 4 -H 2 SO 4 ) treated chromite ore processing residue (COPR) after 400 curing days and the stabilization mechanisms were investigated. FeSO 4 -H 2 SO 4 treatment significantly reduced toxicity characteristic leaching procedure (TCLP) and synthetic precipitation leaching procedure (SPLP) Cr(VI) concentrations to lower than the regulatory limit of 1.5mgL -1 (HJ/T 301-2007, China EPA) even for the samples curing 400days, achieving an outstanding long-term stability. Our independent leaching tests revealed that H + and SO 4 2- have synergistic effect on promoting the release of Cr(VI), which would make Cr(VI) easier accessed by Fe(II) during stabilization. The contributions of H + and SO 4 2- to Cr(VI) release ratio were 25%-44% and 19%-38%, respectively, as 5mol H 2 SO 4 per kg COPR was used. X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and alkaline digestion analyses were also employed to interpret the possible stabilization mechanism. Cr(VI) released from COPR solid was reduced to Cr(III) by Fe(II), and then formed stable Fe x Cr (1-x) (OH) 3 precipitate. This study provides a facile and reliable scheme for COPR stabilization, and verifies the excellent long-term stability of the FeSO 4 -H 2 SO 4 treated COPR. Copyright © 2016 Elsevier B.V. All rights reserved.

Pb4(BO3)2(SO4) and Pb2[(BO2)(OH)](SO4): New lead(II) borate-sulfate mixed-anion compounds with two types of 3D network structures

NASA Astrophysics Data System (ADS)

Ruan, Ting-Ting; Wang, Wen-Wen; Hu, Chun-Li; Xu, Xiang; Mao, Jiang-Gao

2018-04-01

Two new lead(II) borate-sulfate mixed-anion compounds, namely, Pb4(BO3)2(SO4) and Pb2[(BO2)(OH)](SO4), have been prepared by using high-temperature melt method or hydrothermal reaction. These compounds exhibit two different types of 3D structures composed of the same anionic units of BO3 triangles and SO4 tetrahedra which are interconnected by lead(II) cations. In Pb4(BO3)2(SO4), the lead(II) ions are bridged by borate anions into 3D [Pb4(BO3)2]2+ architectures with 1D tunnels of 8-member rings along the a-axis, which are filled by the sulfate anions. In Pb2[(BO2)(OH)](SO4), the lead(II) ions are interconnected by borate and sulfate anions into 2D Pb-B-O and Pb-S-O layers parallel to the ab plane, respectively, and these layers are further condensed into the 3D lead(II) borate-sulfate framework. TGA and DSC studies indicate that Pb4(BO3)2(SO4) is congruently melting with a melting point of 689 °C whereas Pb2[(BO2)(OH)](SO4) decomposes at approximately 335 °C. UV/Vis/NIR optical diffuse reflectance spectrum measurements reveal the optical band gaps of 4.03 and 4.08 eV for Pb4(BO3)2(SO4) and Pb2[(BO2)(OH)](SO4), respectively. Furthermore, the electronic structures of Pb4(BO3)2(SO4) have also been calculated.

Surface tensions of inorganic multicomponent aqueous electrolyte solutions and melts.

PubMed

Dutcher, Cari S; Wexler, Anthony S; Clegg, Simon L

2010-11-25

A semiempirical model is presented that predicts surface tensions (σ) of aqueous electrolyte solutions and their mixtures, for concentrations ranging from infinitely dilute solution to molten salt. The model requires, at most, only two temperature-dependent terms to represent surface tensions of either pure aqueous solutions, or aqueous or molten mixtures, over the entire composition range. A relationship was found for the coefficients of the equation σ = c(1) + c(2)T (where T (K) is temperature) for molten salts in terms of ion valency and radius, melting temperature, and salt molar volume. Hypothetical liquid surface tensions can thus be estimated for electrolytes for which there are no data, or which do not exist in molten form. Surface tensions of molten (single) salts, when extrapolated to normal temperatures, were found to be consistent with data for aqueous solutions. This allowed surface tensions of very concentrated, supersaturated, aqueous solutions to be estimated. The model has been applied to the following single electrolytes over the entire concentration range, using data for aqueous solutions over the temperature range 233-523 K, and extrapolated surface tensions of molten salts and pure liquid electrolytes: HCl, HNO(3), H(2)SO(4), NaCl, NaNO(3), Na(2)SO(4), NaHSO(4), Na(2)CO(3), NaHCO(3), NaOH, NH(4)Cl, NH(4)NO(3), (NH(4))(2)SO(4), NH(4)HCO(3), NH(4)OH, KCl, KNO(3), K(2)SO(4), K(2)CO(3), KHCO(3), KOH, CaCl(2), Ca(NO(3))(2), MgCl(2), Mg(NO(3))(2), and MgSO(4). The average absolute percentage error between calculated and experimental surface tensions is 0.80% (for 2389 data points). The model extrapolates smoothly to temperatures as low as 150 K. Also, the model successfully predicts surface tensions of ternary aqueous mixtures; the effect of salt-salt interactions in these calculations was explored.

Removal of Ca2+ and Zn2+ from aqueous solutions by zeolites NaP and KP.

PubMed

Yusof, Alias Mohd; Malek, Nik Ahmad Nizam Nik; Kamaruzaman, Nurul Asyikin; Adil, Muhammad

2010-01-01

Zeolites P in sodium (NaP) and potassium (KP) forms were used as adsorbents for the removal of calcium (Ca2+) and zinc (Zn2+) cations from aqueous solutions. Zeolite KP was prepared by ion exchange of K+ with Na+ which neutralizes the negative charge of the zeolite P framework structure. The ion exchange capacity of K+ on zeolite NaP was determined through the Freundlich isotherm equilibrium study. Characterization of zeolite KP was determined using infrared spectroscopy and X-ray diffraction (XRD) techniques. From the characterization, the structure of zeolite KP was found to remain stable after the ion exchange process. Zeolites KP and NaP were used for the removal of Ca and Zn from solution. The amount of Ca2+ and Zn2+ in aqueous solution before and after the adsorption by zeolites was analysed using the flame atomic absorption spectroscopy method. The removal of Ca2+ and Zn2+ followed the Freundlich isotherm rather than the Langmuir isotherm model. This result also revealed that zeolite KP adsorbs Ca2+ and Zn2+ more than zeolite NaP and proved that modification of zeolite NaP with potassium leads to an increase in the adsorption efficiency of the zeolite. Therefore, the zeolites NaP and KP can be used for water softening (Ca removal) and reducing water pollution/toxicity (Zn removal).

UV-visible light photocatalytic properties of NaYF4:(Gd, Si)/TiO2 composites

NASA Astrophysics Data System (ADS)

Mavengere, Shielah; Kim, Jung-Sik

2018-06-01

In this study, a new novel composite photocatalyst of NaYF4:(Gd, Si)/TiO2 phosphor has been synthesized by two step method of solution combustion and sol-gel. The photocatalyst powders were characterized by X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), UV-vis spectroscopy and photoluminescence (PL) spectroscopy. Raman spectroscopy confirmed the anatase TiO2 phase which remarkably increased with existence of yttrium silicate compounds between 800 cm-1 and 900 cm-1. Double-addition of Gd3+-Si4+ ions in NaYF4 host introduced sub-energy band levels with intense absorption in the ultraviolet (UV) light region. Photocatalytic activity was examined by exposing methylene blue (MB) solutions mixed with photocatalyst powders to 254 nm UV-C fluorescent lamp and 200 W visible lights. The UV and visible photocatalytic reactivity of the NaYF4:(Gd, 1% Si)/TiO2 phosphor composites showed enhanced MB degradation efficiency. The coating of NaYF4:(Gd, 1% Si) phosphor with TiO2 nanoparticles creates energy band bending at the phosphor/TiO2 interfaces. Thus, these composites exhibited enhanced absorption of UV/visible light and the separation of electron and hole pairs for efficient photocatalysis.

Thermoresponsiveness of hybrid micelles from poly(ethylene glycol)-block-poly(4-vinylpyridium) cations and SO4(2-) anions in aqueous solutions.

PubMed

Wu, Kai; Shi, Linqi; Zhang, Wangqing; An, Yingli; Zhang, Xu; Li, Zhanyong; Zhu, X X

2006-02-14

The SO4(2-)-induced micellization of poly(ethylene glycol)-block-poly(4-vinylpyridium) (PEG110-b-P(4-VPH+)35) and the thermoresponsiveness of these hybrid micelles are studied by dynamic and static light scattering. When the concentration of H2SO4 is high enough, PEG110-b-P(4-VPH+)35 forms stable hybrid micelles with an ionic core of P(4-VPH+)35/SO4(2-) and a PEG corona at 25 degrees C. The formation of the hybrid micelles is reversible. A thermodynamic equilibrium exists between the hybrid micelles and PEG110-b-P(4-VPH+)35 unimers. The shifts of the equilibrium are mainly attributed to the variation of the electrostatic energy and entropic energy of the system. Therefore, the temperature can determine the states of the equilibrium, which means that the dissociation or the formation of the hybrid micelles can be triggered by just varying the temperature.

Effects of Na2MoO4 and Na2WO4 on molybdenum and tungsten electrodes for the alkali metal thermoelectric converter (AMTEC)

NASA Technical Reports Server (NTRS)

Williams, R. M.; Wheeler, B. L.; Jeffries-Nakamura, B.; Loveland, M. E.; Bankston, C. P.

1988-01-01

The effects of adding Na2MoO4 and Na2WO4 to porous Mo and W electrodes, respectively, on the performance and impedance characteristics of the electrodes in an alkali metal thermoelectric converter (AMTEC) were investigated. It was found that corrosion of the porous electrode by Na2MoO4 or Na2WO4 to form Na2MO3O6 and WO2, respectively, and recrystallization of the Mo or W as the salt evaporates, result in major morphological changes including a loss of columnar structure and a significant increase in porosity. This effect is more pronounced in Na2MoO4/Mo electrodes, due to the lower stability of Na2MoO4.

Nanowire Na0.35MnO2 from a hydrothermal method as a cathode material for aqueous asymmetric supercapacitors

NASA Astrophysics Data System (ADS)

Zhang, B. H.; Liu, Y.; Chang, Z.; Yang, Y. Q.; Wen, Z. B.; Wu, Y. P.; Holze, R.

2014-05-01

Nanowire Na0.35MnO2 was prepared by a simple and low energy consumption hydrothermal method; its electrochemical performance as a cathode material for aqueous asymmetric supercapacitors in Na2SO4 solution was investigated. Due to the nanowire structure its capacitance (157 F g-1) is much higher than that of the rod-like Na0.95MnO2 (92 F g-1) from solid phase reaction although its sodium content is lower. When it is assembled into an asymmetric aqueous supercapacitor using activated carbon as the counter electrode and aqueous 0.5 mol L-1 Na2SO4 electrolyte solution, the nanowire Na0.35MnO2 shows an energy density of 42.6 Wh kg-1 at a power density of 129.8 W kg-1 based on the total weight of the two electrode material, higher than those for the rod-like Na0.95MnO2, with an energy density of 27.3 Wh kg-1 at a power density of 74.8 W kg-1, and that of LiMn2O4. The new material presents excellent cycling behavior even when dissolved oxygen is not removed from the electrolyte solution. The results hold great promise for practical applications of this cathode material since sodium is much cheaper than lithium and its natural resources are rich.

The crystal structure of tin sulphate, SnSO[subscript 4], and comparison with isostructural SrSO[subscript 4], PbSO[subscript 4], and BaSO[subscript 4

DOE Office of Scientific and Technical Information (OSTI.GOV)

Antao, Sytle M.

2012-10-23

The crystal structure of tin (II) sulphate, SnSO{sub 4}, was obtained by Rietveld refinement using synchrotron high-resolution powder X-ray diffraction (HRPXRD) data. The structure was refined in space group Pbnm. The unit-cell parameters for SnSO{sub 4} are a = 7.12322(1), b = 8.81041(1), c = 5.32809(1) {angstrom}, and V = 334.383(1) {angstrom}{sup 3}. The average [12] distance is 2.9391(4) {angstrom}. However, the Sn{sup 2+} cation has a pyramidal [3]-coordination to O atoms and the average [3] = 2.271(1) {angstrom}. If Sn is considered as [12]-coordinated, SnSO{sub 4} has a structure similar to barite, BaSO{sub 4}, and its structuralmore » parameters are intermediate between those of BaSO{sub 4} and PbSO{sub 4}. The tetrahedral SO{sub 4} group has an average <S-O> [4] = 1.472(1) {angstrom} in SnSO{sub 4}. Comparing SnSO{sub 4} with the isostructural SrSO{sub 4}, PbSO{sub 4}, and BaSO{sub 4}, several well-defined trends are observed. The radii, rM, of the M{sup 2+}(=Sr, Pb, Sn, and Ba) cations and average <S-O> distances vary linearly with V because of the effective size of the M{sup 2+} cation. Based on the trend for the isostructural sulphates, the average [12] distance is slightly longer than expected because of the lone pair of electrons on the Sn{sup 2+} cation.« less

Effective identification of (NH4)2CO3 and NH4HCO3 concentrations in NaHCO3 regeneration process from desulfurized waste.

PubMed

Govindan, Muthuraman; Karunakaran, Kannan; Nallasamy, Palanisami; Moon, Il Shik

2015-01-01

This work describes the quantitative analysis of (NH4)2CO3 and NH4HCO3 using a simple solution phase titration method. Back titration results at various (NH4)2CO3-NH4HCO3 ratios demonstrated that 6:4 ratio caused a 3% error in their differentiation, but very high errors were found at other ratios. A similar trend was observed for the double indicator method, especially when strong acid HCl was used as a titrant, where still less errors (2.5%) at a middle ratio of (NH4)2CO3-NH4HCO3 was found. Remaining ratios with low (NH4)2CO3 (2:8, 4:6) show high +ve error (found concentration is less) and high (NH4)2CO3 (7:3, 8:2, and 9:1) show high -ve error (found concentration is higher) and vice versa for NH4HCO3. In replacement titration using Na2SO4, at both higher end ratios of (NH4)2CO3-NH4HCO3 (2:8 and 9:1), both -ve and +ve errors were minimized to 75% by partial equilibrium arrest between (NH4)2CO3 and NH2COONH4, instead of more than 100% observed in back titration and only double indicator methods. In the presence of (NH4)2SO4 both -ve and +ve error% are completely reduced to 3±1 at ratios 2:8, 4:6, and 6:4 of (NH4)2CO3-NH4HCO3, which demonstrates that the equilibrium transformation between NH2COONH4 and (NH4)2CO3 is completely controlled. The titration conducted at lower temperature (5 °C) in the presence of (NH4)2SO4 at higher ratios of (NH4)2CO3-NH4HCO3 (7:3, 8:2,and 9:1) shows complete minimization of both -ve and +ve errors to 2±1%, which explains the complete arresting of equilibrium transformation. Finally, the developed method shows 2±1% error in differentiation of CO3(2-) and HCO3(-) in the regeneration process of NaHCO3 from crude desulfurized sample. The developed method is more promising to differentiate CO3(2-) and HCO3(-) in industrial applications. Copyright © 2014 Elsevier B.V. All rights reserved.

NASICON-related Na3.4Mn0.4Fe1.6(PO4)3

PubMed Central

Yatskin, Michael M.; Strutynska, Nataliya Yu.; Baumer, Vyacheslav N.; Ogorodnyk, Ivan V.; Slobodyanik, Nikolay S.

2012-01-01

The solid solution, sodium [iron(III)/manganese(II)] tris­(orthophosphate), Na3.4Mn0.4Fe1.6(PO4)3, was obtained using a flux method. Its crystal structure is related to that of NASICON-type compounds. The [(Mn/Fe)2(PO4)3] framework is built up from an (Mn/Fe)O6 octa­hedron (site symmetry 3.), with a mixed Mn/Fe occupancy, and a PO4 tetra­hedron (site symmetry .2). The Na+ cations are distributed over two partially occupied sites in the cavities of the framework. One Na+ cation (site symmetry -3.) is surrounded by six O atoms, whereas the other Na+ cation (site symmetry .2) is surrounded by eight O atoms. PMID:22807697

Electrochemical Behavior Assessment of As-Cast Mg-Y-RE-Zr Alloy in Phosphate Buffer Solutions (X Na3PO4 + Y Na2HPO4) Using Electrochemical Impedance Spectroscopy and Mott-Schottky Techniques

NASA Astrophysics Data System (ADS)

Fattah-alhosseini, Arash; Asgari, Hamed

2018-05-01

In the present study, electrochemical behavior of as-cast Mg-Y-RE-Zr alloy (RE: rare-earth alloying elements) was investigated using electrochemical tests in phosphate buffer solutions (X Na3PO4 + Y Na2HPO4). X-ray diffraction techniques and Scanning electron microscopy equipped with energy dispersive x-ray spectroscopy were used to investigate the microstructure and phases of the experimental alloy. Different electrochemical tests such as potentiodynamic polarization (PDP), electrochemical impedance spectroscopy (EIS) and Mott-Schottky (M-S) analysis were carried out in order to study the electrochemical behavior of the experimental alloy in phosphate buffer solutions. The PDP curves and EIS measurements indicated that the passive behavior of the as-cast Mg-Y-RE-Zr alloy in phosphate buffer solutions was weakened by an increase in the pH, which is related to formation of an imperfect and less protective passive layer on the alloy surface. The presence of the insoluble zirconium particles along with high number of intermetallic phases of RE elements mainly Mg24Y5 in the magnesium matrix can deteriorate the corrosion performance of the alloy by disrupting the protective passive layer that is formed at pH values over 11. These insoluble zirconium particles embedded in the matrix can detrimentally influence the passivation. The M-S analysis revealed that the formed passive layers on Mg-Y-RE-Zr alloy behaved as an n-type semiconductor. An increase in donor concentration accompanying solutions of higher alkalinity is thought to result in the formation of a less resistive passive layer.

The time dependent growth of H2O-H2SO4 aerosols by heteromolecular condensation

NASA Technical Reports Server (NTRS)

Hamill, P.

1975-01-01

A theory for the time-dependent growth of solution droplets by heteromolecular condensation is presented. The theory is applied to the growth of H2O-H2SO4 aerosols for relative humidities less than 100 per cent. Growth curves (droplet radius as a function of time) for different values of relative humidity are evaluated.

Crown Ether Complexes of Alkali-Metal Chlorides from SO2.

PubMed

Reuter, Kirsten; Rudel, Stefan S; Buchner, Magnus R; Kraus, Florian; von Hänisch, Carsten

2017-07-18

The structures of alkali-metal chloride SO 2 solvates (Li-Cs) in conjunction with 12-crown-4 or 1,2-disila-12-crown-4 show strong discrepancies, despite the structural similarity of the ligands. Both types of crown ethers form 1:1 complexes with LiCl to give [Li(1,2-disila-12-crown-4)(SO 2 Cl)] (1) and [Li(12-crown-4)Cl]⋅4 SO 2 (2). However, 1,2-disila-12-crown-4 proved unable to coordinate cations too large for the cavity diameter, for example, by the formation of sandwich-type complexes. As a result, 12-crown-4 reacts exclusively with the heavier alkali-metal chlorides NaCl, KCl and RbCl. Compounds [Na(12-crown-4) 2 ]Cl⋅4 SO 2 (3) and [M(12-crown-4) 2 (SO 2 )]Cl⋅4 SO 2 (4: M=K; 5: M=Rb) all showed S-coordination to the chloride ions through four SO 2 molecules. Compounds 4 and 5 additionally exhibit the first crystallographically confirmed non-bridging O,O'-coordination mode of SO 2 . Unexpectedly, the disila-crown ether supports the dissolution of RbCl and CsCl in the solvent and gives the homoleptic SO 2 -solvated alkali-metal chlorides [MCl⋅3 SO 2 ] (6: M=Rb; 7: M=Cs), which incorporate bridging μ-O,O'-coordinating moieties and the unprecedented side-on O,O'-coordination mode. All compounds were characterised by single-crystal X-ray diffraction. The crown ether complexes were additionally studied by using NMR spectroscopy, and the presence of SO 2 at ambient temperature was revealed by IR spectroscopy of the neat compounds. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparison of adsorption equilibrium models for the study of CL-, NO3- and SO4(2-) removal from aqueous solutions by an anion exchange resin.

PubMed

Dron, Julien; Dodi, Alain

2011-06-15

The removal of chloride, nitrate and sulfate ions from aqueous solutions by a macroporous resin is studied through the ion exchange systems OH(-)/Cl(-), OH(-)/NO(3)(-), OH(-)/SO(4)(2-), and HCO(3)(-)/Cl(-), Cl(-)/NO(3)(-), Cl(-)/SO(4)(2-). They are investigated by means of Langmuir, Freundlich, Dubinin-Radushkevitch (D-R) and Dubinin-Astakhov (D-A) single-component adsorption isotherms. The sorption parameters and the fitting of the models are determined by nonlinear regression and discussed. The Langmuir model provides a fair estimation of the sorption capacity whatever the system under study, on the contrary to Freundlich and D-R models. The adsorption energies deduced from Dubinin and Langmuir isotherms are in good agreement, and the surface parameter of the D-A isotherm appears consistent. All models agree on the order of affinity OH(-)SO(4)(2-), and distinguish high energy processes (OH(-)/Cl(-), OH(-)/NO(3)(-), OH(-)/SO(4)(2-), Cl(-)/SO(4)(2-)) from lower energy systems (HCO(3)(-)/Cl(-), Cl(-)/NO(3)(-)). The D-A and D-R models provide the best fit to the experimental points, indicating that the micropore volume filling theory is the best representation of the ion exchange processes under study among other adsorption isotherms. The nonlinear regression results are also compared with linear regressions. While the parameter values are not affected, the evaluation of the best fitting model is biased by linearization. Copyright © 2011 Elsevier B.V. All rights reserved.

Low-temperature interaction of U(IV) and XeO{sub 3} in frozen aqueous H{sub 2}SO{sub 4} solutions accompanied by chemiluminescence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lotnik, S.V.; Khamidullina, L.A.; Kazakov, V.P.

Low-temperature (T{ge}180K) oxidation of U(IV) by xenon trioxide accompanied by chemiluminescence is studied in a frozen 0.2 M H{sub 2}SO{sub 4} solution. It is shown that the peak of luminescence at 195-200 K is related to chemiluminescence of the excited uranyl ion (UO{sup 2+}{sub 2}) formed in the oxidation of U(V), an intermediate product of the interaction of U(IV) and XeO{sub 3}.

Effect of H(2)SO(4) and HCl in the anode purging solution for the electrokinetic-Fenton remediation of soil contaminated with phenanthrene.

PubMed

Kim, Jung-Hwan; Kim, Jong Yun; Kim, Soo-Sam

2009-09-01

The Electrokinetic-Fenton (EK-Fenton) process is a powerful technology to remediate organic-contaminated soil. The behavior of salts and acids introduced for the pH control has significant influence on the H(2)O(2) stabilization and destruction of organic contaminants. In this study, the effects of the type and concentration of acids, which were introduced at the anode, were investigated for the treatment of clayey soil contaminated with phenanthrene. In experiments with H(2)SO(4) as the anode solution, H(2)O(2) concentration in the anode reservoir decreased due to reaction between reduced species of sulfate and H(2)O(2), as time elapsed. By contrast, HCl as an electrolyte in the anode reservoir did not decrease the H(2)O(2) concentration in the anode reservoir. The reaction between the reduced species of sulfate and H(2)O(2) hindered the stabilization of H(2)O(2) in the soil and anode reservoir. In experiments with HCl for pH control, Cl(.), and Cl(2)(. -), which could be generated with mineral catalyzed Fenton-like reaction, did not significantly hinder H(2)O(2) stabilization. H(2)O(2) transportation with electro-osmotic flow and mineral catalyzed Fenton-like reaction on the soil surface resulted in the simultaneous transport and degradation of phenanthrene, which are dependent of the advancement rate of the acid front and electro-osmotic flow toward the cathode according to HCl and H(2)SO(4) concentrations in the anode purging solution.

In situ investigation of complex BaSO4 fiber generation in the presence of sodium polyacrylate. 1. Kinetics and solution analysis.

PubMed

Wang, Tongxin; Cölfen, Helmut

2006-10-10

Simple solution analysis of the formation mechanism of complex BaSO(4) fiber bundles in the presence of polyacrylate sodium salt, via a bioinspired approach, is reported. Titration of the polyacrylate solution with Ba(2+) revealed complex formation and the optimum ratio of Ba(2+) to polyacrylate for a slow polymer-controlled mineralization process. This is a much simpler and faster method to determine the appropriate additive/mineral concentration pairs as opposed to more common crystallization experiments in which the additive/mineral concentration is varied. Time-dependent pH measurements were carried out to determine the concentration of solution species from which BaSO(4) supersaturation throughout the fiber formation process can be calculated and the second-order kinetics of the Ba(2+) concentration in solution can be identified. Conductivity measurements, pH measurements, and analytical ultracentrifugation revealed the first formed species to be Ba-polyacrylate complexes. A combination of the solution analysis results and optical microscopic images allows a detailed picture of the complex precipitation and self-organization process, a particle-mediated process involving mesoscopic transformations, to be revealed.

On the existence of a high-temperature polymorph of Na2Ca6Si4O15—implications for the phase equilibria in the system Na2O-CaO-SiO2

NASA Astrophysics Data System (ADS)

Kahlenberg, Volker; Maier, Matthias

2016-12-01

Singe crystals of a new high-temperature polymorph of Na2Ca6Si4O15 have been obtained from solid state reactions performed at 1300 °C. The basic crystallographic data of this so-called β-phase at ambient conditions are as follows: space group P1 c1, a = 9.0112(5) Å, b = 7.3171(5) Å, c = 10.9723(6) Å, β = 107.720(14)°, V = 689.14(7) Å3, Z = 2. The crystals showed twinning by reticular merohedry (mimicking an orthorhombic C-centred unit cell) which was accounted for during data processing and structure solution. Structure determination was accomplished by direct methods. Least-squares refinements resulted in a residual of R(|F|) = 0.043 for 5811 observed reflections with I > 2σ(I). From a structural point of view β-Na2Ca6Si4O15 can be attributed to the group of mixed-anion silicates containing [Si2O7]-dimers as well as isolated [SiO4]-tetrahedra in the ratio 1:2, i.e. more precisely the formula can be written as Na2Ca6[SiO4]2[Si2O7]. The tetrahedral groups are arranged in layers parallel to (100). Sodium and calcium cations are located between the silicate anions for charge compensation and are coordinated by six to eight nearest oxygen ligands. Alternatively, the structure can be described as a mixed tetrahedral-octahedral framework based on kröhnkite-type [Ca(SiO4)2O2]-chains in which the CaO6-octahedra are corner-linked to bridging SiO4-tetrahedra. The infinite chains are running parallel to [001] and are concentrated in layers parallel to (010). Adjacent layers are shifted relative to each other by an amount of +δ or -δ along a*. Consequently, a …ABABAB… stacking sequence is created. A detailed comparison with related structures such as α-Na2Ca6Si4O15 and other A2B6Si4O15 representatives including topological as well as group theoretical aspects is presented. There are strong indications that monoclinic Na2Ca3Si2O8 mentioned in earlier studies is actually misinterpreted β-Na2Ca6Si4O15. In addition to the detailed crystallographic analysis of

Speciation and Structural Properties of Hydrothermal Solutions of Sodium and Potassium Sulfate Studied by Molecular Dynamics Simulations.

PubMed

Reimer, Joachim; Vogel, Frédéric; Steele-MacInnis, Matthew

2016-05-18

Aqueous solutions of salts at elevated pressures and temperatures play a key role in geochemical processes and in applications of supercritical water in waste and biomass treatment, for which salt management is crucial for performance. A major question in predicting salt behavior in such processes is how different salts affect the phase equilibria. Herein, molecular dynamics (MD) simulations are used to investigate molecular-scale structures of solutions of sodium and/or potassium sulfate, which show contrasting macroscopic behavior. Solutions of Na-SO4 exhibit a tendency towards forming large ionic clusters with increasing temperature, whereas solutions of K-SO4 show significantly less clustering under equivalent conditions. In mixed systems (Nax K2-x SO4 ), cluster formation is dramatically reduced with decreasing Na/(K+Na) ratio; this indicates a structure-breaking role of K. MD results allow these phenomena to be related to the characteristics of electrostatic interactions between K(+) and SO4 (2-) , compared with the analogous Na(+) -SO4 (2-) interactions. The results suggest a mechanism underlying the experimentally observed increasing solubility in ternary mixtures of solutions of Na-K-SO4 . Specifically, the propensity of sodium to associate with sulfate, versus that of potassium to break up the sodium-sulfate clusters, may affect the contrasting behavior of these salts. Thus, mutual salting-in in ternary hydrothermal solutions of Na-K-SO4 reflects the opposing, but complementary, natures of Na-SO4 versus K-SO4 interactions. The results also provide clues towards the reported liquid immiscibility in this ternary system. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of Water on the H2SO4 Yield from the Ozonolysis of 2,3-dimethyl-butene (TME) in Presence of SO2

NASA Astrophysics Data System (ADS)

Véronique, D.; Kukui, A.; Chen, H.; Mellouki, A.

2016-12-01

The influence of the water vapor content on the yield of H2SO4 from the ozonolysis of 2,3-dimethyl-butene (TME) in presence of SO2 was studied using laminar flow reactor coupled with Chemical Ionisation Mass Spectrometer (CIMS) for the H2SO4 monitoring within the range of H2O from 10 ppmv to 3×104 ppmv at different concentrations of TME, O3, SO2. The observed dependences of the H2SO4 yield on H2O concentration can be interpreted by assuming two different paths of the H2SO4 formation: 1) via the formation of SO3 in the reaction of Stabilized Criegee Intermediate (SCI) with SO2 (2a) followed by the reaction of SO3 with H2O (3) and 2) via the formation of stabilized secondary ozonide (SOZ) (2b) producing H2SO4 in the reaction with H2O (4a) in competition with the SOZ decomposition to other products (5): O3+TME => (CH3)2COO (1) (CH3)2COO + SO2 => SO3 (2a) => SOZ (2b) SO3 + H2O => H2SO4 (3) SOZ + H2O => H2SO4 (or SO3) (4a) SOZ + M => products (5) The yield of the SCI, SOZ and the rates of the SCI and SOZ decomposition relative to their reactions with SO2 and H2O, respectively, were estimated from the dependencies of the H2SO4 yield on the concentrations of the reactants.

Improved GaSb surfaces using a (NH4)2S/(NH4)2S04 solution

NASA Astrophysics Data System (ADS)

Murape, D. M.; Eassa, N.; Nyamhere, C.; Neethling, J. H.; Betz, R.; Coetsee, E.; Swart, H. C.; Botha, J. R.; Venter, A.

2012-05-01

Bulk (1 0 0) n-GaSb surfaces have been treated with a sulphur based solution ((NH4)2S/(NH4)2SO4) to which sulphur has been added, not previously reported for the passivation of GaSb surfaces. Au/n-GaSb Schottky barrier diodes (SBDs) fabricated on the treated material show significant improvement compared to that of the similar SBDs on the as-received material as evidenced by the lower ideality factor (n), higher barrier height (ϕb) and lower contact resistance obtained. Additionally, the reverse leakage current, although not saturating, has been reduced by almost an order of magnitude at -0.2 V. The sample surfaces were studied by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The native oxide, Sb-O, present on the as-received material is effectively removed on treating with ([(NH4)2S/(NH4)2SO4]+S) and (NH4)2S. Analysis of the as-received surface by XPS, prior to and after argon sputtering, suggests that the native oxide layer is ≤8.5 nm.

Electron excitation cross sections for the 2s(2)2p(3)4S(O) -- 2s(2)2p(3)2D(O) (forbidden) and 4S(O) -- 2s2p(4) 4P (resonance) transitions in O II

NASA Technical Reports Server (NTRS)

Zuo, M.; Smith, Steven J.; Chutjian, A.; Williams, I. D.; Tayal, S. S.; Mclaughlin, Brendan M.

1995-01-01

Experimental and theoretical excitation cross sections are reported for the first forbidden transition 4S(O) -- 2S(2)2p(3) 2D(O) (lambda-lambda 3726, 3729) and the first allowed (resonance) transition 4S(O) -- 2s2p(4) 4P(lambda-833) in O II. Use is made of electron energy loss and merged-beams methods. The electron energy range covered is 3.33 (threshold) to 15 eV for the S -- D transition, and 14.9 (threshold) to 40 eV for the S -- P transition. Care was taken to assess and minimize the metastable fraction of the O II beam. An electron mirror was designed and tested to reflect inelastically backscattered electrons into the forward direction to account for the full range of polar scattering angles. Comparisons are made between present experiments and 11-state R-matrix calculations. Calculations are also presented for the 4S(O) -- 2s(2)2p(3)2P(O) (lambda-2470) transition.

The formation of supercooled brines, viscous liquids, and low-temperature perchlorate glasses in aqueous solutions relevant to Mars

NASA Astrophysics Data System (ADS)

Toner, J. D.; Catling, D. C.; Light, B.

2014-05-01

Salt solutions on Mars can stabilize liquid water at low temperatures by lowering the freezing point of water. The maximum equilibrium freezing-point depression possible, known as the eutectic temperature, suggests a lower temperature limit for liquid water on Mars; however, salt solutions can supercool below their eutectic before crystallization occurs. To investigate the magnitude of supercooling and its variation with salt composition and concentration, we performed slow cooling and warming experiments on pure salt solutions and saturated soil-solutions of MgSO4, MgCl2, NaCl, NaClO4, Mg(ClO4)2, and Ca(ClO4)2. By monitoring solution temperatures, we identified exothermic crystallization events and determined the composition of precipitated phases from the eutectic melting temperature. Our results indicate that supercooling is pervasive. In general, supercooling is greater in more concentrated solutions and with salts of Ca and Mg. Slowly cooled MgSO4, MgCl2, NaCl, and NaClO4 solutions investigated in this study typically supercool 5-15 °C below their eutectic temperature before crystallizing. The addition of soil to these salt solutions has a variable effect on supercooling. Relative to the pure salt solutions, supercooling decreases in MgSO4 soil-solutions, increases in MgCl2 soil-solutions, and is similar in NaCl and NaClO4 soil-solutions. Supercooling in MgSO4, MgCl2, NaCl, and NaClO4 solutions could marginally extend the duration of liquid water during relatively warm daytime temperatures in the martian summer. In contrast, we find that Mg(ClO4)2 and Ca(ClO4)2 solutions do not crystallize during slow cooling, but remain in a supercooled, liquid state until forming an amorphous glass near -120 °C. Even if soil is added to the solutions, a glass still forms during cooling. The large supercooling effect in Mg(ClO4)2 and Ca(ClO4)2 solutions has the potential to prevent water from freezing over diurnal and possibly annual cycles on Mars. Glasses are also

Detoxification of Dissolved SO2 (Bisulfite) by Terricolous Mosses

PubMed Central

BHARALI, BHAGAWAN; BATES, JEFFREY W.

2006-01-01

• Background and Aims The widespread calcifuge moss Pleurozium schreberi is moderately tolerant of SO2, whereas Rhytidiadelphus triquetrus is limited to calcareous soils in regions of the UK that were strongly affected by SO2 pollution in the 20th century. The proposition that tolerance of SO2 by these terricolous mosses depends on metabolic detoxification of dissolved bisulfite was investigated. • Methods The capacities of the two mosses to accelerate loss of bisulfite from aqueous solutions of NaHSO3 were studied using DTNB [5, 5-dithio-(2-nitrobenzoic acid)] to assay bisulfite, and HPLC to assay sulfate in the incubation solutions. Incubations were performed for different durations, in the presence and absence of light, at a range of solution pH values, in the presence of metabolic inhibitors and with altered moss apoplastic Ca2+ and Fe3+ levels. • Key Results Bisulfite disappearance was markedly stimulated in the light and twice as great for R. triquetrus as for P. schreberi. DCMU, an inhibitor of photosynthetic electron chain transport, significantly reduced bisufite loss. • Conclusions Bisulfite (SO2) tolerance in these terricolous mosses involves extracellular oxidation using metabolic (photo-oxidative) energy, passive oxidation by adsorbed Fe3+ (only available to the calcifuge) and probably also internal metabolic detoxification. PMID:16319108

H2O activity in concentrated NaCl solutions at high pressures and temperatures measured by the brucite-periclase equilibrium

NASA Astrophysics Data System (ADS)

Aranovich, L. Y.; Newton, R. C.

1996-10-01

H2O activities in concentrated NaCl solutions were measured in the ranges 600° 900° C and 2 15 kbar and at NaCl concentrations up to halite saturation by depression of the brucite (Mg(OH)2) periclase (MgO) dehydration equilibrium. Experiments were made in internally heated Ar pressure apparatus at 2 and 4.2 kbar and in 1.91-cm-diameter piston-cylinder apparatus with NaCl pressure medium at 4.2, 7, 10 and 15 kbar. Fluid compositions in equilibrium with brucite and periclase were reversed to closures of less than 2 mol% by measuring weight changes after drying of punctured Pt capsules. Brucite-periclase equilibrium in the binary system was redetermined using coarsely crystalline synthetic brucite and periclase to inhibit back-reaction in quenching. These data lead to a linear expression for the standard Gibbs free energy of the brucite dehydration reaction in the experimental temperature range: ΔG° (±120J)=73418 134.95 T(K). Using this function as a baseline, the experimental dehydration points in the system MgO-H2O-NaCl lead to a simple systematic relationship of high-temperature H2O activity in NaCl solution. At low pressure and low fluid densities near 2 kbar the H2O activity is closely approximated by its mole fraction. At pressures of 10 kbar and greater, with fluid densities approaching those of condensed H2O, the H2O activity becomes nearly equal to the square of its mole fraction. Isobaric halite saturation points terminating the univariant brucite-periclase curves were determined at each experimental pressure. The five temperature-composition points in the system NaCl-H2O are in close agreement with the halite saturation curves (liquidus curves) given by existing data from differential thermal analysis to 6 kbar. Solubility of MgO in the vapor phase near halite saturation is much less than one mole percent and could not have influenced our determinations. Activity concentration relations in the experimental P-T range may be retrieved for the binary

Hydrogen-fluorine exchange in NaBH4-NaBF4.

PubMed

Rude, L H; Filsø, U; D'Anna, V; Spyratou, A; Richter, B; Hino, S; Zavorotynska, O; Baricco, M; Sørby, M H; Hauback, B C; Hagemann, H; Besenbacher, F; Skibsted, J; Jensen, T R

2013-11-07

Hydrogen-fluorine exchange in the NaBH4-NaBF4 system is investigated using a range of experimental methods combined with DFT calculations and a possible mechanism for the reactions is proposed. Fluorine substitution is observed using in situ synchrotron radiation powder X-ray diffraction (SR-PXD) as a new Rock salt type compound with idealized composition NaBF2H2 in the temperature range T = 200 to 215 °C. Combined use of solid-state (19)F MAS NMR, FT-IR and DFT calculations supports the formation of a BF2H2(-) complex ion, reproducing the observation of a (19)F chemical shift at -144.2 ppm, which is different from that of NaBF4 at -159.2 ppm, along with the new absorption bands observed in the IR spectra. After further heating, the fluorine substituted compound becomes X-ray amorphous and decomposes to NaF at ~310 °C. This work shows that fluorine-substituted borohydrides tend to decompose to more stable compounds, e.g. NaF and BF3 or amorphous products such as closo-boranes, e.g. Na2B12H12. The NaBH4-NaBF4 composite decomposes at lower temperatures (300 °C) compared to NaBH4 (476 °C), as observed by thermogravimetric analysis. NaBH4-NaBF4 (1:0.5) preserves 30% of the hydrogen storage capacity after three hydrogen release and uptake cycles compared to 8% for NaBH4 as measured using Sievert's method under identical conditions, but more than 50% using prolonged hydrogen absorption time. The reversible hydrogen storage capacity tends to decrease possibly due to the formation of NaF and Na2B12H12. On the other hand, the additive sodium fluoride appears to facilitate hydrogen uptake, prevent foaming, phase segregation and loss of material from the sample container for samples of NaBH4-NaF.

Rare earth activated NaY (MoO4)2 phosphors for NIR emission

NASA Astrophysics Data System (ADS)

Tawalare, P. K.; Bhatkar, V. B.; Talewar, R. A.; Joshi, C. P.; Moharil, S. V.

2018-05-01

Efficient NIR emission is reported for NaY(MoO4)2 activated with Nd3+ or Yb3+. Characteristic emission of rare earth ions is sensitized by MoO4-2 group. The excitation is in the near UV region of 350-400 nm. These phosphors could be useful for modifying the solar spectrum so as to match with the spectral response of c-Si solar cells.

Interaction of Corundum, Wollastonite and Quartz With H2O-NaCl Solutions at 800 C and 10 Kbar

NASA Astrophysics Data System (ADS)

Newton, R. C.; Manning, C. E.

2005-12-01

Aqueous fluids are potentially important transport agents in subduction zones and other high-P metamorphic environments. Recent studies indicate that at high P and T, the solubilities of major rock-forming elements are strongly enhanced by the formation of metal-chloride complexes, metal-hydroxide complexes and polynuclear metal-hydroxide clusters. However, the relative abundances of these species and the energetics of their interactions in high-pressure environments remains largely unknown. We measured the solubilities of corundum (Al2O3) and wollastonite (CaSiO3) at 800 °C and 10 kbar in H2O-NaCl solutions to halite saturation (XNaCl = 0.6) . Both minerals show marked enhancement of solubility with increasing salinity. Al2O3 mol fraction rises rapidly to XNaCl = 0.1, and then declines slowly towards halite saturation. Quenched experimental fluids have neutral pH. Modeling based on ideal solution of ions and molecules leads to a simple dissolution reaction and corresponding molality (m=mol/kg H2O) expression: Al2O3(cor) + Na+ + 3H2O = NaAl(OH)4 + Al(OH)2+ and mAl2O3 = [0.0232(aNaCl)1/4(aH2O)3/2+0.00123][1+2XNaCl/(1-XNaCl)] where H2O and NaCl activities are given by aH2O = (2-XNaCl)/(2+XNaCl) and aNaCl = 4(XNaCl)2/(1 + XNaCl)2. Wollastonite solubility in NaCl solutions is accurately described by: mCaSiO3 = 0.6734XNaCl + 0.1183(XNaCl)1/2 + 0.0204. There is a roughly 50-fold enhancement of dissolved wollastonite at halite saturation. Quenched experimental fluids are strongly basic (pH=11). A consistent dissolution reaction must therefore be similar to: CaSiO3(wo) + Na+ + Cl- = CaCl+ + OH- + HNaSiO3 Quartz solubility declines monotonically from mSiO2 = 1.248 in pure H2O to 0.20 at halite saturation. Quenched fluids are neutral, indicating that quartz does not react with solvent NaCl. The only salinity control on solubility is decrease of H2O activity. The simple dissolution behaviors to be deduced from measurements on these minerals suggest that fluid

Ionic strength dependence of the oxidation of SO2 by H2O2 in sodium chloride particles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ali, Hashim M.; Iedema, Martin J.; Yu, Xiao-Ying

The reaction of sulfur dioxide and hydrogen peroxide in the presence of deliquesced (>75% RH) sodium particles was studied by utilizing a crossflow-mini reactor. The reaction kinetics was followed by observing chloride depletion in particles by computer-controlled scanning electron microscope with energy dispersive X-ray analysis, namely SEM/EDX. The reactions take place in concentrated mixed salt brine aerosols, for which no complete kinetic equilibrium data previously existed. We measured the Henry’s law solubility of H2O2 to close that gap. We also calculated the reaction rate as the particle transforms continuously from concentrated NaCl brine to eventually a mixed NaHSO4 plus H2SO4more » brine solution. The reaction rate of the SO2 oxidation by H2O2 was found to be influenced by the change in ionic strength as the particle undergoes compositional transformation, following closely the dependence of the third order rate constant on ionic strength as predicted rates using previously established rate equations. This is the first study that has measured the ionic strength dependence of sulfate formation (in non-aqueous media) from oxidation of mixed salt brine aerosols in the presence of H2O2. It also gives the first report of the Henry’s law constant of H2O2 dependence on ionic strength.« less

Phase and Physicochemical Properties Diagrams of Quaternary System Li2B4O7 + Na2B4O7 + Mg2B6O11 + H2O

NASA Astrophysics Data System (ADS)

Wang, Shi-qiang; Du, Xue-min; Jing, Yan; Guo, Ya-fei; Deng, Tian-long

2017-12-01

The phase and physicochemical properties diagrams of the quaternary system (Li2B4O7 + Na2B4O7 + Mg2B6O11) at 288.15 K and 0.1 MPa were constructed using the solubilities, densities, and refractive indices measured. In the phase diagrams of the system there are one invariant point, three univariant isothermic dissolution curves, and three crystallization regions corresponding to Li2B4O7 · 3H2O, Na2B4O7 · 10H2O, and Mg2B6O11 · 15H2O, respectively. The solution density, refractive index of the quaternary system changes regularly with the increasing of Li2B4O7 concentration. The calculated values of density and refractive index using empirical equations of the quaternary system are in good agreement with the experimental values.

Structural trends for celestite (SrSO[subscript 4]), anglesite (PbSO[subscript 4]), and barite (BaSO[subscript 4]): Confirmation of expected variations within the SO[subscript 4] groups

DOE Office of Scientific and Technical Information (OSTI.GOV)

Antao, Sytle M.

2012-05-10

The crystal structures of the isostructural orthorhombic sulfates celestite (SrSO{sub 4}), anglesite (PbSO{sub 4}), and barite (BaSO{sub 4}) were refined by Rietveld methods using synchrotron high-resolution powder X-ray diffraction (HRPXRD) data. Their structural model was refined in space group Pbnm. The unit-cell parameters are a = 6.87032(3), b = 8.36030(5), c = 5.34732(1) {angstrom}, and V = 307.139(3) {angstrom}{sup 3} for SrSO{sub 4}; a = 6.95802(1), b = 8.48024(3), c = 5.39754(1) {angstrom}, and V = 318.486(1) {angstrom}{sup 3} for PbSO{sub 4}; and a = 7.15505(1), b = 8.88101(3), c = 5.45447(1) {angstrom}, and V = 346.599(1) {angstrom}{sup 3} formore » BaSO{sub 4}. The average [12] distances are 2.827(1), 2.865(1), and 2.953(1) {angstrom} for SrSO{sub 4}, PbSO{sub 4}, and BaSO{sub 4}, respectively, and their corresponding average <S-O> [4] distances are 1.480(1), 1.477(3), and 1.471(1) {angstrom}. The geometrical features of the SO{sub 4} and MO{sub 12} polyhedra become more symmetrical from SrSO{sub 4} to BaSO{sub 4}. Across the series, the a, b, and c parameters vary non-linearly with increasing V. The radii of the M{sup 2+} cations, rM, [12], and <S-O> [4] distances vary linearly with V. These structural trends arise from the effective size of the M{sup 2+} cation (rM: Sr < Pb < Ba) that is coordinated to 12 O atoms.« less

Dissolution of bovine pulp tissue in solutions consisting of varying NaOCl concentrations and combined with EDTA.

PubMed

Irala, Luis Eduardo Duarte; Grazziotin-Soares, Renata; Salles, Alexandre Azevedo; Munari, Aline Zen; Pereira, Joseani Santos

2010-01-01

This in vitro study evaluated (1) the dissolution of bovine pulp tissue in solutions consisting of varying NaOCl concentrations and combined with EDTA; and (2) the pH of these solutions before and after the experiment. The independent variables were the concentration and the volume of the solution. Thirty bovine pulps were divided in equal fragments, resulting in 90 fragments of pulp tissue. Each fragment was immersed in one of the following solutions: 1% NaOCl (4 ml), 2.5% NaOCl (4 ml), 1% NaOCl + 17% EDTA (2 ml : 2 ml), 1% NaOCl + 17% EDTA (1 ml : 3 ml), 2.5% NaOCl + 17% EDTA (2 ml : 2 ml), and 2.5% NaOCl + 17% EDTA (1 ml : 3 ml). The test solutions were dichotomized as either able or not able to dissolve the tissue, the latter being attributed when the dissolution of the pulp tissue was not complete within 48 hours. When the samples were able to dissolve the tissue, the time required for complete tissue dissolution was submitted to statistical analysis. The pH of the solutions was measured before and after the experiment. The pH variable was dichotomized as either changed or unchanged. The results demonstrated that the NaOCl solutions combined with 17% EDTA were not able to dissolve the tissue. The t-test revealed that the 2.5% NaOCl solution presented a lower mean dissolution time than the 1% NaOCl solution (p < 0.001). The pH of the solutions with equal volumes of NaOCl and EDTA decreased in 48 hours.

Increase in Ice Nucleation Efficiency of Feldspars, Kaolinite and Mica in Dilute NH3 and NH4+-containing Solutions

NASA Astrophysics Data System (ADS)

Kumar, A.; Marcolli, C.; Luo, B.; Krieger, U. K.; Peter, T.

2017-12-01

Semivolatile species present in the atmosphere are prone to adhere to mineral dust particle surfaces during long range transport, and could potentially change the particle surface properties and its ice nucleation (IN) efficiency. Immersion freezing experiments were performed with microcline (K-feldspar), known to be highly IN active, suspended in aqueous solutions of ammonia, (NH4)2SO4, NH4HSO4, NH4NO3, NH4Cl, Na2SO4, H2SO4, K2SO4 and KCl to investigate the effect of solutes on the IN efficiency. Freezing of emulsified droplets investigated with a differential scanning calorimeter (DSC) showed that the heterogeneous ice nucleation temperatures deviate from the water activity-based IN theory, describing heterogeneous ice nucleation temperatures as a function of solution water activity by a constant offset with respect to the ice melting point curve (Zobrist et al. 2008). IN temperatures enhanced up to 4.5 K were observed for very dilute NH3 and NH4+-containing solutions while a decrease was observed as the concentration was further increased. For all solutes with cations other than NH4+, the IN efficiency decreased. An increase of the IN efficiency in very dilute NH3 and NH4+-containing solutions followed by a decrease with increasing concentration was also observed for sanidine (K-feldspar) and andesine (Na/Ca-feldspar). This is an important indication towards specific chemical interactions between solutes and the feldspar surface which is not captured by the water activity-based IN theory. A similar trend is present but less pronounced in case of kaolinite and mica, while quartz is barely affected. We hypothesize that the hydrogen bonding of NH3 molecules with surface -OH groups could be the reason for the enhanced freezing temperatures in dilute ammonia and ammonium containing solutions as they could form an ice-like overlayer providing hydrogen bonding groups for ice to nucleate on top of it. This implies to possibilities of enhanced IN efficiency, especially

Na7Cr4(P2O7)4PO4

PubMed Central

Bourguiba Fakhar, Noura; Zid, Mohamed Faouzi; Driss, Ahmed

2013-01-01

The title compound, hepta­sodium tetra­chromium(III) tetra­kis­(diphosphate) orthophosphate, was synthesized by solid-state reaction. Its structure is isotypic with that of Na7 M 4(P2O7)4PO4 (M = In, Al) compounds and is made up from a three-dimensional [(CrP2O7)4PO4]7− framework with channels running along [001]. The three Na+ cations are located in the voids of the framework. One of the cations is situated on a general position, one is equally disordered around a twofold rotation axis and one is on a fourfold rotoinversion axis. The isolated PO4 tetra­hedron of the anionic framework is also situated on the -4 axis. Structural relationships between the title compound and different diphosphates containing MP2O11 units (M = Mo, V) are discussed. PMID:23723751

Syntheses, crystal structures and optical spectroscopy of Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kazmierczak, Karolina; Hoeppe, Henning A., E-mail: henning@ak-hoeppe.d

2011-05-15

The lanthanide sulphate octahydrates Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) and the respective tetrahydrate Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O were obtained by evaporation of aqueous reaction mixtures of trivalent rare earth oxides and sulphuric acid at 300 K. Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) crystallise in space group C2/c (Z=4, a{sub Ho}=13.4421(4) A, b{sub Ho}=6.6745(2) A, c{sub Ho}=18.1642(5) A, {beta}{sub Ho}=102.006(1) A{sup 3} and a{sub Tm}=13.4118(14) A, b{sub Tm}=6.6402(6) A, c{sub Tm}=18.1040(16) A, {beta}{sub Tm}=101.980(8) A{sup 3}), Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O adopts space group P2{sub 1}/n (a=13.051(3) A, b=7.2047(14) A, c=13.316(3) A, {beta}=92.55(3) A{sup 3}). The vibrationalmore » and optical spectra of Ho{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O are also reported. -- Graphical abstract: In the lanthanide sulphate octahydrates the cations form slightly undulated layers. Between the layers are voids in which sulphate tetrahedra and water molecules are located. The holmium compound exhibits an Alexandrite effect. Display Omitted Highlights: {yields} Determination of the optimum conditions for the growth of single-crystals of Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O. {yields} Single-crystal structure elucidation of Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) including hydrogen bonds. {yields} Single-crystal structure determination of Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O including hydrogen bonds. {yields} UV-vis spectra of Ho{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O recorded and interpreted: Assignation of bands and clarification of the Alexandrite effect of the Ho compound. {yields} IR and Raman spectra of Ln{sub 2}(SO{sub 4}){sub 3}.8H{sub 2}O (Ln=Ho, Tm) and Pr{sub 2}(SO{sub 4}){sub 3}.4H{sub 2}O recorded and interpreted.« less

Leach of the weathering crust elution-deposited rare earth ore for low environmental pollution with a combination of (NH4)2SO4 and EDTA.

PubMed

Tang, Jie; Qiao, Jiyang; Xue, Qiang; Liu, Fei; Chen, Honghan; Zhang, Guochen

2018-05-01

High concentration of ammonium sulfate, a typical leaching agent, was often used in the mining process of the weathering crust elution-deposited rare earth ore. After mining, a lot of ammonia nitrogen and labile heavy metal fractions were residual in tailings, which may result in a huge potential risk to the environment. In this study, in order to achieve the maximum extraction of rare earth elements and reduce the labile heavy metal, extraction effect and fraction changes of lanthanum (La) and lead (Pb) in the weathering crust elution-deposited rare earth ore were studied by using a compound agent of (NH 4 ) 2 SO 4 -EDTA. The extraction efficiency of La was more than 90% by using 0.2% (NH 4 ) 2 SO 4 -0.005 M EDTA, which was almost same with that by using 2.0% (NH 4 ) 2 SO 4 solution. In contrast, the extraction efficiency of Pb was 62.3% when use 0.2% (NH 4 ) 2 SO 4 -0.005 M EDTA, which is much higher than that (16.16%) achieved by using 2.0% (NH 4 ) 2 SO 4 solution. The released Pb fractions were mainly acid extractable and reducible fractions, and the content of reducible fraction being leached accounted for 70.45% of the total reducible fraction. Therefore, the use of 0.2% (NH 4 ) 2 SO 4 -0.005 M EDTA can not only reduce the amount of (NH 4 ) 2 SO 4 , but also decrease the labile heavy metal residues in soil, which provides a new way for efficient La extraction with effective preventing and controlling environmental pollution in the process of mining the weathering crust elution-deposited rare earth ore. Copyright © 2018 Elsevier Ltd. All rights reserved.

Thermodynamic properties and crystal structure refinement of ferricopiapite, coquimbite, rhomboclase, and Fe2(SO4)3(H2O)5

USGS Publications Warehouse

Majzlan, J.; Navrotsky, A.; McCleskey, R. Blaine; Alpers, Charles N.

2006-01-01

Enthalpies of formation of ferricopiapite [nominally Fe4.67(SO4)6(OH)2 (H2O)20]. coquimbite [Fe2(SO4)3(H2O)9], rhomboclase [(H3O)Fe(SO4)2 (H2O)3], and Fe2(SO4)3(H2O)5 were measured by acid (5 N HCl) solution calorimetry. The samples were characterized by wet chemical analyses and synchrotron powder X-ray diffraction (XRD). The refinement of XRD patterns gave lattice parameters, atomic positions, thermal factors, and occupancies of the sites. The calculated formulae differ slightly from the nominal compositions: Fe4.78(SO4)6 (OH)2.34(H2O)20.71 (ferricopiapite), (Fe1.47Al0.53)(SO4)3 (H2O)9.65 (coquimbite), (H3O)1.34Fe(SO4)2.17 (H2O)3.06 (rhomboclase), and Fe2(SO4)3 (H2O)5.03. All thermodynamic data are given per mole of these formulae. The measured standard enthalpies (in kJ/mol) of formation from the elements (crystalline Fe, Al, S, and ideal gases O2 and H2) at T = 298.15 K are -4115.8??4.1 [Fe2(SO4)3 (H2O)5.03], -12045.1??9.2 (ferricopiapite), -5738.4??3.3 (coquimbite), and -3201.1??2.6 (rhomboclase). Standard entropy (S??) was estimated as a sum of entropies of oxide, hydroxide, and sulfate components. The estimated S?? (in J/mol.K) values for the iron sulfates are 488.2 [Fe2(SO4)3 (H2O)5.03], 1449.2 (ferricopiapite), 638.3 (coquimbite), and 380.1 (rhomboclase). The calculated Gibbs free energies of formation (in kJ/mol) are -3499.7??4.2 [Fe2(SO4)3 (H2O)5.03], -10089.8??9.3 (ferricopiapite), -4845.6??3.3 (coquimbite), and -2688.0??2.7 (rhomboclase). These results combined with other available thermodynamic data allow construction of mineral stability diagrams in the FeIII2(SO4)3-FeII SO4-H2O system. One such diagram is provided, indicating that the order of stability of ferric sulfate minerals with decreasing pH in the range of 1.5 to -0.5 is: hydronium jarosite, ferricopiapite, and rhomboclase. ?? 2006 E. Schweizerbart'sche Verlagsbuchhandlung.

Synthesis and characterization of novel Na15 (SO4 )5 F4 Cl:Ce3+ halosulfate phosphors.

PubMed

Bhake, A M; Nair, Govind B; Zade, G D; Dhoble, S J

2016-12-01

A series of Na 15 (SO 4 ) 5 F 4 Cl phosphors doped with Ce 3+ ions was prepared using the wet chemical method. X-Ray diffraction studies were used to determine their phase formation and purity. Fourier transform infrared spectroscopy effectively identified the chemical bonds present in the molecule. The photoluminescence properties of the as-prepared phosphors were investigated and the Ce 3+ ions in these hosts were found to give broadband emission in the UV range. For the thermoluminescence study, phosphors were irradiated with a 5 Gy dose of γ-rays from a 60 Co source. Chen's half-width method was employed to calculate the trapping parameters from the thermoluminescence glow curve. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

OPC Paste Samples Exposed To Aggressive Solutions. Cementitious Barriers Partnership

DOE Office of Scientific and Technical Information (OSTI.GOV)

Langton, C.

2014-11-01

The study presented in this report focused on a low-activity wasteform containing a high-pH pore solution with a significant level of sulfate. The purpose of the study was to improve understanding of the complex concrete/wasteform reactive transport problem, in particular, the role of pH in sulfate attack. Paste samples prepared at three different water-to-cement ratios were tested. The mixtures were prepared with ASTM Type I cement, without additional admixtures. The samples were exposed to two different sodium sulfate contact solutions. The first solution was prepared at 0.15M Na 2SO 4. The second solution also incorporated 0.5M NaOH, to mimic themore » high pH conditions found in Saltstone. The data collected indicated that, in Na 2SO 4 solution, damage occurs to the pastes. In the case of the high-pH sulfate solution (Na 2SO 4 + NaOH), no signs of damage were observed on any of the paste mixtures. These results indicate that the high sulfate content found in the wasteform pore solution will not necessarily lead to severe damage to concrete. Good-quality mixtures could thus prove durable over the long term, and act as an effective barrier to prevent radionuclides from reaching the environment.« less

Comparative study of three magnetic nano-particles (FeSO4, FeSO4/SiO2, FeSO4/SiO2/TiO2) in plasmid DNA extraction.

PubMed

Rahnama, H; Sattarzadeh, A; Kazemi, F; Ahmadi, N; Sanjarian, F; Zand, Z

2016-11-15

Recent updates on Magnetic Nano-Particles (MNPs) based separation of nucleic acids have received more attention due to their easy manipulation, simplicity, ease of automation and cost-effectiveness. It has been indicated that DNA molecules absorb on solid surfaces via hydrogen-bonding, and hydrophobic and electrostatic interactions. These properties highly depend on the surface condition of the solid support. Therefore, surface modification of MNPs may enhance their functionality and specification. In the present study, we functionalized Fe3O4 nano-particle surface utilizing SiO2 and TiO2 layer as Fe3O4/SiO2 and Fe3O4/SiO2/TiO2 and then compare their functionality in the adsorption of plasmid DNA molecules with the naked Fe3O4 nano-particles. The result obtained showed that the purity and amount of DNA extracted by Fe3O4 coated by SiO2 or SiO2/TiO2 were higher than the naked Fe3O4 nano-particles. Furthermore, we obtained pH 8 and 1.5 M NaCl as an optimal condition for desorption of DNA from MNPs. The result further showed that, 0.2 mg nano-particle and 10 min at 55 °C are the optimal conditions for DNA desorption from nano-particles. In conclusion, we recommended Fe3O4/SiO2/TiO2 as a new MNP for separation of DNA molecules from biological sources. Copyright © 2016 Elsevier Inc. All rights reserved.

Effective photodegradation of methomyl pesticide in concentrated solutions by novel enhancement of the photocatalytic activity of TiO2 using CdSO4 nanoparticles.

PubMed

Barakat, N A M; Nassar, M M; Farrag, T E; Mahmoud, M S

2014-01-01

Annihilation of electrons-holes recombination process is the main remedy to enhance the photocatalytic activity of the semiconductors photocatalysts. Doping of this class of photocatalysts by foreign nanoparticles is usually utilized to create high Schottky barrier that facilitates electron capture. In the literature, because nonpolar nanoparticles (usually pristine metals, e.g., Ag, Pt, Au, etc.) were utilized in the doping process, the corresponding improvement was relatively low. In this study, CdSO4-doped TiO2 nanoparticles are introduced as a powerful and reusable photocatalyst for the photocatalytic degradation of methomyl pesticide in concentrated aqueous solutions. The utilized CdSO4 nanoparticles form polar grains in the TiO2 matrix due to the electrons leaving characteristic of the sulfate anion. The introduced nanoparticles could successfully eliminate the harmful pesticide under the sunlight radiation within a very short time (less than 1 h), with a removal capacity reaching 1,000 mg pesticide per gram of the introduced photocatalyst. Moreover, increase in the initial concentration of the methomyl did not affect the photocatalytic performance; typically 300, 500, 1,000, and 2,000 mg/l solutions were completely treated within 30, 30, 40, and 60 min, respectively, using 100 mg catalyst. Interestingly, the photocatalytic efficiency was not affected upon multiple use of the photocatalyst. Moreover, negative activation energy was obtained which reveals super activity of the introduced photocatalyst. The distinct photocatalytic activity indicates the complete annihilation of the electrons-holes recombination process and abundant existence of electrons on the catalyst surfaces due to strong electrons capturing the operation of the utilized polar CdSO4 nanoparticles. The introduced photocatalyst has been prepared using the sol-gel technique. Overall, the simplicity of the synthesizing procedure and the obtained featured photocatalytic activity strongly

Iron(III) solubility and speciation in aqueous solutions. experimental study and modelling: part 1. hematite solubility from 60 to 300°C in NaOH-NaCl solutions and thermodynamic properties of Fe(OH) 4 -(aq)

NASA Astrophysics Data System (ADS)

Diakonov, Igor I.; Schott, Jacques; Martin, Francois; Harrichourry, Jean-Claude; Escalier, Jocelyne

1999-08-01

The solubility of natural and synthetic hematite (α-Fe 2O 3) was measured in NaOH-NaCl solutions (0.007 ≤ m(NaOH) ≤ 2.0) between 60 and 300°C at saturated water vapour pressure and under excess oxygen. Solubility constants determined in the present study and by Yishan et al. (1986) at 300°C were combined with the thermodynamic properties of hematite (Hemingway, 1990) and water (SUPCRT92, Johnson et al., 1992) to generate within the framework of the revised Helgeson-Kirkham-Flowers (HKF) model the standard partial molal thermodynamic properties at 25°C and 1 bar, and the revised HKF equations of state parameters of Fe(OH) 4 -. The extrapolated value for the Gibbs energy of formation for Fe(OH) 4 - at 25°C is -201.97 kcal/mol. Thermodynamic calculations show that Fe(OH) 4 - exhibits a chemical behaviour different from that of Ga(OH) 4 - and Al(OH) 4 -.

Evaluation of different electrochemical methods on the oxidation and degradation of Reactive Blue 4 in aqueous solution.

PubMed

Carneiro, Patricia A; Osugi, Marly E; Fugivara, Cecílio S; Boralle, Nivaldo; Furlan, Maysa; B Zanoni, Maria Valnice

2005-04-01

The oxidation of a reactive dye, Reactive Blue 4, RB4, (C.I. 61205), widely used in the textile industries to color natural fibers, was studied by electrochemical techniques. The oxidation on glassy carbon electrode and reticulated vitreous carbon electrode occurs in only one step at 2.0 < pH < 12 involving a two-electron transfer to the amine group leading to the imide derivative. Dye solution was not decolorized effectively in this electrolysis process. Nevertheless, the oxidation of this dye on Ti/SnO2/SbO(x) (3% mol)/RuO2 (1% mol) electrode showed 100% of decolorization and 60% of total organic carbon removal in Na2SO4 0.2 M at pH 2.2 and potential of +2.4V. Experiments on degradation photoelectrocatalytic were also carried out for RB4 degradation in Na2SO4 0.1 M, pH 12, using a Ti/TiO2 photoanode biased at +1.0 V and UV light. After 1h of electrolysis the results indicated total color removal and 37% of mineralization.

3.0 V High Energy Density Symmetric Sodium-Ion Battery: Na4V2(PO4)3∥Na3V2(PO4)3.

PubMed

Yao, Xuhui; Zhu, Zixuan; Li, Qi; Wang, Xuanpeng; Xu, Xiaoming; Meng, Jiashen; Ren, Wenhao; Zhang, Xinhe; Huang, Yunhui; Mai, Liqiang

2018-03-28

Symmetric sodium-ion batteries (SIBs) are considered as promising candidates for large-scale energy storage owing to the simplified manufacture and wide abundance of sodium resources. However, most symmetric SIBs suffer from suppressed energy density. Here, a superior congeneric Na 4 V 2 (PO 4 ) 3 anode is synthesized via electrochemical preintercalation, and a high energy density symmetric SIB (Na 3 V 2 (PO 4 ) 3 as a cathode and Na 4 V 2 (PO 4 ) 3 as an anode) based on the deepened redox couple of V 4+ /V 2+ is built for the first time. When measured in half cell, both electrodes show stabilized electrochemical performance (over 3000 cycles). The symmetric SIBs exhibit an output voltage of 3.0 V and a cell-level energy density of 138 W h kg -1 . Furthermore, the sodium storage mechanism under the expanded measurement range of 0.01-3.9 V is disclosed through an in situ X-ray diffraction technique.

The stability of Cl-CO3-scapolite relative to plagioclase + CaCO3 + CaSO4 in the presence of NaCl brines as a function of P-T-XNaCl

NASA Astrophysics Data System (ADS)

Harlov, D. E.; Budzyn, B.

2008-12-01

Cl-CO3-scapolite [(Na,Ca)4[Al3 (Al,Si) 3 Si3 O24](Cl, CO3 , SO4 )] occurs as a common partial to total alteration of plagioclase in deep-crustal xenoliths, skarns, marbles, gabbros, metabasites, calc-silicate gneisses, as well as in quartzofeldspathic granulite-facies rocks in general (Moecher and Essene, 1990, J Petrol 31, 997). Alteration of plagioclase to Cl-CO3-scapolite is presumed due to metasomatism by CO2-NaCl-H2O fluids (Satish-Kumar and Santosh, 1998, Geol Mag 135, 27). Previous experimental work on CO3-scapolite has focused on reversing the equilibrium 3 CaAl2 Si2 O8 + CaCO3 = Ca4 Al6 Si6 O24 CO3 in either pure CO2 (Goldschmidt and Newton, 1977, Am Mineral 62, 1063) or in CO2-H2O (Huckenholz and Seiberl, 1989 Abs IGC 28, 2.79). These experiments have determined that the anorthite- calcite-scapolite equilibrium is nearly pressure-invariant in P-T space (200 to 1500 MPa) occurring at approximately 790 to 820 °C (Huckenholz and Seiberl, 1989). In this study, a series of experiments, involving the equilibrium 3 Plagioclase(An60) + 0.5 CaCO3 + 0.5 CaSO4 = [(Na,Ca)4[Al3 (Al,Si)3 Si3 O24](Cl, CO3, SO4 )] plus an NaCl brine (10/90, 20/80, 30/70, and 50/50 molar NaCl/H2O) have been done at 500, 1000, and 1500 MPa and 600 to 900 °C. Natural plagioclase and scapolite, along with synthetic calcite and anhydrite, were lightly ground together in equi-molar amounts in ethanol. The mineral mix (10 mg) + NaCl brine (5 mg), or pure H2O (1.5 mg), were loaded into 3 mm diameter/1.3 mm long Pt capsules which were arc-welded shut, folded, and placed horizontally in a CaF2 setup (with graphite oven), such that the thermocouple tip touched the Pt capsule, or placed in a hydrothermal autoclave (600 and 700 °C; 500 MPa) with an internal thermocouple. A series of duplicate experiments for the same mineral mix, at the same P-T conditions, were done utilizing pure H2O as the flux. The H2O-only experiments duplicated the P-T reversals of Huckenholz and Seiberl (1989). In contrast

Ceramic oxide reactions with V2O5 and SO3

NASA Technical Reports Server (NTRS)

Jones, R. L.; Williams, C. E.

1985-01-01

Ceramic oxides are not inert in combustion environments, but can react with, inter alia, SO3, and Na2SO4 to yield low melting mixed sulfate eutectics, and with vanadium compounds to produce vanadates. Assuming ceramic degradation to become severe only when molten phases are generated in the surface salt (as found for metallic hot corrosion), the reactivity of ceramic oxides can be quantified by determining the SO3 partial pressure necessary for molten mixed sulfate formation with Na2SO3. Vanadium pentoxide is an acidic oxide that reacts with Na2O, SO3, and the different ceramic oxides in a series of Lux-Flood type of acid-base displacement reactions. To elucidate the various possible vanadium compound-ceramic oxide interactions, a study was made of the reactions of a matrix involving, on the one axis, ceramix oxides of increasing acidity, and on the other axis, vanadium compounds of increasing acidity. Resistance to vanadium compound reaction increased as the oxide acidity increased. Oxides more acidic than ZrO2 displaced V2O5. Examination of Y2O3- and CeO2-stabilized ZrO2 sintered ceramics which were degraded in 700 C NaVO3 has shown good agreement with the reactions predicted above, except that the CeO2-ZrO2 ceramic appears to be inexplicably degraded by NaVO3.

Na3.4Zr1.8Mg0.2Si2PO12 filled poly(ethylene oxide)/Na(CF3SO2)2N as flexible composite polymer electrolyte for solid-state sodium batteries

NASA Astrophysics Data System (ADS)

Zhang, Zhizhen; Xu, Kaiqi; Rong, Xiaohui; Hu, Yong-Sheng; Li, Hong; Huang, Xuejie; Chen, Liquan

2017-12-01

Solid electrolytes with high ionic conductivity and excellent electrochemical stability are of prime significance to enable the application of solid-state batteries in energy storage and conversion. In this study, solid composite polymer electrolytes (CPEs) based on sodium bis(trifluorosulfonyl) imide (NaTFSI) and poly (ethylene oxide) (PEO) incorporated with active ceramic filler (NASICON) are reported for the first time. With the addition of NASICON fillers, the thermal stability and electrochemical stability of the CPEs are improved. A high conductivity of 2.8 mS/cm (at 80 °C) is readily achieved when the content of the NASICON filler in the composite polymer reaches 50 wt%. Furthermore, Na3V2(PO4)3/CPE/Na solid-state batteries using this composite electrolyte display good rate and excellent cycle performance.

Water-separated ion pairs cause the slow dielectric mode of magnesium sulfate solutions

NASA Astrophysics Data System (ADS)

Mamatkulov, Shavkat I.; Rinne, Klaus F.; Buchner, Richard; Netz, Roland R.; Bonthuis, Douwe Jan

2018-06-01

We compare the dielectric spectra of aqueous MgSO4 and Na2SO4 solutions calculated from classical molecular dynamics simulations with experimental data, using an optimized thermodynamically consistent sulfate force field. Both the concentration-dependent shift of the static dielectric constant and the spectral shape match the experimental results very well for Na2SO4 solutions. For MgSO4 solutions, the simulations qualitatively reproduce the experimental observation of a slow mode, the origin of which we trace back to the ion-pair relaxation contribution via spectral decomposition. The radial distribution functions show that Mg2+ and SO42 - ions form extensive water-separated—and thus strongly dipolar—ion pairs, the orientational relaxation of which provides a simple physical explanation for the prominent slow dielectric mode in MgSO4 solutions. Remarkably, the Mg2+-SO42 - ion-pair relaxation extends all the way into the THz range, which we rationalize by the vibrational relaxation of tightly bound water-separated ion pairs. Thus, the relaxation of divalent ion pairs can give rise to widely separated orientational and vibrational spectroscopic features.

Na2.5Fe1.75(SO4)3/Ketjen/rGO: An advanced cathode composite for sodium ion batteries

NASA Astrophysics Data System (ADS)

Goñi, A.; Iturrondobeitia, A.; Gil de Muro, I.; Lezama, L.; Rojo, T.

2017-11-01

An advanced cathode composite Na2.5Fe1.75(SO4)3/Ketjen/rGO for sodium ion batteries has been prepared, joining together the excellent electrochemical properties of the three components: off stoichiometric iron sulfate alluaudite, Ketjen Black carbon and reduced graphene oxide (rGO). This electrode material has been exhaustively characterized by XRD, thermogravimetric analysis, Raman spectroscopy and SEM and TEM microscopy. The study has demonstrated that a high quality electrode material has been designed containing a porous sulfate core properly coated by interweaved rGO fibers and Ketjen Black nanoparticles. The electrochemical study has revealed an excellent performance providing specific capacities close to the theoretical one at 1C. Additionally, this composite has shown a very good rate capability and a great cycling stability for at least 200 cycles maintaining a coulombic efficiency of 96%. The post mortem analysis, which includes EPR and XPS measurements, has demonstrated that the carbonaceous coating on the composite generates a stable and protective SEI layer over the active material guaranteeing a successful performance during a long cycle life.

Thermodynamic description of Tc(iv) solubility and hydrolysis in dilute to concentrated NaCl, MgCl2 and CaCl2 solutions.

PubMed

Yalçıntaş, Ezgi; Gaona, Xavier; Altmaier, Marcus; Dardenne, Kathy; Polly, Robert; Geckeis, Horst

2016-06-07

We present the first systematic investigation of Tc(iv) solubility, hydrolysis and speciation in dilute to concentrated NaCl, MgCl2 and CaCl2 systems, and comprehensive thermodynamic and activity models for the system Tc(4+)-H(+)-Na(+)-Mg(2+)-Ca(2+)-OH(-)-Cl(-)-H2O using both SIT and Pitzer approaches. The results are advancing the fundamental scientific understanding of Tc(iv) solution chemistry and are highly relevant in the applied context of nuclear waste disposal. The solubility of Tc(iv) was investigated in carbonate-free NaCl-NaOH (0.1-5.0 M), MgCl2 (0.25-4.5 M) and CaCl2 (0.25-4.5 M) solutions within 2 ≤ pHm≤ 14.5. Undersaturation solubility experiments were performed under an Ar atmosphere at T = 22 ± 2 °C. Strongly reducing conditions (pe + pHm≤ 2) were imposed with Na2S2O4, SnCl2 and Fe powder to stabilize technetium in the +IV redox state. The predominance of Tc(iv) in the aqueous phase was confirmed by solvent extraction and XANES/EXAFS spectroscopy. Solid phase characterization was accomplished after attaining thermodynamic equilibrium using XRD, SEM-EDS, XANES/EXAFS, TG-DTA and quantitative chemical analysis, and indicated that TcO2·0.6H2O(s) exerts solubility-control in all evaluated systems. The definition of the polyatomic Tc3O5(2+) species instead of TcO(2+) is favoured under acidic conditions, consistently with slope analysis (mTcvs. pHm) of the solubility data gained in this work and spectroscopic evidence previously reported in the literature. The additional formation of Tc(iv)-OH/O-Cl aqueous species in concentrated chloride media ([Cl(-)] = 9 M) and pHm≤ 4 is suggested by solubility and EXAFS data. The pH-independent behaviour of the solubility observed under weakly acidic to weakly alkaline pHm conditions can be explained with the equilibrium reaction TcO2·0.6H2O(s) + 0.4H2O(l) ⇔ TcO(OH)2(aq). Solubility data determined in dilute NaCl systems with pHm≥ 11 follow a well-defined slope of +1, consistent with the predominance of

β-Li0.37Na0.63Fe(MoO4)2

PubMed Central

Souilem, Amira; Zid, Mohamed Faouzi; Driss, Ahmed

2014-01-01

The title compound, lithium/sodium iron(III) bis­[ortho­molyb­date(VI)], was obtained by a solid-state reaction. The main structure units are an FeO6 octa­hedron, a distorted MoO6 octa­hedron and an MoO4 tetra­hedron sharing corners. The crystal structure is composed of infinite double MoFeO11 chains along the b-axis direction linked by corner-sharing to MoO4 tetra­hedra so as to form Fe2Mo3O19 ribbons. The cohesion between ribbons via mixed Mo—O—Fe bridges leads to layers arranged parallel to the bc plane. Adjacent layers are linked by corners shared between MoO4 tetra­hedra of one layer and FeO6 octa­hedra of the other layer. The Na+ and Li+ ions partially occupy the same general position, with a site-occupancy ratio of 0.631 (9):0.369 (1). A comparison is made with AFe(MoO4)2 (A = Li, Na, K and Cs) structures. PMID:24764805

Corrosion study on high power feeding of telecomunication copper cable in 5 wt.% CaSO4.2H2O solution

NASA Astrophysics Data System (ADS)

Shamsudin, Shaiful Rizam; Hashim, Nabihah; Ibrahim, Mohd Saiful Bahri; Rahman, Muhammad Sayuzi Abdul; Idrus, Muhammad Amin; Hassan, Mohd Rezadzudin; Abdullah, Wan Razli Wan

2016-07-01

The studies were carried out to find out the best powering scheme over the copper telephone line. It was expected that the application of the higher power feeding could increase the data transfer and capable of providing the customer's satisfaction. To realize the application of higher remote power feeding, the potential of corrosion problem on Cu cables was studied. The natural corrosion behaviour of copper cable in the 0.5% CaSO4.2H2O solution was studied in term of open circuit potential for 30 days. The corrosion behaviour of higher power feeding was studied by the immersion and the planned interval test to determine the corrosion rate as well as the effect of voltage magnitudes and the current scheme i.e. positive direct (DC+) and alternating current (AC) at about 0.40 ± 0.01 mA/ cm2 current density. In the immersion test, both DC+ and AC scheme showed the increasing of feeding voltage magnitude has increased the corrosion rate of Cu samples starting from 60 to 100 volts. It was then reduced at about 100 - 120 volts which may due to the passive and transpassive mechanism. The corrosion rate was slowly reduced further from 120 to 200 volts. Visually, the positively charged of Cu cable was seems susceptible to severe corrosion, while AC scheme exhibited a slight corrosion reaction on the surface. However, the planned interval test and XRD results showed the corrosion activity of the copper cable in the studied solution was a relatively slow process and considered not to be corroded as a partially protective scale of copper oxide formed on the surface.

Kinetic and thermodynamic factors controlling the distribution of SO32- and Na+ in calcites and selected aragonites

USGS Publications Warehouse

Busenberg, E.; Plummer, Niel

1985-01-01

Significant amounts of SO42-, Na+, and OH- are incorporated in marine biogenic calcites. Biogenic high Mg-calcites average about 1 mole percent SO42-. Aragonites and most biogenic low Mg-calcites contain significant amounts of Na+, but very low concentrations of SO42-. The SO42- content of non-biogenic calcites and aragonites investigated was below 100 ppm. The presence of Na+ and SO42- increases the unit cell size of calcites. The solid-solutions show a solubility minimum at about 0.5 mole percent SO42- beyond which the solubility rapidly increases. The solubility product of calcites containing 3 mole percent SO42- is the same as that of aragonite. Na+ appears to have very little effect on the solubility product of calcites. The amounts of Na+ and SO42- incorporated in calcites vary as a function of the rate of crystal growth. The variation of the distribution coefficient (D) of SO42- in calcite at 25.0??C and 0.50 molal NaCl is described by the equation D = k0 + k1R where k0 and k1 are constants equal to 6.16 ?? 10-6 and 3.941 ?? 10-6, respectively, and R is the rate of crystal growth of calcite in mg??min-1??g-1 of seed. The data on Na+ are consistent with the hypothesis that a significant amount of Na+ occupies interstitial positions in the calcite structure. The distribution of Na+ follows a Freundlich isotherm and not the Berthelot-Nernst distribution law. The numerical value of the Na+ distribution coefficient in calcite is probably dependent on the number of defects in the calcite structure. The Na+ contents of calcites are not very accurate indicators of environmental salinities. ?? 1985.

Experimentally determined standard thermodynamic properties of synthetic MgSO(4)·4H(2)O (Starkeyite) and MgSO(4)·3H(2)O: a revised internally consistent thermodynamic data set for magnesium sulfate hydrates.

PubMed

Grevel, Klaus-Dieter; Majzlan, Juraj; Benisek, Artur; Dachs, Edgar; Steiger, Michael; Fortes, A Dominic; Marler, Bernd

2012-11-01

The enthalpies of formation of synthetic MgSO(4)·4H(2)O (starkeyite) and MgSO(4)·3H(2)O were obtained by solution calorimetry at T=298.15 K. The resulting enthalpies of formation from the elements are [Formula: see text] (starkeyite)=-2498.7±1.1 kJ·mol(-1) and [Formula: see text] (MgSO(4)·3H(2)O)=-2210.3±1.3 kJ·mol(-1). The standard entropy of starkeyite was derived from low-temperature heat capacity measurements acquired with a physical property measurement system (PPMS) in the temperature range 5 K2.0 J·K(-1)·mol(-1). Additionally, differential scanning calorimetry (DSC) measurements with a Perkin Elmer Diamond DSC in the temperature range 270 K2). The hydration state of all Mg sulfate hydrates changes in response to local temperature and humidity conditions. Based on recently reported equilibrium relative humidities and the new standard properties described above, the internally consistent thermodynamic database for the MgSO(4)·nH(2)O system was refined by a mathematical programming (MAP) analysis. As can be seen from the resulting phase diagrams, starkeyite is metastable in the entire T-%RH range. Due to kinetic limitations of kieserite formation, metastable occurrence of starkeyite might be possible under martian conditions.

Study on improving viscosity of polymer solution based on complex reaction

NASA Astrophysics Data System (ADS)

Sun, G.; Li, D.; Zhang, D.; Xu, T. H.

2018-05-01

The current status of polymer flooding Technology on high salinity oil reservoir is not ideal. A method for increasing the viscosity of polymer solutions is urgently needed. This paper systematically studied the effect of ions with different mass concentrations on the viscosity of polymer solutions. Based on the theory of complex reaction, a countermeasure of increasing viscosity of polymer solution under conditions of high salinity reservoir was proposed. The results show that Ca2+ and Mg2+ have greater influence on the solution viscosity than K+ and Na+. When the concentration of divalent ions increases from 0 mg/L to 80 mg/L, the viscosity of the polymer solution decreases from 210 mPa·s to 38.6 mPa·s. The viscosity of the polymer solution prepared from the sewage treated with the Na2C2O4 increased by 25.3%. Atomic force microscopy test results show that Na2C2O4 can effectively shield the divalent metal ions, so that the polymer molecules in the solution stretch more, thereby increasing the solution viscosity. Atomic force microscopy test results show that Na2C2O4 can effectively shield the divalent metal ions, so that the polymer molecules in the solution stretch more, thereby increasing the solution viscosity.

Dithallium(III)-Containing 30-Tungsto-4-phosphate, [Tl2Na2(H2O)2(P2W15O56)2]16-: Synthesis, Structural Characterization, and Biological Studies.

PubMed

Ayass, Wassim W; Fodor, Tamás; Farkas, Edit; Lin, Zhengguo; Qasim, Hafiz M; Bhattacharya, Saurav; Mougharbel, Ali S; Abdallah, Khaled; Ullrich, Matthias S; Zaib, Sumera; Iqbal, Jamshed; Harangi, Sándor; Szalontai, Gábor; Bányai, István; Zékány, László; Tóth, Imre; Kortz, Ulrich

2018-06-18

Here we report on the synthesis and structural characterization of the dithallium(III)-containing 30-tungsto -4-phosphate [Tl 2 Na 2 (H 2 O) 2 {P 2 W 15 O 56 } 2 ] 16- (1) by a multitude of solid-state and solution techniques. Polyanion 1 comprises two octahedrally coordinated Tl 3+ ions sandwiched between two trilacunary {P 2 W 15 } Wells-Dawson fragments and represents only the second structurally characterized, discrete thallium-containing polyoxometalate to date. The two outer positions of the central rhombus are occupied by sodium ions. The title polyanion is solution-stable as shown by 31 P and 203/205 Tl NMR. This was also supported by Tl NMR spectra simulations including several spin systems of isotopologues with half-spin nuclei ( 203 Tl, 205 Tl, 31 P, 183 W). 23 Na NMR showed a time-averaged signal of the Na + counter cations and the structurally bonded Na + ions. 203/205 Tl NMR spectra also showed a minor signal tentatively attributed to the trithallium-containing derivative [Tl 3 Na(H 2 O) 2 (P 2 W 15 O 56 ) 2 ] 14- , which could also be identified in the solid state by single-crystal X-ray diffraction. The bioactivity of polyanion 1 was also tested against bacteria and Leishmania.

Effect of the cation size on the framework structures of magnesium tungstate, A4Mg(WO4)3 (A = Na, K), R2Mg2(WO4)3 (R = Rb, Cs).

PubMed

Han, Shujuan; Wang, Ying; Jing, Qun; Wu, Hongping; Pan, Shilie; Yang, Zhihua

2015-03-28

A series of alkali metal magnesium tungstates, A4Mg(WO4)3 (A = Na, K), R2Mg2(WO4)3 (R = Rb, Cs), were synthesized from a high temperature solution, and their structures were determined by single-crystal X-ray diffraction. Interestingly, Na4Mg(WO4)3 crystallizes in the monoclinic space group C2/c, while K4Mg(WO4)3 having an identical stoichiometry with Na4Mg(WO4)3, exhibits a different framework structure belonging to triclinic symmetry with the space group P1[combining macron]. Isostructural Rb2Mg2(WO4)3 and Cs2Mg2(WO4)3 crystallize in the space group P213 of cubic symmetry and reveal a three dimensional framework composed of isolated WO4 tetrahedra, MgO6 octahedra and RO12 (R = Rb, Cs) polyhedra. The effect of the alkali metal cation size on the framework structures of magnesium tungstate has been discussed in detail. In addition, the infrared spectra, as well as the UV-Vis-NIR diffuse reflectance spectroscopy data, are reported. The first-principles theoretical studies are also carried out to aid the understanding of electronic structures and linear optical properties.

The mixed anion mineral parnauite Cu 9[(OH) 10|SO 4|(AsO 4) 2]·7H 2O—A Raman spectroscopic study

NASA Astrophysics Data System (ADS)

Frost, Ray L.; Keeffe, Eloise C.

2011-10-01

The mixed anion mineral parnauite Cu 9[(OH) 10|SO 4|(AsO 4) 2]·7H 2O from two localities namely Cap Garonne Mine, Le Pradet, France and Majuba Hill mine, Pershing County, Nevada, USA has been studied by Raman spectroscopy. The Raman spectrum of the French sample is dominated by an intense band at 975 cm -1 assigned to the ν1 (SO 4) 2- symmetric stretching mode and Raman bands at 1077 and 1097 cm -1 may be attributed to the ν3 (SO 4) 2- antisymmetric stretching mode. Two Raman bands 1107 and 1126 cm -1 are assigned to carbonate CO 32- symmetric stretching bands and confirms the presence of carbonate in the structure of parnauite. The comparatively sharp band for the Pershing County mineral at 976 cm -1 is assigned to the ν1 (SO 4) 2- symmetric stretching mode and a broad spectral profile centered upon 1097 cm -1 is attributed to the ν3 (SO 4) 2- antisymmetric stretching mode. Two intense bands for the Pershing County mineral at 851 and 810 cm -1 are assigned to the ν1 (AsO 4) 3- symmetric stretching and ν3 (AsO 4) 3- antisymmetric stretching modes. Two Raman bands for the French mineral observed at 725 and 777 cm -1 are attributed to the ν3 (AsO 4) 3- antisymmetric stretching mode. For the French mineral, a low intensity Raman band is observed at 869 cm -1 and is assigned to the ν1 (AsO 4) 3- symmetric stretching vibration. Chemical composition of parnauite remains open and the question may be raised is parnauite a solid solution of two or more minerals such as a copper hydroxy-arsenate and a copper hydroxy sulphate.

Cephradine as corrosion inhibitor for copper in 0.9% NaCl solution

NASA Astrophysics Data System (ADS)

Tasić, Žaklina Z.; Petrović Mihajlović, Marija B.; Radovanović, Milan B.; Simonović, Ana T.; Antonijević, Milan M.

2018-05-01

The effect of (6R,7R)-7-[[(2R)-2-amino-2-cyclohexa-1,4-dien-1-ylacetyl]amino]-3-methyl-8-oxo-5-thia-1-azobicyclo[4.2.0]oct-2-ene-2-carboxylic acid (cephradine) on corrosion behavior of copper in 0.9% NaCl solution was investigated. The electrochemical methods including the open circuit potential measurements, potentiodynamic polarization and electrochemical impedance spectroscopy measurements, scanning electron microscopy with energy dispersive X-ray spectroscopy and quantum chemical calculations were used for this investigation. According to the results obtained by potentiodynamic polarization, cephradine acts as mixed type inhibitor. Also, the results obtained by electrochemical impedance spectroscopy indicate that cephradine provides good copper protection in 0.9% NaCl solution. The inhibition efficiency of cephradine increases with increasing its concentration. The scanning electron microscopy with energy dispersive X-ray spectroscopy confirms that a protective layer is formed on the copper surface due to the adsorption of cephradine on the active sites on the copper surface. Adsorption of cephradine in 0.9% NaCl solution follows the Langmuir adsorption isotherm. Quantum chemical calculations are in agreement with results obtained by electrochemical measurements.

Equilibrium, Kinetics, and Spectroscopic Studies of SF6 Hydrate in NaCl Electrolyte Solution.

PubMed

Seo, Youngrok; Moon, Donghyun; Lee, Changho; Park, Jeong-Woo; Kim, Byeong-Soo; Lee, Gang-Woo; Dotel, Pratik; Lee, Jong-Won; Cha, Minjun; Yoon, Ji-Ho

2015-05-19

Many studies have focused on desalination via hydrate formation; however, for their potential application, knowledge pertaining to thermodynamic stability, formation kinetics, and guest occupation behavior in clathrate hydrates needs to be determined. Herein, the phase equilibria of SF6 hydrates in the presence of NaCl solutions (0, 2, 4, and 10 wt %) were monitored in the temperature range of 277-286 K and under pressures of up to 1.4 MPa. The formation kinetics of SF6 hydrates in the presence of NaCl solutions (0, 2, and 4 wt %) was also investigated. Gas consumption curves of SF6 hydrates showed that a pure SF6 hydrate system allowed fast hydrate growth as well as high conversion yield, whereas SF6 hydrate in the presence of NaCl solutions showed retarded hydrate growth rate as well as low conversion yield. In addition, structural identification of SF6 hydrates with and without NaCl solutions was performed using spectroscopic tools such as Raman spectroscopy and X-ray diffraction. The Raman spectrometer was also used to evaluate the temperature-dependent release behavior of guest molecules in SF6 and SF6 + 4 wt % NaCl hydrates. The results indicate that whereas SF6 hydrate starts to decompose at around 240 K, the escape of SF6 molecules in SF6 + 4 wt % NaCl hydrate is initiated rapidly at around 205 K. The results of this study can provide a better understanding of guest-host interaction in electrolyte-containing systems.

Effects of SO42- ions on the corrosion of GH3535 weld joint in FLiNaK molten salt

NASA Astrophysics Data System (ADS)

Zhu, Yasheng; Qiu, Jie; Hou, Juan; Liu, Wenguan; Chen, Huaican; Ai, Hua; Yu, Guojun; Wang, Jianqiang; Zhou, Xingtai

2017-08-01

The present work studied the impact of SO42- ions on the corrosion behaviors of GH3535 weld joint in FLiNaK molten salt. The concentration of SO42- ions in the FLiNaK molten salt was controlled by adjusting the quantity of Na2SO4 added into the salt. Results indicate that the SO42- ions in the FLiNaK salt speed up the corrosion rate remarkably by promoting the dissolution of Cr from the alloy matrix into the salt. With the concentration of SO42- ions in the FLiNaK salt increases from 100 ppm to 1000 ppm, the weight losses and the Cr depletion layer depths of the corroded specimens increase linearly. Even in the case of the heavy corrosion attack caused by the SO42- ions, the corrosion performance is similar between the base zone and fusion zone in the GH3535 weld joint. It is demonstrated that the structural diversity caused by the welding process has little impact on the corrosion performances of GH3535 alloy in FLiNaK molten salt.

Interaction of NaOH solutions with silica surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rimsza, Jessica M.; Jones, Reese E.; Criscenti, Louise J.

Sodium adsorption on silica surfaces depends on the solution counter-ion. Here, we use NaOH solutions to investigate basic environments. Sodium adsorption on hydroxylated silica surfaces from NaOH solutions were investigated through molecular dynamics with a dissociative force field, allowing for the development of secondary molecular species. Furthermore, across the NaOH concentrations (0.01 M – 1.0 M), ~50% of the Na + ions were concentrated in the surface region, developing silica surface charges between –0.01 C/m 2 (0.01 M NaOH) and –0.76 C/m 2 (1.0 M NaOH) due to surface site deprotonation. Five inner-sphere adsorption complexes were identified, including monodentate, bidentate,more » and tridentate configurations and two additional structures, with Na + ions coordinated by bridging oxygen and hydroxyl groups or water molecules. Coordination of Na + ions by bridging oxygen atoms indicates partial or complete incorporation of Na + ions into the silica surface. Residence time analysis identified that Na + ions coordinated by bridging oxygen atoms stayed adsorbed onto the surface four times longer than the mono/bi/tridentate species, indicating formation of relatively stable and persistent Na + ion adsorption structures. Such inner-sphere complexes form only at NaOH concentrations of > 0.5 M. Na + adsorption and lifetimes have implications for the stability of silica surfaces.« less

Interaction of NaOH solutions with silica surfaces

DOE PAGES

Rimsza, Jessica M.; Jones, Reese E.; Criscenti, Louise J.

2018-01-16

Sodium adsorption on silica surfaces depends on the solution counter-ion. Here, we use NaOH solutions to investigate basic environments. Sodium adsorption on hydroxylated silica surfaces from NaOH solutions were investigated through molecular dynamics with a dissociative force field, allowing for the development of secondary molecular species. Furthermore, across the NaOH concentrations (0.01 M – 1.0 M), ~50% of the Na + ions were concentrated in the surface region, developing silica surface charges between –0.01 C/m 2 (0.01 M NaOH) and –0.76 C/m 2 (1.0 M NaOH) due to surface site deprotonation. Five inner-sphere adsorption complexes were identified, including monodentate, bidentate,more » and tridentate configurations and two additional structures, with Na + ions coordinated by bridging oxygen and hydroxyl groups or water molecules. Coordination of Na + ions by bridging oxygen atoms indicates partial or complete incorporation of Na + ions into the silica surface. Residence time analysis identified that Na + ions coordinated by bridging oxygen atoms stayed adsorbed onto the surface four times longer than the mono/bi/tridentate species, indicating formation of relatively stable and persistent Na + ion adsorption structures. Such inner-sphere complexes form only at NaOH concentrations of > 0.5 M. Na + adsorption and lifetimes have implications for the stability of silica surfaces.« less

Neutron scattering studies of K3H(SO4)2 and K3D(SO4)2: the particle-in-a-box model for the quantum phase transition.

PubMed

Fillaux, François; Cousson, Alain

2012-08-21

In the crystal of K(3)H(SO(4))(2) or K(3)D(SO(4))(2), dimers SO(4)···H···SO(4) or SO(4)···D···SO(4) are linked by strong centrosymmetric hydrogen or deuterium bonds whose O···O length is ≈2.50 Å. We address two open questions. (i) Are H or D sites split or not? (ii) Is there any structural counterpart to the phase transition observed for K(3)D(SO(4))(2) at T(c) ≈ 85.5 K, which does not exist for K(3)H(SO(4))(2)? Neutron diffraction by single-crystals at cryogenic or room temperature reveals no structural transition and no resolvable splitting of H or D sites. However, the width of the probability densities suggest unresolved splitting of the wavefunctions suggesting rigid entities H(L1/2)-H(R1/2) or D(L1/2)-D(R1/2) whose separation lengths are l(H) ≈ 0.16 Å or l(D) ≈ 0.25 Å. The vibrational eigenstates for the center of mass of H(L1/2)-H(R1/2) revealed by inelastic neutron scattering are amenable to a square-well and we suppose the same potential holds for D(L1/2)-D(R1/2). In order to explain dielectric and calorimetric measurements of mixed crystals K(3)D((1-ρ))H(ρ)(SO(4))(2) (0 ≤ ρ ≤ 1), we replace the classical notion of order-disorder by the quantum notion of discernible (e.g., D(L1/2)-D(R1/2)) or indiscernible (e.g., H(L1/2)-H(R1/2)) components depending on the separation length of the split wavefunction. The discernible-indiscernible isostructural transition at finite temperatures is induced by a thermal pure quantum state or at 0 K by ρ.

Formation of apatitic calcium phosphates in a Na-K-phosphate solution of pH 7.4.

PubMed

Tas, A C; Aldinger, F

2005-02-01

Poorly crystalline, apatitic calcium phosphate powders have been synthesized by slowly adding a Na- and K-containing reference phosphate solution with a pH value of 7.4 to an aqueous calcium nitrate solution at 37 degrees C. Nano-particulated apatitic powders obtained were shown to contain small amounts of Na and K, which render them more similar in chemical composition to that of the bone mineral. Precipitated and dried powders were found to exhibit self-hardening cement properties when kneaded in a mortar with a sodium citrate- and sodium phosphate-containing starter solution. The same phosphate solution used in powder synthesis was found to be able to partially convert natural, white and translucent marble pieces of calcite (CaCO3) into calcium-deficient hydroxyapatite upon aging the samples in that solution for 3 days at 60 degrees C. Sample characterization was performed by using scanning electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, inductively-coupled plasma atomic emission spectroscopy, and simultaneous thermogravimetry and differential thermal analysis.

Novel Rechargeable M3V2(PO4)3//Zinc (M = Li, Na) Hybrid Aqueous Batteries with Excellent Cycling Performance

PubMed Central

Zhao, H. B.; Hu, C. J.; Cheng, H. W.; Fang, J. H.; Xie, Y. P.; Fang, W. Y.; Doan, T. N. L.; Hoang, T. K. A.; Xu, J. Q.; Chen, P.

2016-01-01

A rechargeable hybrid aqueous battery (ReHAB) containing NASICON-type M3V2(PO4)3 (M = Li, Na) as the cathodes and Zinc metal as the anode, working in Li2SO4-ZnSO4 aqueous electrolyte, has been studied. Both of Li3V2(PO4)3 and Na3V2(PO4)3 cathodes can be reversibly charge/discharge with the initial discharge capacity of 128 mAh g−1 and 96 mAh g−1 at 0.2C, respectively, with high up to 84% of capacity retention ratio after 200 cycles. The electrochemical assisted ex-XRD confirm that Li3V2(PO4)3 and Na3V2(PO4)3 are relative stable in aqueous electrolyte, and Na3V2(PO4)3 showed more complicated electrochemical mechanism due to the co-insertion of Li+ and Na+. The effect of pH of aqueous electrolyte and the dendrite of Zn on the cycling performance of as designed MVP/Zn ReHABs were investigated, and weak acidic aqueous electrolyte with pH around 4.0–4.5 was optimized. The float current test confirmed that the designed batteries are stable in aqueous electrolytes. The MVP//Zn ReHABs could be a potential candidate for future rechargeable aqueous battery due to their high safety, fast dynamic speed and adaptable electrochemical window. Moreover, this hybrid battery broadens the scope of battery material research from single-ion-involving to double-ions -involving rechargeable batteries. PMID:27174224

Novel Rechargeable M3V2(PO4)3//Zinc (M = Li, Na) Hybrid Aqueous Batteries with Excellent Cycling Performance

NASA Astrophysics Data System (ADS)

Zhao, H. B.; Hu, C. J.; Cheng, H. W.; Fang, J. H.; Xie, Y. P.; Fang, W. Y.; Doan, T. N. L.; Hoang, T. K. A.; Xu, J. Q.; Chen, P.

2016-05-01

A rechargeable hybrid aqueous battery (ReHAB) containing NASICON-type M3V2(PO4)3 (M = Li, Na) as the cathodes and Zinc metal as the anode, working in Li2SO4-ZnSO4 aqueous electrolyte, has been studied. Both of Li3V2(PO4)3 and Na3V2(PO4)3 cathodes can be reversibly charge/discharge with the initial discharge capacity of 128 mAh g-1 and 96 mAh g-1 at 0.2C, respectively, with high up to 84% of capacity retention ratio after 200 cycles. The electrochemical assisted ex-XRD confirm that Li3V2(PO4)3 and Na3V2(PO4)3 are relative stable in aqueous electrolyte, and Na3V2(PO4)3 showed more complicated electrochemical mechanism due to the co-insertion of Li+ and Na+. The effect of pH of aqueous electrolyte and the dendrite of Zn on the cycling performance of as designed MVP/Zn ReHABs were investigated, and weak acidic aqueous electrolyte with pH around 4.0-4.5 was optimized. The float current test confirmed that the designed batteries are stable in aqueous electrolytes. The MVP//Zn ReHABs could be a potential candidate for future rechargeable aqueous battery due to their high safety, fast dynamic speed and adaptable electrochemical window. Moreover, this hybrid battery broadens the scope of battery material research from single-ion-involving to double-ions -involving rechargeable batteries.

Delayed rectifier potassium channels are involved in SO2 derivative-induced hippocampal neuronal injury.

PubMed

Li, Guangke; Sang, Nan

2009-01-01

Recent studies implicate the possible neurotoxicity of SO(2), however, its mechanisms remain unclear. In the present study, we investigated SO(2) derivative-induced effect on delayed rectifier potassium channels (I(K)) and cellular death/apoptosis in primary cultured hippocampal neurons. The results demonstrate that SO(2) derivatives (NaHSO(3) and Na(2)SO(3), 3:1M/M) effectively augmented I(K) and promoted the activation of delayed rectifier potassium channels. Also, SO(2) derivatives increased neuronal death percentage and contributed to the formation of DNA ladder in concentration-dependent manners. Interestingly, the neuronal death and DNA ladder formation, caused by SO(2) derivatives, could be attenuated by the delayed rectifier potassium channel blocker (tetraethylammonium, TEA), but not by the transient outward potassium channel blocker (4-aminopyridine, 4-AP). It implies that stimulating delayed rectifier potassium channels were involved in SO(2) derivative-caused hippocampal neuronal insults, and blocking these channels might be one of the possibly clinical treatment for SO(2)-caused neuronal dysfunction.

X-ray and Mössbauer study of structural changes in K3Na(FeO4)2

NASA Astrophysics Data System (ADS)

Dedushenko, S. K.; Zhizhin, M. G.; Perfiliev, Yu. D.

2005-11-01

Mixed potassium sodium ferrate(VI), K3Na(FeO4)2, has been synthesized by precipitation from alkaline solution. At room temperature it decomposes spontaneously giving Fe(III) compounds and ferrate(VI) with a structure similar to that of K2FeO4, which is confirmed by X-ray diffraction and Mössbauer spectroscopy.

(C6N2H16)[Co(H2O)6](SO4)2.2H2O: A new hybrid material based on sulfate templated by diprotonated trans-1,4-diaminocyclohexane

NASA Astrophysics Data System (ADS)

Hamdi, N.; Ngopoh, F. A. I.; da Silva, I.; El Bali, B.; Lachkar, M.

2018-03-01

Employing trans-1,4-diaminocyclohexane (DACH) as template, the new hybrid sulphate (C6N2H16)[Co(H2O)6](SO4)2.2H2O was prepared in solution. Single-crystal X-ray diffraction analysis shows that it crystallizes in the monoclinic system (S.G.: P 21/n), with the following unit-cell parameters (Å,°): a = 6.2897(2), b = 12.3716(6), c = 13.1996(4), β = 98.091(3) V = 1016.89(7) Å3, Z = 4. Its 3D crystal structure is made upon isolated [Co(H2O)6] octahedra, regular [SO4] tetrahedra, protonated DACH and free H2O molecules, which interact through N-H···O and O-H···O hydrogen bonds. The Fourier transform infrared result exhibits bands corresponding to the vibrations of DACH, sulfate group and water molecules. The thermal decomposition of the phase consists mainly in the loss of the organic moiety and one sulfate group, leading thus to the formation of anhydrous cobalt sulfate.

A potential model for sodium chloride solutions based on the TIP4P/2005 water model

NASA Astrophysics Data System (ADS)

Benavides, A. L.; Portillo, M. A.; Chamorro, V. C.; Espinosa, J. R.; Abascal, J. L. F.; Vega, C.

2017-09-01

Despite considerable efforts over more than two decades, our knowledge of the interactions in electrolyte solutions is not yet satisfactory. Not even one of the most simple and important aqueous solutions, NaCl(aq), escapes this assertion. A requisite for the development of a force field for any water solution is the availability of a good model for water. Despite the fact that TIP4P/2005 seems to fulfill the requirement, little work has been devoted to build a force field based on TIP4P/2005. In this work, we try to fill this gap for NaCl(aq). After unsuccessful attempts to produce accurate predictions for a wide range of properties using unity ionic charges, we decided to follow recent suggestions indicating that the charges should be scaled in the ionic solution. In this way, we have been able to develop a satisfactory non-polarizable force field for NaCl(aq). We evaluate a number of thermodynamic properties of the solution (equation of state, maximum in density, enthalpies of solution, activity coefficients, radial distribution functions, solubility, surface tension, diffusion coefficients, and viscosity). Overall the results for the solution are very good. An important achievement of our model is that it also accounts for the dynamical properties of the solution, a test for which the force fields so far proposed failed. The same is true for the solubility and for the maximum in density where the model describes the experimental results almost quantitatively. The price to pay is that the model is not so good at describing NaCl in the solid phase, although the results for several properties (density and melting temperature) are still acceptable. We conclude that the scaling of the charges improves the overall description of NaCl aqueous solutions when the polarization is not included.

Frequency of Application of AmF/NaF/SnCl2 Solution and Its Potential in Inhibiting the Progression of Erosion in Human Dental Enamel - An In Vitro Study.

PubMed

da Silva, Camilla Vieira; Nazello, Jessica Laporta; de Freitas, Patricia Moreira

To evaluate whether increasing the frequency of its use can enhance the protective effect of AmF/NaF/SnCl2 solution against dental erosion. Sixty human enamel samples were obtained from sound human third molars, and after the formation of incipient erosive lesions (1% citric acid, pH 4.0, for 3 min), they were divided into five treatment groups (n = 12): G1 - deionised water (negative control); G2 - NaF solution (positive control) once a day; G3 - NaF solution (positive control) twice a day; G4 - AmF/NaF/SnCl2 solution once a day; G5 - AmF/NaF/SnCl2 solution twice a day. The samples were then subjected to 5 days of erosive cycling through 6 daily immersions (2 min each) in citric acid solution (0.05 M, pH 2.6). At the end of erosive cycling, surface wear was determined by means of optical profilometry. One-way ANOVA showed that the surface wear was affected by surface treatments (p < 0.001). Tukey's test showed no difference between the groups in which NaF was applied once or twice, but they showed limited reduction in wear compared to the deionised water group (G1). In the groups treated with the AmF/NaF/SnCl2 solution, there was a statistically significant difference between one and two application times (p < 0.001). Although both demonstrated statistically significantly reduced tissue loss, increasing the frequency increased its anti-erosive potential. The AmF/NaF/SnCl2 solution proved to be effective in reducing dental enamel surface loss and its use twice a day potentiated its anti-erosive effect.

High performance sodium-ion hybrid capacitor based on Na2Ti2O4(OH)2 nanostructures

NASA Astrophysics Data System (ADS)

Babu, Binson; Shaijumon, M. M.

2017-06-01

Hybrid Na-ion capacitors bridge the performance gap between Na-ion batteries and supercapacitors and offer excellent energy and power characteristics. However, designing efficient anode and cathode materials with improved kinetics and long cycle life is essential for practical implementation of this technology. Herein, layered sodium titanium oxide hydroxide, Na2Ti2O4(OH)2, synthesized through hydrothermal technique, is studied as efficient anode material for hybrid Na-ion capacitor. Half-cell electrochemical studies vs. Na/Na+ showed excellent performance for Na2Ti2O4(OH)2 electrode, with ∼57.2% of the total capacity (323.3 C g-1 at 1.0 mV s-1) dominated by capacitive behavior and the remaining due to Na-intercalation. The obtained values are in good agreement with Trasatti plots indicating the potential of this material as efficient anode for hybrid Na-ion capacitor. Further, a full cell Na-ion capacitor is fabricated with Na2Ti2O4(OH)2 as anode and chemically activated Rice Husk Derived Porous Carbon (RHDPC-KOH) as cathode by using organic electrolyte. The hybrid device, operated at a maximum cell voltage of 4 V, exhibits stable electrochemical performance with a maximum energy density of ∼65 Wh kg-1 (at 500 W kg-1, 0.20 A g-1) and with more than ∼ 93% capacitive retention after 3000 cycles.

Thermo and mechanoluminescence of Dy3+ activated K2Mg2(SO4)3 phosphor

NASA Astrophysics Data System (ADS)

Panigrahi, A. K.; Dhoble, S. J.; Kher, R. S.; Moharil, S. V.

2003-08-01

A solid state diffusion method for the preparation of (K2 : Dy)Mg2(SO4)3 and (K2 : Dy,P)Mg2(SO4)3 phosphors is reported. Thermoluminescence (TL) and mechanoluminescence (ML) characteristics are studied. TL, shown by the (K2 : Dy,P)Mg2(SO4)3 phosphor is 60% as intense as the conventional CaSO4 : Dy phosphor used in the TLD of ionization radiation. It has a linear TL dose response and a negligible fading. These properties of (K2 : Dy,P)Mg2(SO4)3 should be suitable in dosimetry of ionization radiation using TL technique. ML of (K2 : Dy)Mg2(SO4)3 shows one peak which has been observed in ML intensity versus time curve. The ML peak shows the recombination of electrons with free radicals (anion radicals produced by γ-irradiation) released from traps during the mechanical pressure applied on the Dy activated K2Mg2(SO4)3 phosphor. This ML mechanism is proposed for γ-irradiated sulfate based phosphors. It has been found that the total light output, i.e. ML intensity, increases with concentration of dopant, strain rate and irradiation dose of the phosphor. Mechanoluminescence and ML emission spectra of (K2 : Dy)Mg2(SO4)3 were recorded for better understanding of the ML process. The TL and ML measurements have also been performed to elucidate the mechanism of ML. Some correlation between ML and TL has also been found.

Na/beta-alumina/NaAlCl4, Cl2/C circulating cell

NASA Technical Reports Server (NTRS)

Cherng, Jing-Yih; Bennion, Douglas N.

1987-01-01

A study was made of a high specific energy battery based on a sodium negative electrode and a chlorine positive electrode with molten AlCl3-NaCl electrolyte and a solid beta alumina separator. The basic performance of a Na beta-alumina NaAlCl4, Cl2/C circulating cell at 200 C was demonstrated. This cell can be started at 150 C. The use of melting sodium chloroaluminate electrolyte overcomes some of the material problems associated with the high working temperatures of present molten salt systems, such as Na/S and LiAl/FeS, and retains the advantages of high energy density and relatively efficient electrode processes. Preliminary investigations were conducted on a sodium-chlorine static cell, material compability, electrode design, wetting, and theoretical calculations to assure a better chance of success before assembling a Na/Cl2 circulating cell. Mathematical models provide a theoretical explanation for the performance of the NaCl2 battery. The results of mathematical models match the experimental results very well. According to the result of the mathematical modeling, an output at 180 mA/sq cm and 3.2 V can be obtained with optimized cell design.

Nedd4-2 Modulates Renal Na+-Cl− Cotransporter via the Aldosterone-SGK1-Nedd4-2 Pathway

PubMed Central

Arroyo, Juan Pablo; Lagnaz, Dagmara; Ronzaud, Caroline; Vázquez, Norma; Ko, Benjamin S.; Moddes, Lauren; Ruffieux-Daidié, Dorothée; Hausel, Pierrette; Koesters, Robert; Yang, Baoli; Stokes, John B.; Hoover, Robert S.

2011-01-01

Regulation of renal Na+ transport is essential for controlling blood pressure, as well as Na+ and K+ homeostasis. Aldosterone stimulates Na+ reabsorption by the Na+-Cl− cotransporter (NCC) in the distal convoluted tubule (DCT) and by the epithelial Na+ channel (ENaC) in the late DCT, connecting tubule, and collecting duct. Aldosterone increases ENaC expression by inhibiting the channel's ubiquitylation and degradation; aldosterone promotes serum-glucocorticoid-regulated kinase SGK1-mediated phosphorylation of the ubiquitin-protein ligase Nedd4-2 on serine 328, which prevents the Nedd4-2/ENaC interaction. It is important to note that aldosterone increases NCC protein expression by an unknown post-translational mechanism. Here, we present evidence that Nedd4-2 coimmunoprecipitated with NCC and stimulated NCC ubiquitylation at the surface of transfected HEK293 cells. In Xenopus laevis oocytes, coexpression of NCC with wild-type Nedd4-2, but not its catalytically inactive mutant, strongly decreased NCC activity and surface expression. SGK1 prevented this inhibition in a kinase-dependent manner. Furthermore, deficiency of Nedd4-2 in the renal tubules of mice and in cultured mDCT15 cells upregulated NCC. In contrast to ENaC, Nedd4-2-mediated inhibition of NCC did not require the PY-like motif of NCC. Moreover, the mutation of Nedd4-2 at either serine 328 or 222 did not affect SGK1 action, and mutation at both sites enhanced Nedd4-2 activity and abolished SGK1-dependent inhibition. Taken together, these results suggest that aldosterone modulates NCC protein expression via a pathway involving SGK1 and Nedd4-2 and provides an explanation for the well-known aldosterone-induced increase in NCC protein expression. PMID:21852580

Corrosion of Type 7075-T73 Aluminum in a 10% HNO3 + Fe2(SO4)3 Deoxidizer Solution

NASA Astrophysics Data System (ADS)

Savas, Terence P.; Earthman, James C.

2009-03-01

Localized corrosion damage in Type 7075-T73 aluminum was investigated for a HNO3 + Fe2(SO4)3 deoxidizer solution which is frequently used for surface pretreatment prior to anodizing. The corrosion damage was quantified in the time domain using the electrochemical noise resistance ( Rn) and in the frequency domain using the spectral noise impedance ( Rsn). The Rsn was derived from an equivalent electrical circuit model that represented the corrosion cell implemented in the present study. These data are correlated to scanning electron microscopy (SEM) examinations and corresponding statistical analysis based on digital image analysis of the corroded surfaces. Other data used to better understand the corrosion mechanisms include the open circuit potential (OCP) and coupling-current time records. Based on statistical analysis of the pit structures for 600 and 1200 s exposures, the best fit was achieved with a 3-paramater lognormal distribution. It was observed for the 1200 s exposure that a small population of pits continued to grow beyond a threshold critical size of 10 μm. In addition, significant grain boundary attack was observed after 1200 s exposure. These data are in good agreement with the electrochemical data. Specifically, the Rn was computed to be 295 and 96 Ω-cm2 for 600 and 1200 s exposures, respectively. The calculated value of Rsn, theoretically shown to be equal to Rn in the low frequency limit, was higher than Rn for a 1200 s exposure period. However, better agreement between the Rn and Rsn was found for frequencies above 0.01 Hz. Experimental results on the measurement performance for potassium chloride (KCl) saturated double-junction Ag/AgCl and single-junction Hg/Hg2Cl2 reference electrodes in the low-pH deoxidizer solution are also compared.

Distinctly Different Glass Transition Behaviors of Trehalose Mixed with Na2HPO 4 or NaH 2PO 4: Evidence for its Molecular Origin.

PubMed

Weng, Lindong; Elliott, Gloria D

2015-07-01

The present study is aimed at understanding how the interactions between sugar molecules and phosphate ions affect the glass transition temperature of their mixtures, and the implications for pharmaceutical formulations. The glass transition temperature (Tg) and the α-relaxation temperature (Tα) of dehydrated trehalose/sodium phosphate mixtures (monobasic or dibasic) were determined by differential scanning calorimetry and dynamic mechanical analysis, respectively. Molecular dynamics simulations were also conducted to investigate the microscopic interactions between sugar molecules and phosphate ions. The hydrogen-bonding characteristics and the self-aggregation features of these mixtures were quantified and compared. Thermal analysis measurements demonstrated that the addition of NaH2PO4 decreased both the glass transition temperature and the α-relaxation temperature of the dehydrated trehalose/NaH2PO4 mixture compared to trehalose alone while both Tg and Tα were increased by adding Na2HPO4 to pure trehalose. The hydrogen-bonding interactions between trehalose and HPO4(2-) were found to be stronger than both the trehalose-trehalose hydrogen bonds and those formed between trehalose and H2PO4(-). The HPO4(2-) ions also aggregated into smaller clusters than H2PO4(-) ions. The trehalose/Na2HPO4 mixture yielded a higher T g than pure trehalose because marginally self-aggregated HPO4(2-) ions established a strengthened hydrogen-bonding network with trehalose molecules. In contrast H2PO4(-) ions served only as plasticizers, resulting in a lower Tg of the mixtures than trehalose alone, creating large-sized ionic pockets, weakening interactions, and disrupting the original hydrogen-bonding network amongst trehalose molecules.

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.

Thermal decomposition of sodium amide, NaNH2, and sodium amide hydroxide composites, NaNH2-NaOH.

PubMed

Jepsen, Lars H; Wang, Peikun; Wu, Guotao; Xiong, Zhitao; Besenbacher, Flemming; Chen, Ping; Jensen, Torben R

2016-09-14

Sodium amide, NaNH 2 , has recently been shown to be a useful catalyst to decompose NH 3 into H 2 and N 2 , however, sodium hydroxide is omnipresent and commercially available NaNH 2 usually contains impurities of NaOH (<2%). The thermal decomposition of NaNH 2 and NaNH 2 -NaOH composites is systematically investigated and discussed. NaNH 2 is partially dissolved in NaOH at T > 100 °C, forming a non-stoichiometric solid solution of Na(OH) 1-x (NH 2 ) x (0 < x < ∼0.30), which crystallizes in an orthorhombic unit cell with the space group P2 1 2 1 2 1 determined by synchrotron powder X-ray diffraction. The composite xNaNH 2 -(1 - x)NaOH (∼0.70 < x < 0.72) shows a lowered melting point, ∼160 °C, compared to 200 and 318 °C for neat NaNH 2 and NaOH, respectively. We report that 0.36 mol of NH 3 per mol of NaNH 2 is released below 400 °C during heating in an argon atmosphere, initiated at its melting point, T = 200 °C, possibly due to the formation of the mixed sodium amide imide solid solution. Furthermore, NaOH reacts with NaNH 2 at elevated temperatures and provides the release of additional NH 3 .

Effect of NaNO3 concentration on anodic electrochemical behavior on the Sb surface in NaOH solution

NASA Astrophysics Data System (ADS)

He, Yun-long; Xu, Rui-dong; He, Shi-wei; Chen, Han-sen; Li, Kuo; Zhu, Yun; Shen, Qing-feng

2018-03-01

The effect of NaNO3 concentration on the anodic electrochemical behavior of antimony in 4 M NaOH solution was investigated using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) analyses. The mechanism of NO 3 - concentration effect on the anodic electrochemical behavior of antimony was proposed, and its availability was confirmed by experimental results. The effect of NaNO3 on the anodic behavior of antimony in NaOH solution can be interpreted as a stepwise formation of different antimony compounds with different NaNO3 concentrations. Metallic antimony is apt to be oxidized into Sb2O3 within the NaNO3 concentration range of 0-0.48 M. NaSbO3 can be found on the antimony surface when the NaNO3 concentration increases gradually. Insoluable NaSbO3 inhibits the anodic oxidation of antimony due to its shielding effect on the mass transport of the reactants and products. Surface morphology and composition were analyzed by X-ray photoelectron spectroscopy (XPS), scanning electronic microscopy (SEM), and electron dispersion spectroscopy (EDS) analyses. Results indicate that the anodic oxidation layer is composed of Sb2O3, NaSbO3, and Sb. The atomic proportion of antimony in the form of NaSbO3 increases with increasing NaNO3 concentration due to the powerful oxidizing property of NaNO3.

Effect of SO2 on the transport properties of an imidazolium ionic liquid and its lithium solution.

PubMed

Monteiro, Marcelo J; Ando, Rômulo A; Siqueira, Leonardo J A; Camilo, Fernanda F; Santos, Paulo S; Ribeiro, Mauro C C; Torresi, Roberto M

2011-08-11

Transport coefficients have been measured as a function of the concentration of sulfur dioxide, SO(2), dissolved in 1-butyl-2,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide, [BMMI][Tf(2)N], as well as in its lithium salt solution, Li[Tf(2)N]. The SO(2) reduces viscosity and density and increases conductivity and diffusion coefficients in both the neat [BMMI][Tf(2)N] and the [BMMI][Tf(2)N]-Li[Tf(2)N] solution. The conductivity enhancement is not assigned to a simple viscosity effect; the weakening of ionic interactions upon SO(2) addition also plays a role. Microscopic details of the SO(2) effect were unraveled using Raman spectroscopy and molecular dynamics (MD) simulations. The Raman spectra suggest that the Li(+)-[Tf(2)N] interaction is barely affected by SO(2), and the SO(2)-[Tf(2)N] interaction is weaker than previously observed in an investigation of an ionic liquid containing the bromide anion. Transport coefficients calculated by MD simulations show the same trend as the experimental data with respect to SO(2) content. The MD simulations provide structural information on SO(2) molecules around [Tf(2)N], in particular the interaction of the sulfur atom of SO(2) with oxygen and fluorine atoms of the anion. The SO(2)-[BMMI] interaction is also important because the [BMMI] cations with above-average mobility have a larger number of nearest-neighbor SO(2) molecules. © 2011 American Chemical Society

NaGd(MoO4)2 nanocrystals with diverse morphologies: controlled synthesis, growth mechanism, photoluminescence and thermometric properties.

PubMed

Li, Anming; Xu, Dekang; Lin, Hao; Yang, Shenghong; Shao, Yuanzhi; Zhang, Yueli

2016-08-10

Pure tetragonal phase, uniform and well-crystallized sodium gadolinium molybdate (NaGd(MoO4)2) nanocrystals with diverse morphologies, e.g. nanocylinders, nanocubes and square nanoplates have been selectively synthesized via oleic acid-mediated hydrothermal method. The phase, structure, morphology and composition of the as-synthesized products are studied. Contents of both sodium molybdate and oleic acid of the precursor solutions are found to affect the morphologies of the products significantly, and oleic acid plays a key role in the morphology-controlled synthesis of NaGd(MoO4)2 nanocrystals with diverse morphologies. Growth mechanism of NaGd(MoO4)2 nanocrystals is proposed based on time-dependent morphology evolution and X-ray diffraction analysis. Morphology-dependent down-shifting photoluminescence properties of NaGd(MoO4)2: Eu(3+) nanocrystals, and upconversion photoluminescence properties of NaGd(MoO4)2: Yb(3+)/Er(3+) and Yb(3+)/Tm(3+) nanoplates are investigated in detail. Charge transfer band in the down-shifting excitation spectra shows a slight blue-shift, and the luminescence intensities and lifetimes of Eu(3+) are decreased gradually with the morphology of the nanocrystals varying from nanocubes to thin square nanoplates. Upconversion energy transfer mechanisms of NaGd(MoO4)2: Yb(3+)/Er(3+), Yb(3+)/Tm(3+) nanoplates are proposed based on the energy level scheme and power dependence of upconversion emissions. Thermometric properties of NaGd(MoO4)2: Yb(3+)/Er(3+) nanoplates are investigated, and the maximum sensitivity is determined to be 0.01333 K(-1) at 285 K.

NaGd(MoO4)2 nanocrystals with diverse morphologies: controlled synthesis, growth mechanism, photoluminescence and thermometric properties

PubMed Central

Li, Anming; Xu, Dekang; Lin, Hao; Yang, Shenghong; Shao, Yuanzhi; Zhang, Yueli

2016-01-01

Pure tetragonal phase, uniform and well-crystallized sodium gadolinium molybdate (NaGd(MoO4)2) nanocrystals with diverse morphologies, e.g. nanocylinders, nanocubes and square nanoplates have been selectively synthesized via oleic acid-mediated hydrothermal method. The phase, structure, morphology and composition of the as-synthesized products are studied. Contents of both sodium molybdate and oleic acid of the precursor solutions are found to affect the morphologies of the products significantly, and oleic acid plays a key role in the morphology-controlled synthesis of NaGd(MoO4)2 nanocrystals with diverse morphologies. Growth mechanism of NaGd(MoO4)2 nanocrystals is proposed based on time-dependent morphology evolution and X-ray diffraction analysis. Morphology-dependent down-shifting photoluminescence properties of NaGd(MoO4)2: Eu3+ nanocrystals, and upconversion photoluminescence properties of NaGd(MoO4)2: Yb3+/Er3+ and Yb3+/Tm3+ nanoplates are investigated in detail. Charge transfer band in the down-shifting excitation spectra shows a slight blue-shift, and the luminescence intensities and lifetimes of Eu3+ are decreased gradually with the morphology of the nanocrystals varying from nanocubes to thin square nanoplates. Upconversion energy transfer mechanisms of NaGd(MoO4)2: Yb3+/Er3+, Yb3+/Tm3+ nanoplates are proposed based on the energy level scheme and power dependence of upconversion emissions. Thermometric properties of NaGd(MoO4)2: Yb3+/Er3+ nanoplates are investigated, and the maximum sensitivity is determined to be 0.01333 K−1 at 285 K. PMID:27506629

High temperature redox reactions with uranium: Synthesis and characterization of Cs(UO{sub 2})Cl(SeO{sub 3}), Rb{sub 2}(UO{sub 2}){sub 3}O{sub 2}(SeO{sub 3}){sub 2}, and RbNa{sub 5}U{sub 2}(SO{sub 4}){sub 7}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Babo, Jean-Marie; Department of Civil and Environmental Engineering and Earth Sciences and Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, IN 46556; Albrecht-Schmitt, Thomas E., E-mail: talbrechtschmitt@gmail.com

2013-10-15

Cs(UO{sub 2})Cl(SeO{sub 3}) (1), Rb{sub 2}(UO{sub 2}){sub 3}O{sub 2}(SeO{sub 3}){sub 3} (2), and RbNa{sub 5}U{sub 2}(SO{sub 4}){sub 7} (3) single crystals were synthesized using CsCl, RbCl, and a CuCl/NaCl eutectic mixture as fluxes, respectively. Their lattice parameters and space groups are as follows: P2{sub 1}/n (a=6.548(1) Å, b=11.052(2) Å, c=10.666(2) Å and β=93.897(3)°), P1{sup ¯} (a=7.051(2) Å, b=7.198(2) Å, c=8.314(2) Å, α=107.897(3)°, β=102.687(3)° and γ=100.564(3)°) and C2/c (a=17.862(4) Å, b=6.931(1) Å, c=20.133(4) Å and β=109.737(6)°. The small anionic building units found in these compounds are SeO{sub 3}{sup 2−} and SO{sub 4}{sup 2−} tetrahedra, oxide, and chloride. The crystal structure ofmore » the first compound is composed of [(UO{sub 2}){sub 2}Cl{sub 2}(SeO{sub 3}){sub 2}]{sup 2−} chains separated by Cs{sup +} cations. The structure of (2) is constructed from [(UO{sub 2}){sub 3}O{sub 11}]{sup 16−} chains further connected through selenite units into layers stacked perpendicularly to the [0 1 0] direction, with Rb{sup +} cations intercalating between them. The structure of compound (3) is made of uranyl sulfate layers formed by edge and vertex connections between dimeric [U{sub 2}O{sub 16}] and [SO{sub 4}] polyhedra. These layers contain unusual sulfate–metal connectivity as well as large voids. - Graphical abstract: A new family of uranyl selenites and sulfates has been prepared by high-temperature redox reactions. This compounds display new bonding motifs. Display Omitted - Highlights: • Low-dimensional Uranyl Oxoanion compounds. • Conversion of U(IV) to U(VI) at high temperatures. • Dimensional reduction by both halides and stereochemically active lone-pairs.« less

Large hydrogen-bonded pre-nucleation (HSO4-)(H2SO4)m(H2O)k and (HSO4-)(NH3)(H2SO4)m(H2O)k clusters in the earth's atmosphere.

PubMed

Herb, Jason; Xu, Yisheng; Yu, Fangqun; Nadykto, A B

2013-01-10

The importance of pre-nucleation cluster stability as the key parameter controlling nucleation of atmospheric airborne ions is well-established. In this Article, large ternary ionic (HSO(4)(-))(H(2)SO(4))(m)(NH(3))(H(2)O)(n) clusters have been studied using Density Functional Theory (DFT) and composite ab initio methods. Twenty classes of clusters have been investigated, and thermochemical properties of common atmospheric (HSO(4)(-))(H(2)SO(4))(m)(NH(3))(0)(H(2)O)(k) and (HSO(4)(-))(H(2)SO(4))(m)(NH(3))(1)(H(2)O)(n) clusters (with m, k, and n up to 3) have been obtained. A large amount of new themochemical and structural data ready-to-use for constraining kinetic nucleation models has been reported. We have performed a comprehensive thermochemical analysis of the obtained data and have investigated the impacts of ammonia and negatively charged bisulfate ion on stability of binary clusters in some detail. The comparison of theoretical predictions and experiments shows that the PW91PW91/6-311++G(3df,3pd) results are in very good agreement with both experimental data and high level ab initio CCSD(T)/CBS values and suggest that the PW91PW91/6-311++G(3df,3pd) method is a viable alternative to higher level ab initio methods in studying large pre-nucleation clusters, for which the higher level computations are prohibitively expensive. The uncertainties in both theory and experiments have been investigated, and possible ways of their reduction have been proposed.

Comparative investigation of the solution species [U(CO3)5]6- and the crystal structure of Na6[U(CO3)5].12H2O.

PubMed

Hennig, Christoph; Ikeda-Ohno, Atsushi; Emmerling, Fanziska; Kraus, Werner; Bernhard, Gert

2010-04-21

The limiting U(IV) carbonate species in aqueous solution was investigated by comparing its structure parameters with those of the complex preserved in a crystal structure. The solution species prevails in aqueous solution of 0.05 M U(IV) and 1 M NaHCO(3) at pH 8.3. Single crystals of Na(6)[U(CO(3))(5)].12H(2)O were obtained directly from this mother solution. The U(IV) carbonate complex in the crystal structure was identified as a monomeric [U(CO(3))(5)](6-) anionic complex. The interatomic distances around the U(IV) coordination polyhedron show average distances of U-O = 2.461(8) A, U-C = 2.912(4) A and U-O(dist) = 4.164(6) A. U L(3)-edge EXAFS spectra were collected from the solid Na(6)[U(CO(3))(5)].12H(2)O and the corresponding solution. The first shell of the Fourier transforms (FTs) revealed, in both samples, a coordination of ten oxygen atoms at an average U-O distance of 2.45 +/- 0.02 A, the second shell originates from five carbon atoms with a U-C distance of 2.91 +/- 0.02 A, and the third shell was fit with single and multiple scattering paths of the distal oxygen at 4.17 +/- 0.02 A. These data indicate the identity of the [U(CO(3))(5)](6-) complex in solid and solution state. The high negative charge of the [U(CO(3))(5)](6-) anion is compensated by Na(+) cations. In solid state the Na(+) cations form a bridging network between the [U(CO(3))(5)](6-) units, while in liquid state the Na(+) cations seem to be located close to the anionic complex. The average metal-oxygen distances of the coordination polyhedron show a linear correlation to the radius contraction of the neighbouring actinide(IV) ions and indicate the equivalence of the [An(CO(3))(5)](6-) coordination within the series of thorium, uranium, neptunium and plutonium.

Enhanced near-infrared photocatalysis of NaYF4:Yb, Tm/CdS/TiO2 composites.

PubMed

Guo, Xingyuan; Di, Weihua; Chen, Changfeng; Liu, Chunxu; Wang, Xue; Qin, Weiping

2014-01-21

The previous works by our group (Chem. Commun., 2010, 46, 2304-2306; ACS Catal., 2013, 3, 405-412; Phys. Chem. Chem. Phys., 2013, 15, 14681-14688) have reported the near-infrared-driven photocatalysis of broadband semiconductor TiO2 or ZnO that was combined with upconverting luminescence particles to form a core-shell structure. However, the photocatalytic efficiency is low for this new type of photocatalysts. In this work, NaYF4:Yb,Tm/CdS/TiO2 composites for NIR photocatalysis were prepared by linking CdS and TiO2 nanocrystals on the NaYF4:Yb,Tm microcrystal surfaces. CdS and TiO2 were well interacted to form a heterojunction structure. The energy transfer between NaYF4:Yb,Tm and the semiconductors CdS and TiO2 was investigated by steady-state and dynamic fluorescence spectroscopy. The photocatalytic activities of the as-prepared composites were evaluated by the degradation of methylene blue in aqueous solution upon NIR irradiation. Significantly, it was found that the united adhesions of CdS and TiO2 on the NaYF4:Yb,Tm particle surfaces showed much higher catalytic activities than the individual adhesion of CdS or TiO2 on the NaYF4:Yb,Tm surfaces. This was attributed mainly to the effective separation of the photogenerated electron-hole pairs due to the charge transfer across the CdS-TiO2 interface driven by the band potential difference between them. The presented composite structure of upconverting luminescence materials coupled with narrow/wide semiconductor heterojunctions provides a new model for improved NIR photocatalysis.

Adsorption of SO2 and NO from incineration flue gas onto activated carbon fibers.

PubMed

Liu, Zhen-Shu

2008-11-01

Activated carbon fibers (ACFs) were used to remove SO2 and NO from incineration flue gas. Three types of ACFs in their origin state and after pretreatment with HNO3, NaOH, and KOH were investigated. The removal efficiencies of SO2 and NO were determined experimentally at defined SO2 and NO concentrations and at temperatures of 150, 200 and 260 degrees C. Experimental results indicated that the removal efficiencies of SO2 and NO using the original ACFs were < 56% and < 27%, respectively. All ACFs modified with HNO3, NaOH, and KOH solution could increase the removal efficiencies of SO(2) and NO. The mesopore volumes and functional groups of ACFs are important in determining the removal of SO2 and NO. When the mesopore volumes of the ACFs are insufficient for removing SO2 and NO, the functional groups on the ACFs are not important in determining the removal of SO2 and NO. On the contrary, the effects of the functional groups on the removal of SO2 and NO are more important than the mesopore volumes as the amount of mesopores on the ACFs is sufficient to remove SO2 and NO. Moreover, the removal efficiencies of SO2 and NO were greatest at 200 degrees C. When the inlet concentration of SO2 increased to 600 ppm, the removal efficiency of SO2 increased slightly and the removal efficiency of NO decreased.

Simultaneous removal of SO2 and NOx from flue gas by wet scrubbing using a urea solution.

PubMed

Li, Ge; Wang, Baodong; Xu, Wayne Qiang; Li, Yonglong; Han, Yifan; Sun, Qi

2018-03-27

Nitrogen oxides (NO x ) and sulfur dioxide (SO 2 ) are major air pollutants, so simultaneously removing them from gases emitted during fossil fuel combustion in stationary systems is important. Wet denitrification using urea is used for a wide range of systems. Additives have strong effects on wet denitrification using urea, and different mechanisms are involved and different effects found using different additives. In this study, the effects of different additives, initial urea concentrations, reaction temperatures, initial pH values, gas flow rates, and reaction times on the simultaneous desulfurization and denitrification efficiencies achieved using wet denitrification using urea were studied in single factor experiment. The optimum reaction conditions for desulfurization and denitrification were found. Desulfurization and denitrification efficiencies of 97.5% and 96.3%, respectively, were achieved at a KMnO 4 concentration 5 mmol/L, a reaction temperature of 70°C, initial urea solution pH 8, a urea concentration of 9%, and a gas flow rate of 40 L/h. The concentrations of the desulfurization and denitrification reaction products in the solution were determined. NO x was mainly transformed into N 2 , and the [Formula: see text] and [Formula: see text] concentrations in the solution became very low. The reactions involved in SO 2 and NO x removal using urea were analyzed from the thermodynamic viewpoint. Increasing the temperature was not conducive to the reactions but increased the rate constant, so an optimum temperature was determined. The simultaneous desulfurization and denitrification kinetics were calculated. The urea consumption and [Formula: see text], [Formula: see text], and [Formula: see text] generation reactions were all zero order. The [Formula: see text] generation rate was greater than the [Formula: see text] generation rate. The simultaneous desulfurization and denitrification process and mechanism were studied. The results provide reference

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.

Effect of HCl and H2SO4 treatment of TiO2 powder on the photosensitized degradation of aqueous rhodamine B under visible light.

PubMed

Park, Se-Keun; Shin, Hyunho

2014-10-01

The acid treatments of TiO2 nanopowder with HCI or H2SO4 solution increase the concentration of the hydroxyl group on TiO2 surfaces compared to bare TiO2, which acts as a Brønsted acid site. For the case of the HCl-treated TiO2, the dissociation of Brønsted acid (proton donor) sites on TiO2 leads to a drop in the pH levels of rhodamine B (RhB) dye solutions (leading to the protonation of the RhB molecule), which allows the physisorption of the uncharged carboxyl acid group on the positively charged TiO2 surface. The carboxyl acid group is believed to afford a more efficient charge injection from the Visible-light-excited RhB to the conduction band of TiO2 compared to the N-ethyl group, yielding a significantly enhanced photodegradation of RhB mainly via the N-de-ethylation pathway. For the case of the H2SO4-treated TiO2, although the dissociation of Brønsted acid sites on TiO2 is also achieved, its photoactivity is much lower than that of the HCl-treated TiO2. It seems that the presence of SO4(2-) on the H2SO4-treated TiO2 behaves as an *OH scavenger to prevent the photodegradation of the dye.

Acidosis Differentially Modulates Inactivation in NaV1.2, NaV1.4, and NaV1.5 Channels

PubMed Central

Vilin, Yury Y.; Peters, Colin H.; Ruben, Peter C.

2012-01-01

NaV channels play a crucial role in neuronal and muscle excitability. Using whole-cell recordings we studied effects of low extracellular pH on the biophysical properties of NaV1.2, NaV1.4, and NaV1.5, expressed in cultured mammalian cells. Low pH produced different effects on different channel subtypes. Whereas NaV1.4 exhibited very low sensitivity to acidosis, primarily limited to partial block of macroscopic currents, the effects of low pH on gating in NaV1.2 and NaV1.5 were profound. In NaV1.2 low pH reduced apparent valence of steady-state fast inactivation, shifted the τ(V) to depolarizing potentials and decreased channels availability during onset to slow and use-dependent inactivation (UDI). In contrast, low pH delayed open-state inactivation in NaV1.5, right-shifted the voltage-dependence of window current, and increased channel availability during onset to slow and UDI. These results suggest that protons affect channel availability in an isoform-specific manner. A computer model incorporating these results demonstrates their effects on membrane excitability. PMID:22701426

Theoretical prediction of morphotropic compositions in Na1/2Bi1/2TiO3-based solid solutions from transition pressures

NASA Astrophysics Data System (ADS)

Gröting, Melanie; Albe, Karsten

2014-02-01

In this article we present a method based on ab initio calculations to predict compositions at morphotropic phase boundaries in lead-free perovskite solid solutions. This method utilizes the concept of flat free energy surfaces and involves the monitoring of pressure-induced phase transitions as a function of composition. As model systems, solid solutions of Na1/2Bi1/2TiO3 with the alkali substituted Li1/2Bi1/2TiO3 and K1/2Bi1/2TiO3 and the alkaline earth substituted CaTiO3 and BaTiO3 are chosen. The morphotropic compositions are identified by determining the composition at which the phase transition pressure equals zero. In addition, we discuss the different effects of hydrostatic pressure (compression and tension) and chemical substitution on the antiphase tilts about the [111] axis (a-a-a-) present in pure Na1/2Bi1/2TiO3 and how they develop in the two solid solutions Na1/2Bi1/2TiO3-CaTiO3 and Na1/2Bi1/2TiO3-BaTiO3. Finally, we discuss the advantages and shortcomings of this simple computational approach.

Interpretation of the microwave effect on induction time during CaSO4 primary nucleation by a cluster coagulation model

NASA Astrophysics Data System (ADS)

Guo, Zhichao; Li, Liye; Han, Wenxiang; Li, Jiawei; Wang, Baodong; Xiao, Yongfeng

2017-10-01

The effects of microwave on the induction time of CaSO4 are studied experimentally and theoretically. In the experiments, calcium sulfate is precipitated by mixing aqueous CaCl2 solution and Na2SO4 solution. The induction time is measured by recording the change of turbidity in solution. Various energy inputs are used to investigate the effect of energy input on nucleation. The results show that the induction time decreases with increasing supersaturation and increasing energy input. Employing the classical nucleation theory, the interfacial tension is estimated. In addition, the microwave effects on nucleation order (n) and nucleation coefficient (kN) are also investigated, and the corresponding values of homogeneous nucleation are compared with the values of heterogeneous nucleation in the microwave field. A cluster coagulation model, which brings together the classic nucleation models and the theories describing the behavior of colloidal suspension, was applied to estimate the induction time under various energy inputs. It is found that when nucleation is prominently homogeneous, the microwave energy input does not change the number of monomers in dominating clusters. And when nucleation is prominently heterogeneous, although the dominating cluster size increases with supersaturation increasing, at the same supersaturation level, the dominating cluster size remains constant in the microwave field.

Electrogenic Na+/Ca2+ Exchange

PubMed Central

Danaceau, Jonathan P.; Lucero, Mary T.

2000-01-01

Olfactory receptor neurons (ORNs) from the squid, Lolliguncula brevis, respond to the odors l-glutamate or dopamine with increases in internal Ca2+ concentrations ([Ca2+]i). To directly asses the effects of increasing [Ca2+]i in perforated-patched squid ORNs, we applied 10 mM caffeine to release Ca2+ from internal stores. We observed an inward current response to caffeine. Monovalent cation replacement of Na+ from the external bath solution completely and selectively inhibited the caffeine-induced response, and ruled out the possibility of a Ca2+-dependent nonselective cation current. The strict dependence on internal Ca2+ and external Na+ indicated that the inward current was due to an electrogenic Na+/Ca2+ exchanger. Block of the caffeine-induced current by an inhibitor of Na+/Ca2+ exchange (50–100 μM 2′,4′-dichlorobenzamil) and reversibility of the exchanger current, further confirmed its presence. We tested whether Na+/Ca2+ exchange contributed to odor responses by applying the aquatic odor l-glutamate in the presence and absence of 2′,4′-dichlorobenzamil. We found that electrogenic Na+/Ca2+ exchange was responsible for ∼26% of the total current associated with glutamate-induced odor responses. Although Na+/Ca2+ exchangers are known to be present in ORNs from numerous species, this is the first work to demonstrate amplifying contributions of the exchanger current to odor transduction. PMID:10828249

High-performance carbon-coated ZnMn2O4 nanocrystallite supercapacitors with tailored microstructures enabled by a novel solution combustion method

NASA Astrophysics Data System (ADS)

Abdollahifar, Mozaffar; Huang, Sheng-Siang; Lin, Yu-Hsiang; Lin, Yan-Cheng; Shih, Bing-Yi; Sheu, Hwo-Shuenn; Liao, Yen-Fa; Wu, Nae-Lih

2018-02-01

Although ZnMn2O4 is widely studied as Li-ion battery anodes, it remains a challenge to tailor suitable microstructures of the oxide for supercapacitor applications. Carbon-coated ZnMn2O4 (C@ZMO) nanocrystallites showing high-performance pseudocapacitor behaviours in neutral aqueous electrolyte are for the first time successfully synthesised via a novel solution combustion process using polyethylene glycol as a multifunctional microstructure-directing agent. Controlling the molecular weight and amount of the polymer in the combustion solution enables the formation of highly-crystalline C@ZMO having substantially higher, by more than 5 folds, specific surface areas with mesoporous structures and conformal carbon coating via the one-pot synthesis process. The resulting C@ZMO supercapacitor electrodes in Na2SO4(aq) electrolyte exhibit ideal capacitive behaviours with specific capacitances up to 150 F g-1 and cycle stability showing no capacitance fade after 10,000 cycles at 60% of full capacity and >99% Coulombic efficiency. This study not only illustrates a new powerful synthesis route capable of producing conductive mesoporous crystalline oxide-based nanomaterials for energy storage applications but also reveals a new class of high-performance pseudocapacitive materials for neutral aqueous electrolytes.

Study of different solutes for determination of neutron source strength based on the water bath

NASA Astrophysics Data System (ADS)

Khabaz, Rahim

2018-09-01

Time required for activation to saturation and background measurement is considered a limitation of strength determination of radionuclide neutron sources using manganese bath system (MBS). The objective of this research was to evaluate the other solutes based on water bath for presentation of the suitable replacement with MBS. With the aid Monte Carlo simulation, for three neutron sources, having different neutron spectra, immersed in six aqueous solutions, i.e., Na2SO4, VOSO4, MnSO4, Rh2(SO4)3, In2(SO4)3, I2O5, the correction factors in all nuclei of solutions for neutron losses with different process were obtained. The calculations results indicate that the Rh2(SO4)3 and VOSO4 are best options for replacing with MnSO4.