Heterogeneous kinetics of H2O, HNO3 and HCl on HNO3 hydrates (α-NAT, β-NAT, NAD in the range 175–200 K

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R. Iannarelli

2016-09-01

Full Text Available Experiments on the title compounds have been performed using a multidiagnostic stirred-flow reactor (SFR in which the gas phase as well as the condensed phase has been simultaneously investigated under stratospheric temperatures in the range 175–200 K. Wall interactions of the title compounds have been taken into account using Langmuir adsorption isotherms in order to close the mass balance between deposited and desorbed (recovered compounds. Thin solid films at 1 µm typical thickness have been used as a proxy for atmospheric ice particles and have been deposited on a Si window of the cryostat, with the optical element being the only cold point in the deposition chamber. Fourier transform infrared (FTIR absorption spectroscopy in transmission as well as partial and total pressure measurement using residual gas mass spectrometry (MS and sensitive pressure gauges have been employed in order to monitor growth and evaporation processes as a function of temperature using both pulsed and continuous gas admission and monitoring under SFR conditions. Thin solid H2O ice films were used as the starting point throughout, with the initial spontaneous formation of α-NAT (nitric acid trihydrate followed by the gradual transformation of α- to β-NAT at T > 185 K. Nitric acid dihydrate (NAD was spontaneously formed at somewhat larger partial pressures of HNO3 deposited on pure H2O ice. In contrast to published reports, the formation of α-NAT proceeded without prior formation of an amorphous HNO3 ∕ H2O layer and always resulted in β-NAT. For α- and β-NAT, the temperature-dependent accommodation coefficient α(H2O and α(HNO3, the evaporation flux Jev(H2O and Jev(HNO3 and the resulting saturation vapor pressure Peq(H2O and Peq(HNO3 were measured and compared to binary phase diagrams of HNO3 ∕ H2O in order to afford a thermochemical check of the kinetic parameters. The resulting kinetic and thermodynamic parameters of activation

Vapor pressures of nitric acid and water in the systems HNO3-H2O and HNO3-Th(NO3)4-H2O at 50oC

International Nuclear Information System (INIS)

Lemire, R.J.; Brown, C.P.; Campbell, A.B.

1985-01-01

The equilibrium compositions of the vapor above nitric acid-water, thorium nitrate-water, and nitric acid-thorium nitrate-water mixtures at 50 o C have been studied as a function of solution concentration by using a transpiration technique. Nitric acid concentrations were varied from 0 to 20 m and thorium nitrate concentrations from 0 to 2.5 m. Our data for the nitric acid-water system have been combined with literature data to obtain parameters for Scatchard's ion-component model, and these parameters provide a satisfactory description of the system at 50 o C over a wide concentration range. The enhancement, at 50 o C, of the nitric acid vapor pressure by added thorium nitrate was found to be less than that previously determined at 25 o C. The data for the nitric acid-thorium nitrate-water system at 50 o C were fitted to a single multiparameter function. (author)

Investigation of SiO{sub 2} film growth on 4H-SiC by direct thermal oxidation and postoxidation annealing techniques in HNO{sub 3} and H{sub 2}O vapor at varied process durations

Energy Technology Data Exchange (ETDEWEB)

Poobalan, Banu [Electronic Materials Research Group, School of Materials and Mineral Resources Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Seberang Perai Selatan, Penang (Malaysia); Moon, Jeong Hyun; Kim, Sang-Cheol; Joo, Sung-Jae; Bahng, Wook; Kang, In Ho; Kim, Nam-Kyun [Power Semiconductor Research Centre, Korea Electrotechnology Research Institute, PO Box 20, Changwon, Gyungnam 641120 (Korea, Republic of); Cheong, Kuan Yew, E-mail: cheong@eng.usm.my [Electronic Materials Research Group, School of Materials and Mineral Resources Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Seberang Perai Selatan, Penang (Malaysia)

2014-11-03

This study has revealed that HNO{sub 3} and H{sub 2}O vapors can be utilized as direct thermal oxidation or postoxidation annealing agents at a temperature above 1000 °C; as they play a major role in simultaneous oxidation/nitridation/hydrogenation processes at the bulk oxide and SiO{sub 2}/SiC interface. The varied process durations of the above-mentioned techniques contribute to the development of thicker gate oxides for high power device applications with improved electrical properties, lower interface-state density and higher breakdown voltage as compared to oxides grown through a more conventional wet (H{sub 2}O vapor only) oxidation technique. The study highlights the effects of hydrogen and nitrogen species on the passivation of structural defects at the bulk oxide and the SiO{sub 2}/SiC interface, which are revealed through the use of Time-of-Flight Secondary Ion Mass Spectroscopy and X-ray Photoelectron Spectroscopy. The physical properties of the substrate after oxide removal show that the surface roughness decreases as the process durations increase with longer hours of H{sub 2}O and HNO{sub 3} vapor exposures on the samples, which is mainly due to the significant reduction of carbon content at the SiO{sub 2}/SiC interface. - Highlights: • Direct thermal oxidation and postoxidation annealing techniques in HNO{sub 3}/H{sub 2}O vapor • SiO{sub 2} film growth in H{sub 2}O/HNO{sub 3}vapor at varied process durations • Thicker SiO{sub 2} film growth via annealing than direct growth in HNO{sub 3}/H{sub 2}O vapor • Nitrogen and hydrogen as passivation elements in SiO{sub 2}/SiC interface and SiO{sub 2} bulk • Significant reduction of carbon and Si-dangling bonds at the SiC/SiO{sub 2} interface.

Low temperature vapor phase digestion of graphite

Energy Technology Data Exchange (ETDEWEB)

Pierce, Robert A.

2017-04-18

A method for digestion and gasification of graphite for removal from an underlying surface is described. The method can be utilized to remove graphite remnants of a formation process from the formed metal piece in a cleaning process. The method can be particularly beneficial in cleaning castings formed with graphite molding materials. The method can utilize vaporous nitric acid (HNO.sub.3) or vaporous HNO.sub.3 with air/oxygen to digest the graphite at conditions that can avoid damage to the underlying surface.

Equilibrium Model for the Extraction of Am(III), Eu(III), and HNO{sub 3} into DMDOHEMA in TPH

Energy Technology Data Exchange (ETDEWEB)

Geist, Andreas [Forschungszentrum Karlsruhe, Institut fuer Nukleare Entsorgung, P.O. Box 3640, 76021 Karlsruhe (Germany)

2008-07-01

The extraction of americium(III), europium(III), and nitric acid into DMDOHEMA (N,N'-dimethyl-N,N'-di-octyl-2-[2-hexyl-oxy-ethyl]-malonamide) dissolved in TPH (a kerosene-type diluent) was studied as a function of initial nitric acid and DMDOHEMA concentrations. Nitric acid extraction can be described by the formation of three complexes, HNO{sub 3}-L{sub 2}, HNO{sub 3}-L, and (HNO{sub 3}){sub 2}-L. Americium(III) extraction is best described by the formation of three complexes, Am(NO{sub 3}){sub 3}-L{sub 4}, Am(NO{sub 3}){sub 3}-HNO{sub 3}-L{sub 3}, and Am(NO{sub 3}){sub 3}-(HNO{sub 3}){sub 2}-L{sub 2}. However, some deviations occur at higher nitric acid concentrations. These deviations may be explained by the simplified but questionable assumption of constant activity coefficients in the organic phase. (author)

Comparison of two microwave-assisted sample digestions of sediment and soils for trace metals using ICP-MS. HNO3 and HNO3/HF (P2)

International Nuclear Information System (INIS)

Howard, C.; Vandervort, A.; Bloom, N.S.

2002-01-01

Full text: Our goal was to develop an accurate and dependable digestion method for extracting trace metals from soil and sediment samples. This method would be applied to analytes at low concentrations in various sediments, including soil, contaminated soil, and marine sediment. Analysis was performed for a wide spectrum of trace metals (Ag, Al, As, Cd, Ce, Co, Cr, Cu, Eu, Fe, Hf, Ho, La, Mg, Mn, Mo, Nd, Ni, Pb, Th, Ti, Tl, Sb, Se, Sm, Sn, Yb, and Zn) using an Elan 6000 ICP-MS (Perkin-Elmer). Two sample preparation procedures were adjusted and applied to three certified reference materials (CRM); NIST2709, NIST2710, and MESS-3. The first procedure involved digestion with 10 ml nitric acid (HNO3) at 180 o C for 25 min in a microwave (Milestone-ETHOS plus). The process included four acid blanks, one blank spike, three replicates of each CRM, and one matrix spike on each of the CRM. The second procedure involved digestion with 8 ml HNO3, and 4 ml hydrofluoric acid (HF) at 180 o C for 25 min in the microwave. Digestion included four acid blanks, one blank spike, three reps of each CRM, and one matrix spike on each of the CRM. Each method proved to be robust and accurate for different analytes. Rare earth elements worked particularly well using the HNO 3 digest. By utilizing both digestions, all trace metals examined were successfully and completely extracted. (author)

The extraction of uranyl nitrate and chloride in octaethyltetraamidopyrophosphate (OETAPP)-HCl, HNO3 systems

International Nuclear Information System (INIS)

Jankowska, M.; Kulawik, J.; Mikulski, J.

1975-01-01

The extraction of uranium was studied in the system of 0.1 M OETAPP in CHCl 3 /HCl or HNO 3 . The distribution coefficients of HCl and HNO 3 were calculated as a function of OETAPP concentration. The amount of OETAPP in the aqueous phase containing HCl and HNO 3 was found from the measurements of surface tension of this phase. The distribution of HCl or HNO 3 between the organic and aqueous phases was studied as a function of the concentration of the acid used in the aqueous phase. The solvation energy of the extracted complexes was calculated from the measured potential differences. Cohesion and adhesion energies of the studied systems are also given. (author)

Measurements of HCl and HNO3 with the new research aircraft HALO - Quantification of the stratospheric contribution to the O3 and HNO3 budget in the UT/LS

Science.gov (United States)

Jurkat, Tina; Kaufmann, Stefan; Voigt, Christiane; Zahn, Andreas; Schlager, Hans; Engel, Andreas; Bönisch, Harald; Dörnbrack, Andreas

2013-04-01

Dynamic and chemical processes modify the ozone (O3) budget of the upper troposphere/lower stratosphere, leading to locally variable O3 trends. In this region, O3 acts as a strong greenhouse gas with a net positive radiative forcing. It has been suggested, that the correlation of the stratospheric tracer hydrochloric acid (HCl) with O3 can be used to quantify stratospheric O3 in the UT/LS region (Marcy et al., 2004). The question is, whether the stratospheric contribution to the nitric acid (HNO3) budget in the UT/LS can be determined by a similar approach in order to differentiate between tropospheric and stratospheric sources of HNO3. To this end, we performed in situ measurements of HCl and HNO3 with a newly developed Atmospheric chemical Ionization Mass Spectrometer (AIMS) during the TACTS (Transport and Composition in the UTLS) / ESMVal (Earth System Model Validation) mission in August/September 2012. The linear quadrupole mass spectrometer deployed aboard the new German research aircraft HALO was equipped with a new discharge source generating SF5- reagent ions and an in-flight calibration allowing for accurate, spatially highly resolved trace gas measurements. In addition, sulfur dioxide (SO2), nitrous acid (HONO) and chlorine nitrate (ClONO2) have been simultaneously detected with the AIMS instrument. Here, we show trace gas distributions of HCl and HNO3 measured during a North-South transect from Northern Europe to Antarctica (68° N to 65° S) at 8 to 15 km altitude and discuss their latitude dependence. In particular, we investigate the stratospheric ozone contribution to the ozone budget in the mid-latitude UT/LS using correlations of HCl with O3. Differences in these correlations in the subtropical and Polar regions are discussed. A similar approach is used to quantify the HNO3 budget of the UT/LS. We identify unpolluted atmospheric background distributions and various tropospheric HNO3 sources in specific regions. Our observations can be compared to

Uptake of methanol on mixed HNO3/H2O clusters: An absolute pickup cross section

Science.gov (United States)

Pysanenko, A.; Lengyel, J.; Fárník, M.

2018-04-01

The uptake of atmospheric oxidized organics on acid clusters is relevant for atmospheric new particle formation. We investigate the pickup of methanol (CH3OH) on mixed nitric acid-water clusters (HNO3)M(H2O)N by a combination of mass spectrometry and cluster velocity measurements in a molecular beam. The mass spectra of the mixed clusters exhibit (HNO3)m(H2O)nH+ series with m = 0-3 and n = 0-12. In addition, CH3OH.(HNO3)m(H2O)nH+ series with very similar patterns appear in the spectra after the methanol pickup. The velocity measurements prove that the undoped (HNO3)m(H2O)nH+ mass peaks in the pickup spectra originate from the neutral (HNO3)M(H2O)N clusters which have not picked up any CH3OH molecule, i.e., methanol has not evaporated upon the ionization. Thus the fraction of the doped clusters can be determined and the mean pickup cross section can be estimated, yielding σs ¯ ≈ 20 Å2. This is compared to the lower estimate of the mean geometrical cross section σg ¯ ≈ 60 Å2 obtained from the theoretical cluster geometries. Thus the "size" of the cluster corresponding to the methanol pickup is at least 3-times smaller than its geometrical size. We have introduced a method which can yield the absolute pickup cross sections relevant to the generation and growth of atmospheric aerosols, as illustrated in the example of methanol and nitric acid clusters.

Mechanism of nitric acid generation on Ag-X Zeolite

International Nuclear Information System (INIS)

Kanazawa, T.; Kishimoto, T.; Haseba, S.; Mitoh, Y.; Itoh, S.; Nakai, I.

1983-01-01

When Ag-X Zeolite is used for the removal of iodine from the off gas streams of nuclear facilities, it is possible that nitric acid is formed on Ag-X Zeolite from co-existing nitrogen dioxide and water vapor. If nitric acid is formed on the surface of Ag-X zeolite, Ag-X zeolite is damaged and is not able to operate for a long time. When Ag-X zeolite is used in NO 2 -O 2 -H 2 O mixture, the nitric acid generation reaction is varied, depending upon the reaction temperature, and concentration of NO 2 and H 2 O. At a temperature of more than 40 deg. C, however, only the surface reaction will be progressed on the zeolite surface. The generation of nitric acid solution on the zeolite can be forecasted through the relationship between the concentration of nitric acid solution, equilibrium vapor pressure of H 2 O, and equilibrium vapor pressure of HNO 3 . Concerning the surface reaction caused on the zeolite, the adsorption water reacts on NO 2 , and the resulting HNO 3 is adsorbed firmly by the zeolite, which is thought to interfere with the surface reaction for generation of the HNO 3 . When the adsorption bed is long, the time required for adsorbed HNO 3 to saturate is increased in proportion to the bed length

Distribution and identification of Plutonium(IV) species in tri-n-butyl phosphate/HNO3 extraction system containing acetohydroxamic acid

International Nuclear Information System (INIS)

Tkac, P.; Paulenova, A.; Vandegrift, G.F.; Krebs, J.F.

2009-01-01

There was a significant research progress achieved with the aim to modify conventional PUREX process by stripping of plutonium from the tri-n-butyl phosphate (TBP) extraction product in the form of non-extractable complexes upon addition of back-hold complexation agents. The present paper reports effects of such salt-free complexant, acetohydroxamic acid (HAHA), on distribution ratio of Pu(IV) under wide concentration of nitric acid and additional nitrate. General formula of plutonium species present in the organic phase can be described as Pu(OH) x (AHA) y (NO3) 4-x-y x 2TBP x wHNO 3 . (author)

Alloy 33: A new material for the handling of HNO3/HF media in reprocessing of nuclear fuel

International Nuclear Information System (INIS)

Koehler, M.; Heubner, U.; Eichenhofer, K.W.; Renner, M.

1997-01-01

Alloy 33, an austenitic 33Cr-32Fe-31Ni-1.6Mo-0.6Cu-0.4N material shows excellent resistance to corrosion when exposed to highly oxidizing media as e.g. HNO 3 and HNO 3 /HF mixtures which are encountered in reprocessing of nuclear fuel. According to the test results available so far, resistance to corrosion in boiling azeotropic (67%) HNO 3 is about 6 and 2 times superior to AISI 304 L and 310 L. In higher concentrated nitric acid it can be considered corrosion resistant up to 95% HNO 3 at 25 C, up to 90% HNO 3 at 50 C and up to somewhat less than 85% HNO 3 at 75 C. In 20% HNO 3 /7% HF at 50 C its resistance to corrosion is superior to AISI 316 Ti and Alloy 28 by factors of about 200 and 2.4. Other media tested with different results include 12% HNO 3 with up to 3.5% HF and 0.4% HF with 32 to 67.5% HNO 3 at 90 C. Alloy 33 is easily fabricated into all product forms required for chemical plants (e.g. plate, sheet, strip, wire, tube and flanges). Components such as dished ends and tube to tube sheet weldments have been successfully fabricated facilitating the use of Alloy 33 for reprocessing of nuclear fuel

Validation of MIPAS HNO3 operational data

Directory of Open Access Journals (Sweden)

C. D. Boone

2007-09-01

Full Text Available Nitric acid (HNO3 is one of the key products that are operationally retrieved by the European Space Agency (ESA from the emission spectra measured by the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS onboard ENVISAT. The product version 4.61/4.62 for the observation period between July 2002 and March 2004 is validated by comparisons with a number of independent observations from ground-based stations, aircraft/balloon campaigns, and satellites. Individual HNO3 profiles of the ESA MIPAS level-2 product show good agreement with those of MIPAS-B and MIPAS-STR (the balloon and aircraft version of MIPAS, respectively, and the balloon-borne infrared spectrometers MkIV and SPIRALE, mostly matching the reference data within the combined instrument error bars. In most cases differences between the correlative measurement pairs are less than 1 ppbv (5–10% throughout the entire altitude range up to about 38 km (~6 hPa, and below 0.5 ppbv (15–20% or more above 30 km (~17 hPa. However, differences up to 4 ppbv compared to MkIV have been found at high latitudes in December 2002 in the presence of polar stratospheric clouds. The degree of consistency is further largely affected by the temporal and spatial coincidence, and differences of 2 ppbv may be observed between 22 and 26 km (~50 and 30 hPa at high latitudes near the vortex boundary, due to large horizontal inhomogeneity of HNO3. Similar features are also observed in the mean differences of the MIPAS ESA HNO3 VMRs with respect to the ground-based FTIR measurements at five stations, aircraft-based SAFIRE-A and ASUR, and the balloon campaign IBEX. The mean relative differences between the MIPAS and FTIR HNO3 partial columns are within ±2%, comparable to the MIPAS systematic error of ~2%. For the vertical profiles, the biases between the MIPAS and FTIR data are generally below 10% in the altitudes of 10 to 30 km. The MIPAS and SAFIRE HNO3 data generally match within their total error

Hydroxyurea reaction with HNO2 and Pu(III) stabilization

International Nuclear Information System (INIS)

Zhu Zhaowu; He Jianyu; Zhang Zefu; Zheng Weifang; Song Tianbao; Lin Min

2004-01-01

Reaction kinetics of hydroxyurea (HU) with HNO 2 in nitric acid solution is studied. The results show that the reaction rate follows the equation as: -dc(HNO 2 )/dt=k 0 c(HNO 2 )c 1.1 (HNO 3 ) c 0 (HU), where k 0 =(0.18±0.01)L 1.1 ·mol -1.1 ·s -1 at 10 degree C and c(HNO 2 )=5 mmol/L; the activation energy is deduced to be about 63 kJ/mol. The reaction appears zero order relative to HU. Kinetic study performed at various NaNO 3 solutions shows that salt ions have little effect on the reaction rate. Excess HU can stabilize Pu(III) well in nitric solutions

Application of the chemical vapor-etching in polycrystalline silicon solar cells

International Nuclear Information System (INIS)

Ben Rabha, M.; Saadoun, M.; Boujmil, M.F.; Bessais, B.; Ezzaouia, H.; Bennaceur, R.

2005-01-01

This paper reports a study of the application of chemical vapor-etching (CVE) for the rear surface and in the emitter of polycrystalline silicon (pc-Si) solar cells. The CVE technique consists of exposing pc-Si wafers to a mixture of HF/HNO 3 . This technique is used to groove the rear surface of the pc-Si wafers for acid vapors rich in HNO 3 (HNO 3 /HF > 1/4), in order to realize rear-buried metallic contacts (RBMC) and the formation of a porous silicon (PS) layer on the frontal surface of the cell for volume ratio of HNO 3 /HF = 1/7. A significant increase of the spectral response in the long wavelength range was observed when a RBMC is formed. This increase was attributed to the reduction of the effective thickness of the base of the cells and grain boundary Al gettering. The achievement of a PS layer on the emitter of the pc-Si cells passivates the surface and reduces the reflectivity. The dark I-V characteristics of pc-Si cells with emitter-based PS show an important reduction of the reverse current together with an improvement of the rectifying behaviour. The I-V characteristic under AM1.5 illumination shows an enhancement of both short circuit current density and fill factor. The internal quantum efficiency is improved, particularly in the short wavelengths region

Extraction of Am, Pu and U by dicyclohexano-18-crown-6/1-octanol from HNO3 solution and simulated HLLW

International Nuclear Information System (INIS)

Wang Xinghai; Wang Jianchen; Liu Xiuqin; Song Chongli

1999-01-01

The extraction of americium, plutonium and uranium by dicyclohexano-18-crown-6 (DCH18C6)/1-octanol from HNO 3 solution and simulated HLLW are studied. The influences of acidity and dilution factor of simulated HLLW are studied. At low HNO 3 concentration and dilution factor above 2, 0.1 mol/L DCH18C6/1-octanol extracts very little americium, plutonium and uranium. the distribution ratios of Am, Pu and U increase with the increase of HNO 3 concentration in aqueous phase, and decrease with increasing of dilution factor of HLLW. The distribution ratio of extraction of Pu(IV) increases with the increase of extractant concentration

Interactions of aerosols (ammonium sulfate, ammonium nitrate and ammonium chloride) and of gases (HCl, HNO 3) with fogwater

Science.gov (United States)

Ruprecht, Heidi; Sigg, Laura

The concentrations of aerosols (NH 4NO 3, (NH 4) 2SO 4 and NH 4Cl) and of gases (HCl (g), HNO 3(g), NH 3(g) were determined by denuder methods under different conditions (in the absence of fog, before, during and after fog events). At this site situated in an urban region, high concentrations of the gaseous strong acids HCl (g) and HNO 3(g) are observed. NH 4Cl and NH 4NO 3 aerosols represent a major fraction of the Cl - and NO 3- aerosols (fogwater and are released again after fog dissipation.

Redox reactions of Pu(IV) and Pu(III) in the presence of acetohydroxamic acid in HNO(3) solutions.

Science.gov (United States)

Tkac, Peter; Precek, Martin; Paulenova, Alena

2009-12-21

The reduction of Pu(IV) in the presence of acetohydroxamic acid (HAHA) was monitored by vis-NIR spectroscopy. All experiments were performed under low HAHA/Pu(IV) ratios, where only the Pu(IV)-monoacetohydroxamate complex and Pu uncomplexed with HAHA were present in relevant concentrations. Time dependent concentrations of all absorbing species were resolved using molar extinction coefficients for Pu(IV), Pu(III), and the Pu(AHA)(3+) complex by deconvolution of spectra. From fitting of the experimental data by rate equations integrated by a numeric method three reactions were proposed to describe a mechanism responsible for the reduction and oxidation of plutonium in the presence of HAHA and HNO(3). Decomposition of Pu(AHA)(3+) follows a second order reaction mechanism with respect to its own concentration and leads to the formation of Pu(III). At low HAHA concentrations, a two-electron reduction of uncomplexed Pu(IV) with HAHA also occurs. Formed Pu(III) is unstable and slowly reoxidizes back to Pu(IV), which, at the point when all HAHA is decomposed, can be catalyzed by the presence of nitrous acid.

African biomass burning plumes over the Atlantic: aircraft based measurements and implications for H2SO4 and HNO3 mediated smoke particle activation

Directory of Open Access Journals (Sweden)

A. Dörnbrack

2011-04-01

Full Text Available Airborne measurements of trace gases and aerosol particles have been made in two aged biomass burning (BB plumes over the East Atlantic (Gulf of Guinea. The plumes originated from BB in the Southern-Hemisphere African savanna belt. On the day of our measurements (13 August 2006, the plumes had ages of about 10 days and were respectively located in the middle troposphere (MT at 3900–5500 m altitude and in the upper troposphere (UT at 10 800–11 200 m. Probably, the MT plume was lifted by dry convection and the UT plume was lifted by wet convection. In the more polluted MT-plume, numerous measured trace species had markedly elevated abundances, particularly SO2 (up to 1400 pmol mol−1, HNO3 (5000–8000 pmol mol−1 and smoke particles with diameters larger than 270 nm (up to 2000 cm−3. Our MT-plume measurements indicate that SO2 released by BB had not experienced significant loss by deposition and cloud processes but rather had experienced OH-induced conversion to gas-phase sulfuric acid. By contrast, a significant fraction of the released NOy had experienced loss, most likely as HNO3 by deposition. In the UT-plume, loss of NOy and SO2 was more pronounced compared to the MT-plume, probably due to cloud processes. Building on our measurements and accompanying model simulations, we have investigated trace gas transformations in the ageing and diluting plumes and their role in smoke particle processing and activation. Emphasis was placed upon the formation of sulfuric acid and ammonium nitrate, and their influence on the activation potential of smoke particles. Our model simulations reveal that, after 13 August, the lower plume traveled across the Atlantic and descended to 1300 m and hereafter ascended again. During the travel across the Atlantic, the soluble mass fraction of smoke particles and their mean diameter increased sufficiently to allow the processed smoke particles to act as water vapor condensation nuclei already at very low water

Waste acid detoxification and reclamation: Summary of bench-scale tests for FY 1986 and FY 1987

Energy Technology Data Exchange (ETDEWEB)

Stewart, T.L.

1987-09-01

Processes to reduce the volume, quantity, and toxicity of metal-bearing waste acid are being demonstrated at Pacific Northwest Laboratory. Two precipitation processes and a distillation process are being developed to minimize waste from fuel fabrication operations, which comprise a series of metal-finishing operations. Waste process acids such as HF-HNO/sub 3/, etch solutions containing Zr as a major metal impurity, and HNO/sub 3/ strip solution containing Cu as a major metal impurity are detoxified and reclaimed by concurrently precipitating heavy metals and regenerating acid for recycle. Acid from a third waste acid stream generated from chemical milling operations will be reclaimed using distillation. This stream comprises HNO/sub 3/ and H/sub 2/SO/sub 4/ containing U as the major metal impurity. Distillation allows NO/sub 3//sup -/ to be displaced by SO/sub 4//sup -2/ in metal salts; free HNO/sub 3/ is then vaporized from the U-bearing sulfate stream. Uranium can be recovered from the sulfate stream in a downstream precipitation step. 10 refs., 15 figs., 13 tabs.

Mathematical modeling of radiation-chemical processes in HNO3 solutions of Pu. 5. Effect of [HNO3] on rate constants of radiation-chemical and chemical reactions of Pu ions

International Nuclear Information System (INIS)

Vladimirova, M.V.

1993-01-01

Dependences of rate constants on [HNO 3 ] are obtained for the reactions Pu(IV) + OH, Pu(IV) + NO 3 , Pu(V) + NO 2 , Pu(III) + NO 2 , Pu(V) + Pu(III), Pu(IV) + Pu(IV), and Pu(V) + Pu(V). These dependences are obtained for [HNO 3 ] = 0.3-6 M using existing experimental and literature data and the data obtained using mathematical modeling. The correctness of the resulting dependences is checked by comparing the calculated and experimental kinetic laws for the behavior of Pu in 0.3, 0.4, 0.6, and 1.6 M HNO 3 . 17 refs., 15 figs., 2 tabs

Titanium and zirconium based wrought alloys and bulk metallic glasses for fluoride ion containing 11.5 M HNO3 medium

International Nuclear Information System (INIS)

Jayaraj, J.; Ningshen, S.; Mallika, C.; Kamachi Mudali, U.

2016-01-01

Aqueous reprocessing of plutonium-rich mixed oxide fuels require fluoride as a catalyst in boiling nitric acid for an effective dissolution of the spent fuel. The corrosion behavior of the candidate dissolver materials zircaloy-4 (Zr-4) and commercial pure titanium (CP-Ti grade 2) in boiling 11.5 M HNO 3 + 0.05 M NaF has been established. High corrosion rates were obtained for Zr- 4 and CP-Ti in nitric acid containing fluoride ions. Complexing the fluoride ions either with Al(NO 3 ) 3 or ZrO(NO 3 ) 2 aided in decreasing the corrosion rates of Zr-4 and CP-Ti. High corrosion resistance is claimed as one of the principal property of the amorphous alloy when compared to the crystalline alloy. Thus Ni 60 Nb 40 and Ni 60 Nb 30 Ta 10 amorphous ribbons were prepared and exposed in boiling 11.5 M HNO 3 and 11.5 M HNO 3 + 0.05 M NaF. In nitric acid these alloys did not show any sign of corrosion attack. XPS analysis confirmed that the passivity was due to the formation passive films of thickness ≈3 nm enriched with Nb 2 O 5 and of ≈1.5 nm enriched with both Nb 2 O 5 and Ta 2 O 5 on the respective surfaces of the ribbons. In boiling 11.5 M HNO 3 + 0.05 M NaF, severe corrosion attack was observed on Ni 60 Nb 40 ribbon, due to the instability of the oxide/metal interface. The Ni 60 Nb 30 Ta 10 amorphous ribbon exhibited corrosion resistance of at least an order of magnitude higher than that for Ni 60 Nb 40 ribbon

Comparison of field data with a thermodynamic model for the H/sub 2/SO/sub 4/ - HNO/sub 3/ - NH/sub 3/ system at high humidities and in fogs

Energy Technology Data Exchange (ETDEWEB)

Jacob, D.J.; Munger, J.W.; Waldman, J.M.; Hoffmann, M.R.

1986-04-01

A systematic characterization of the atmospheric H/sub 2/SO/sub 4/ - NH/sub 2/ system was conducted in the fogwater, the aerosol, and the gas phase at a network of sites in the San Joaquin Valley of California. Spatial patterns of concentrations were established that reflect the distribution of SO/sub 2/, NO/sub X/, and NH/sub 3/ emissions within the valley. The concept of atmospheric alkalinity was introduced to interpret these concentrations in terms of the buffering capacity of the atmosphere with respect to inputs of strong acids. Regions of predominantly acidic and alkaline fogwater were identified. Fogwater was found to be alkaline in most of the valley, but small changes in emission budgets could lead to widespread acid fog. An extended stagnation episode was studied in detail: progressive accumulation of H/sub 2/SO/sub 4/ - HNO/sub 3/ - NH/sub 3/ species was documented over the course of the episode, and interpreted in terms of production and removal mechanisms. Secondary production of strong acids H/sub 2/SO/sub 4/ and HNO/sub 3/ under stagnant conditions resulted in a complete titration of available alkalinity at sites furthest from NH/sub 3/ sources. A steady SO/sub 2/ conversion rate of 0.4 - 1.1% h/sup -1/ was estimated in the stagnant mixed layer of haze aerosol under overcast conditions, and was attributed to non-photochemical heterogeneous processes. Removal of SO/sub 2/ was enhanced in fog as compared to non-foggy conditions. Conversion of NO/sub X/ to HNO/sub 3/ slowed down during the stagnation episode because of reduced photochemical activity: fog did not appear to enhance conversion of NO/sub X/. Decreases in total HNO/sub 3/ concentrations were observed upon acidification of the atmosphere, and were attributed to displacement of NO/sub 3-/ by H/sub 2/SO/sub 4/ in the aerosol followed by rapid deposition of HNO/sub 3/(g). The occurrence of fog was associated with general decreases of aerosol concentrations due to enhanced removal by deposition.

Evaluation of sampling methods for measuring exposure to volatile inorganic acids in workplace air. Part 2: Sampling capacity and breakthrough tests for sodium carbonate-impregnated filters.

Science.gov (United States)

Demange, Martine; Oury, Véronique; Rousset, Davy

2011-11-01

In France, the MétroPol 009 method used to measure workplace exposure to inorganic acids, such as HF, HCl, and HNO3, consists of a closed-face cassette fitted with a prefilter to collect particles, and two sodium carbonate-impregnated filters to collect acid vapor. This method was compared with other European methods during the development of a three-part standard (ISO 21438) on the determination of inorganic acids in workplace air by ion chromatography. Results of this work, presented in a companion paper, led to a need to go deeper into the performance of the MétroPol 009 method regarding evaluation of the breakthrough of the acids, both alone and in mixtures, interference from particulate salts, the amount of sodium carbonate required to impregnate the sampling filter, the influence of sampler components, and so on. Results enabled improvements to be made to the sampling device with respect to the required amount of sodium carbonate to sample high HCl or HNO3 concentrations (500 μL of 5% Na2CO3 on each of two impregnated filters). In addition, a PVC-A filter used as a prefilter in a sampling device showed a propensity to retain HNO3 vapor so a PTFE filter was considered more suitable for use as a prefilter. Neither the material of the sampling cassette (polystyrene or polypropylene) nor the sampling flowrate (1 L/min or 2 L/min) influenced the performance of the sampling device, as a recovery of about 100% was achieved in all experiments for HNO3, HCl, and HF, as well as HNO3+HF and HNO3+HCl mixtures, over a wide range of concentrations. However, this work points to the possibility of interference between an acid and salts of other acids. For instance, interference can occur through interaction of HNO3 with chloride salts: the stronger the acid, the greater the interference. Methods based on impregnated filters are reliable for quantitative recovery of inorganic volatile acids in workplace atmosphere but are valuable only in the absence of interferents.

Density study of the ternary mixture Mg(NO3)2-HNO3-H2O

International Nuclear Information System (INIS)

Jubin, R.T.; Marley, J.L.; Counce, R.M.

1985-06-01

Densities for the Mg(NO 3 ) 2 -HNO 3 -H 2 O system have been experimentally measured; more than 140 measurements were made covering ranges of 30 to 70 wt % Mg(NO 3 ) 2 , 0 to 40 wt % HNO 3 , and temperatures of 50 to 145 0 C. A mathematical model for the observed density relationships has been developed. 6 refs., 3 figs., 8 tabs

Hydrogen-bonding behavior of various conformations of the HNO3…(CH3OH)2 ternary system.

Science.gov (United States)

Özsoy, Hasan; Uras-Aytemiz, Nevin; Balcı, F Mine

2017-12-21

Nine minima were found on the intermolecular potential energy surface for the ternary system HNO 3 (CH 3 OH) 2 at the MP2/aug-cc-pVDZ level of theory. The cooperative effect, which is a measure of the hydrogen-bonding strength, was probed in these nine conformations of HNO 3 …(CH 3 OH) 2 . The results are discussed here in terms of structures, energetics, infrared vibrational frequencies, and topological parameters. The cooperative effect was observed to be an important contributor to the total interaction energies of the cyclic conformers of HNO 3 …(CH 3 OH) 2 , meaning that it cannot be neglected in simulations in which the pair-additive potential is applied. Graphical abstract The H-bonding behavior of various conformations of the HNO 3 (CH 3 OH) 2 trimer was investigated.

Gas-particle interactions above a Dutch heathland: I. Surface exchange fluxes of NH3, SO2, HNO3 and HCl

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E. Nemitz

2004-01-01

Full Text Available A field measurement campaign was carried out over a Dutch heathland to investigate the effect of gas-to-particle conversion and ammonium aerosol evaporation on surface/atmosphere fluxes of ammonia and related species. Continuous micrometeorological measurements of the surface exchange of NH3, SO2, HNO3 and HCl were made and are analyzed here with regard to average fluxes, deposition velocities (Vd, canopy resistances (Rc and canopy compensation point for NH3. Gradients of SO2, HNO3 and HCl were measured with a novel wet-denuder system with online anion chromatography. Measurements of HNO3 and HCl indicate an Rc of 100 to 200 s m-1 during warm daytime periods, probably at least partly due to non-zero acid partial pressures above NH4NO3 and NH4Cl on the leaf surfaces. Although it is likely that this observation is exacerbated by the effect of the evaporation of airborne NH4+ on the gradient measurements, the findings nevertheless add to the growing evidence that HNO3 and HCl are not always deposited at the maximum rate. Ammonia (NH3 fluxes show mainly deposition, with some periods of significant daytime emission. The net exchange could be reproduced both with an Rc model (deposition fluxes only using resistance parameterizations from former measurements, as well as with the canopy compensation point model, using parameterizations derived from the measurements. The apoplastic ratio of ammonium and hydrogen concentration (Γs=[NH4+]/[H+] of 1200 estimated from the measurements is large for semi-natural vegetation, but smaller than indicated by previous measurements at this site.

Gas-particle interactions above a Dutch heathland: I. Surface exchange fluxes of NH3, SO2, HNO3 and HCl

Science.gov (United States)

Nemitz, E.; Sutton, M. A.; Wyers, G. P.; Jongejan, P. A. C.

2004-07-01

A field measurement campaign was carried out over a Dutch heathland to investigate the effect of gas-to-particle conversion and ammonium aerosol evaporation on surface/atmosphere fluxes of ammonia and related species. Continuous micrometeorological measurements of the surface exchange of NH3, SO2, HNO3 and HCl were made and are analyzed here with regard to average fluxes, deposition velocities (Vd), canopy resistances (Rc) and canopy compensation point for NH3. Gradients of SO2, HNO3 and HCl were measured with a novel wet-denuder system with online anion chromatography. Measurements of HNO3 and HCl indicate an Rc of 100 to 200 s m-1 during warm daytime periods, probably at least partly due to non-zero acid partial pressures above NH4NO3 and NH4Cl on the leaf surfaces. Although it is likely that this observation is exacerbated by the effect of the evaporation of airborne NH4+ on the gradient measurements, the findings nevertheless add to the growing evidence that HNO3 and HCl are not always deposited at the maximum rate. Ammonia (NH3) fluxes show mainly deposition, with some periods of significant daytime emission. The net exchange could be reproduced both with an Rc model (deposition fluxes only) using resistance parameterizations from former measurements, as well as with the canopy compensation point model, using parameterizations derived from the measurements. The apoplastic ratio of ammonium and hydrogen concentration (Γs=[NH4+]/[H+]) of 1200 estimated from the measurements is large for semi-natural vegetation, but smaller than indicated by previous measurements at this site.

Third phase formation revisited: the U(VI), HNO3 - TBP, n-dodecane system

International Nuclear Information System (INIS)

Chiarizia, R.; Jensen, M.P.; Borkowski, M.; Ferraro, J.R.; Thiyagarajan, P.; Littrell, K.C.

2003-01-01

In this work, the system U(VI), HNO 3 -tri-n-butylphosphate (TBP), n-dodecane has been revisited with the objective of gaining information on the coordination chemistry and structural evolution of the species formed in the organic phase before and after third phase formation. Chemical analyses, spectroscopic and EXAFS data indicate that U(VI) is extracted as the UO 2 (NO 3 ) 2 ·2TBP adduct, while the third phase species have the average composition UO 2 (NO 3 ) 2 ·2TBP·HNO 3 . Small-angle neutron scattering (SANS) measurements on TBP solutions loaded with only HNO 3 or with increasing amounts of U(VI) have revealed the presence, before phase splitting, of ellipsoidal aggregates with the major and minor axes up to about 64 and 15 A, respectively. The formation of these aggregates, very likely of the reverse micelle-type, is observed in all cases, that is, when only HNO 3 , only UO 2 (NO 3 ) 2 , or both HNO 3 and UO 2 (NO 3 ) 2 are extracted by the TBP solution. Upon third phase formation, the SANS data reveal the presence of smaller aggregates in the light organic phase, while the heavy organic phase contains pockets of diluent, each with an average of about two molecules of n-dodecane.

Investigation into radiolysis of tbp labelled with 32P in the 30%tbp-diluent-HNO3 systems

International Nuclear Information System (INIS)

Novak, M.; Novak, Z.; Rokhon', A.

1975-01-01

Phosphorus-containing compounds, prepared by radiolysis of the TBP-diluent-HNO 3 system, are determined quantitatively. Effects of the HNO 3 concentration and the diluent type upon the degree of the TBP decomposition in the system under investigation were determined as well. To separate the TBP decomposition products the thin layer chromatography method was used, and for the quantitative determination TBP, labelled with 32 P was used. As a result of TBP radiolysis except dibutyl phosphate and monobutylphosphate other compounds are prepared, which contain phosphorus in a molecule, besides, their quantity depends on the nitric acid concentration and the diluent type (n-dodecan, carbon tetrachloride, mesitylen), together with which TBP was irradiated. The prepared compounds are grouped in the aqueous and organic phases

Development of mathematical model of H{sub 2}O-HNO{sub 3}-UO{sub 2}(NO{sub 3}){sub 2}-TBP-Diluent System

Energy Technology Data Exchange (ETDEWEB)

Ochkin, A.; Gladilov, D.; Nekhaevskiy, S.; Merkushkin, A. [D. Mendeleev University of Chemical Technology of Russia, 9 Miusskay Sqr., Moscow, 125047 (Russian Federation)

2016-07-01

The nuclear fuel reprocessing is based on the PUREX process. Usually 30% TBP in hydrocarbon diluents is applied, then the composition of the organic phase can be expressed as H{sub 2}O-HNO{sub 3}-UO{sub 2}(NO{sub 3}){sub 2}-Pu(NO{sub 3}){sub 4}-TBP-diluent. The mathematical model of H{sub 2}O-HNO{sub 3}-UO{sub 2}(NO{sub 3}){sub 2}-TBP-dodecane system has been elaborated. Mole fractions and volume ones and rational activity coefficients have been used in order to create the system of equations on the base of mass action law. The method for calculating activity coefficients was provided. The formation constants of uranyl nitrate di-solvate and mono-solvate and di-solvate of acid have been determined. Interaction between uranyl nitrate di-solvate and dodecane and between TBP and dodecane was taken into account. Activity coefficients of nitric acid and uranyl nitrate in mixed solutions were considered. Errors of adequacy have been determined for the systems containing 30% and 12% TBP concentrations.

Distillation Separation of Hydrofluoric Acid and Nitric Acid from Acid Waste Using the Salt Effect on Vapor-Liquid Equilibrium

Science.gov (United States)

Yamamoto, Hideki; Sumoge, Iwao

2011-03-01

This study presents the distillation separation of hydrofluoric acid with use of the salt effect on the vapor-liquid equilibrium for acid aqueous solutions and acid mixtures. The vapor-liquid equilibrium of hydrofluoric acid + salt systems (fluorite, potassium nitrate, cesium nitrate) was measured using an apparatus made of perfluoro alkylvinylether. Cesium nitrate showed a salting-out effect on the vapor-liquid equilibrium of the hydrofluoric acid-water system. Fluorite and potassium nitrate showed a salting-in effect on the hydrofluoric acid-water system. Separation of hydrofluoric acid from an acid mixture containing nitric acid and hydrofluoric acid was tested by the simple distillation treatment using the salt effect of cesium nitrate (45 mass%). An acid mixture of nitric acid (5.0 mol · dm-3) and hydrofluoric acid (5.0 mol · dm-3) was prepared as a sample solution for distillation tests. The concentration of nitric acid in the first distillate decreased from 5.0 mol · dm-3 to 1.13 mol · dm-3, and the concentration of hydrofluoric acid increased to 5.41 mol · dm-3. This first distillate was further distilled without the addition of salt. The concentrations of hydrofluoric acid and nitric acid in the second distillate were 7.21 mol · dm-3 and 0.46 mol · dm-3, respectively. It was thus found that the salt effect on vapor-liquid equilibrium of acid mixtures was effective for the recycling of acids from acid mixture wastes.

Removal of fluoride from aqueous nitric acid

International Nuclear Information System (INIS)

Pruett, D.J.; Howerton, W.B.; Mailen, J.C.

1981-06-01

Several methods for removing fluoride from aqueous nitric acid were investigated and compared with the frequently used aluminum nitrate-calcium nitrate (Ca 2+ -Al 3+ ) chemical trap-distillation system. Zirconium oxynitrate solutions were found to be superior in preventing volatilization of fluoride during distillation of the nitric acid, producing decontamination factors (DFs) on the order of 2 x 10 3 (vs approx. 500 for the Ca 2+ -Al 3+ system). Several other metal nitrate systems were tested, but they were less effective. Alumina and zirconia columns proved highly effective in removing HF from HF-HNO 3 vapors distilled through the columns; fluoride DFs on the order of 10 6 and 10 4 , respectively, were obtained. A silica gel column was very effective in adsorbing HF from HF-HNO 3 solutions, producing a fluoride DF of approx. 10 4

Corrosion of high Ni-Cr alloys and Type 304L stainless steel in HNO3-HF

International Nuclear Information System (INIS)

Ondrejcin, R.S.; McLaughlin, B.D.

1980-04-01

Nineteen alloys were evaluated as possible materials of construction for steam heating coils, the dissolver vessel, and the off-gas system of proposed facilities to process thorium and uranium fuels. Commercially available alloys were found that are satisfactory for all applications. With thorium fuel, which requires HNO 3 -HF for dissolution, the best alloy for service at 130 0 C when complexing agents for fluoride are used is Inconel 690; with no complexing agents at 130 0 C, Inconel 671 is best. At 95 0 C, six other alloys tested would be adequate: Haynes 25, Ferralium, Inconel 625, Type 304L stainless steel, Incoloy 825, and Haynes 20 (in order of decreasing preference); based on composition, six untested alloys would also be adequate. The ions most effective in reducing fluoride corrosion were the complexing agents Zr 4+ and Th 4+ ; Al 3+ was less effective. With uranium fuel, modestly priced Type 304L stainless steel is adequate. Corrosion will be most severe in HNO 3 -HF used occasionally for flushing and in solutions of HNO 3 and corrosion products (ferric and dichromate ions). HF corrosion can be minimized by complexing the fluoride ion and by passivation of the steel with strong nitric acid. Corrosion caused by corrosion products can be minimized by operating at lower temperatures

Waste acid detoxification and reclamation: Phase 1, Project planning and concept development

Energy Technology Data Exchange (ETDEWEB)

Stewart, T.L.; Brouns, T.M.

1988-02-01

The objectives of this project are to develop processes for reducing the volume, quantity, and toxicity of metal-bearing waste acids. The primary incentives for implemeting these types of waste minimization processes are regulatory and economic in that they meet requirements in the Resource Conservation and Recovery Act and reduce the cost for treatment, storage, and disposal. Two precipitation processes and a distillation process are being developed to minimize waste from fuel fabrication operations, which comprise a series of metal-finishing operations. Waste process acids, such as HF/--/HNO/sub 3/ etch solutions contianing Zr as a major metal impurity and HNO/sub 3/ strip solutions containing Cu as a major metal impurity, are detoxified and reclaimed by concurrently precipitating heavy metals and regenerating acid for recycle. Acid from a third waste acid stream generated from chemical milling operations will be reclaimed using distillation. This stream comprises HNO/sub 3/ and H/sub 2/SO/sub 4/ which contains U as the major metal impurity. Distillation allows NO/sub 3//sup /minus// to be displaced by SO/sub 4//sup /minus/2/ in metal salts; free HNO/sub 3/ is then vaporized from the U-bearing sulfate stream. Uranium can be recovered from the sulfate stream in downstream precipitation step. These waste minimization processes were developed to meet Hanford's fuel fabrication process needs. 7 refs., 4 figs., 1 tab.

Waste acid detoxification and reclamation: Phase 1, Project planning and concept development

International Nuclear Information System (INIS)

Stewart, T.L.; Brouns, T.M.

1988-02-01

The objectives of this project are to develop processes for reducing the volume, quantity, and toxicity of metal-bearing waste acids. The primary incentives for implemeting these types of waste minimization processes are regulatory and economic in that they meet requirements in the Resource Conservation and Recovery Act and reduce the cost for treatment, storage, and disposal. Two precipitation processes and a distillation process are being developed to minimize waste from fuel fabrication operations, which comprise a series of metal-finishing operations. Waste process acids, such as HF/--/HNO 3 etch solutions contianing Zr as a major metal impurity and HNO 3 strip solutions containing Cu as a major metal impurity, are detoxified and reclaimed by concurrently precipitating heavy metals and regenerating acid for recycle. Acid from a third waste acid stream generated from chemical milling operations will be reclaimed using distillation. This stream comprises HNO 3 and H 2 SO 4 which contains U as the major metal impurity. Distillation allows NO 3 /sup /minus// to be displaced by SO 4 /sup /minus/2/ in metal salts; free HNO 3 is then vaporized from the U-bearing sulfate stream. Uranium can be recovered from the sulfate stream in downstream precipitation step. These waste minimization processes were developed to meet Hanford's fuel fabrication process needs. 7 refs., 4 figs., 1 tab

The mid-IR Absorption Cross Sections of α- and β-NAT (HNO3 · 3H2O) in the range 170 to 185 K and of metastable NAD (HNO3 · 2H2O) in the range 172 to 182 K

Science.gov (United States)

Iannarelli, R.; Rossi, M. J.

2015-11-01

Growth and Fourier transform infrared (FTIR) absorption in transmission of the title nitric acid hydrates have been performed in a stirred flow reactor (SFR) under tight control of the H2O and HNO3 deposition conditions affording a closed mass balance of the binary mixture. The gas and condensed phases have been simultaneously monitored using residual gas mass spectrometry and FTIR absorption spectroscopy, respectively. Barrierless nucleation of the metastable phases of both α-NAT (nitric acid trihydrate) and NAD (nitric acid dihydrate) has been observed when HNO3 was admitted to the SFR in the presence of a macroscopic thin film of pure H2O ice of typically 1 µm thickness. The stable β-NAT phase was spontaneously formed from the precursor α-NAT phase through irreversible thermal rearrangement beginning at 185 K. This facile growth scheme of nitric acid hydrates requires the presence of H2O ice at thicknesses in excess of approximately hundred nanometers. Absolute absorption cross sections in the mid-IR spectral range (700-4000 cm-1) of all three title compounds have been obtained after spectral subtraction of excess pure ice at temperatures characteristic of the upper troposphere/lower stratosphere. Prominent IR absorption frequencies correspond to the antisymmetric nitrate stretch vibration (ν3(NO3-)) in the range 1300 to 1420 cm-1 and the bands of hydrated protons in the range 1670 to 1850 cm-1 in addition to the antisymmetric O-H stretch vibration of bound H2O in the range 3380 to 3430 cm-1 for NAT.

Study of plutonium sorption in aluminia column in the system HNO3-HF

International Nuclear Information System (INIS)

Araujo, J.A. de.

1977-01-01

The column chromatographic method using alumina has been applied successfully to study the sorption-desorption behavior of plutonium traces in HNO 3 -HF and HNO 3 -HF-UO 2 (NO 3 ) 2 systems, aiming to elaborate a process for recovering plutonium traces from reprocessing wastes, mainly in existing solutions where uranium is presented in macro quantities. Basically, the method consists in the sorption of plutonium by percolating a solution containing HNO 3 (0,1 to 0,8M) or uranyl nitrate (1-50 gU/l) and HF(0,1 to 0,3M) through an Al 2 O 3 collumn. The plutonium is fixed on Al 2 O 3 whereas the uranyl ions is collected in the efluent. The adsorption of Pu-III, Pu-IV and Pu-VI in the presence of HF was determined and Pu-IV can be almost completely sorbed. The Pu-IV is eluted by reduction to Pu-III in the column using 3 M HNO 3 -0,005M FeSO 4 at 50 0 C as elutrient. This method is very simple and can be applied for separation and purification of plutonium (traces) from uranyl nitrate or others coming solutions from wet chemistry of irradiated fuels [pt

Studies on avoiding second organic phase in DHDECMP-TBP/kerosene with the extraction of HNO3-Gd

International Nuclear Information System (INIS)

Huang Zilin; Zhao Hugen; Hu Jingxin

1998-01-01

The bidentate extractant of DHDECMP (CMP) may by more practical in the treatment of high-level liquid waste (HLLW) if it could be diluted by kerosene. Bu it is difficult to avoid the formation of second organic phase in CMP/kerosene with the extraction of HNO 3 and RE. It is advantageous to avoid the formation of second organic phase after the extraction of HNO 3 and Gd by adding TBP. The formation conditions of second organic phase are studied and the loaded capacity of RE-HNO 3 is measured. The results are as follows. Raising temperature has a slight advantage to avoid formation of second organic phase. The addition of TBP is beneficial to avoid second organic phase. An organic system of 0.60 mol/L CMP-1.20 mol/L TBP/kerosene contacting with an aqueous solution containing 6.0 mol/L HNO 3 does not appear second organic phase. The extraction of RE leads to form second organic phase which does not occur when it only extracts HNO 3 . It is able to avoid second organic phase with a low concentration of CMP. The higher concentration of CMP, the higher loaded capacity of Gd 3+ and HNO 3 . It is advantageous to avoid second organic phase formation and also to get a higher loaded capacity of Gd 3+ and HNO 3 with increasing concentration of TBP. The loaded capacity of Gd decreases with an increasing initial concentration of HNO 3 in aqueous phase because of an increasing concentration of HNO 3 in the organic phase. The loaded capacity of Gd increases with raising temperature. To treat HLLW, the organic system containing 0.60 mol/L CMP and 1.40 mol/L TBP is recommended

Radiation chemical behavior of Rh(III) in HClO4 and HNO3

International Nuclear Information System (INIS)

Vladimirova, M.V.; Khalkina, E.V.

1995-01-01

The radiation chemical behavior of Rh is very interesting since Rh accumulates in irradiated U but has not been reported in the literature. Scattered data do exist for the radiation chemical behavior of Rh(III) in weakly acidic and alkaline solutions. Pulsed radiolysis was used to investigate the formation of unstable oxidation states of Rh during reduction and oxidation of Rh(III) in neutral solutions. The rate constant of the reaction Rh(III) + e aq - was found to be 6·10 10 liter/mole·sec. The radiation chemical behavior of Rh(III) toward γ-radiolysis in neutral, weakly acidic (up to 0.1 N), and alkaline solutions was examined. In neutral solutions of [Rh(NH 3 ) 5 Cl]Cl 2 and RhCl 3 , metallic Rh is formed. The degree of reduction is ∼ 1%. In neutral and weakly acidic solutions of Rh(NO 3 ) 3 , Rh 2 O 3 ·xH 2 O is formed. Irradiation of Rh(ClO 4 ) 3 solutions produces no reduction. The radiation chemical behavior of Rh(III) in HClO 4 and HNO 3 solutions at concentrations > 1 M is studied in the present work

Measurements of HNO3 and N2O5 using ion drift-chemical ionization mass spectrometry during the MILAGRO/MCMA-2006 campaign

Science.gov (United States)

Zheng, J.; Zhang, R.; Fortner, E. C.; Volkamer, R. M.; Molina, L.; Aiken, A. C.; Jimenez, J. L.; Gaeggeler, K.; Dommen, J.; Dusanter, S.; Stevens, P. S.; Tie, X.

2008-11-01

An ion drift-chemical ionization mass spectrometer (ID-CIMS) was deployed in Mexico City between 7 and 31 March to measure gas-phase nitric acid (HNO3) and dinitrogen pentoxide (N2O5 during the Mexico City Metropolitan Area (MCMA)-2006 field campaign. The observation site was located at the Instituto Mexicano del Petróleo in the northern part of Mexico City urban area with major emissions of pollutants from residential, vehicular and industrial sources. Diurnally, HNO3 was less than 200 parts per trillion (ppt) during the night and early morning. The concentration of HNO3 increased steadily from around 09:00 a.m. central standard time (CST), reached a peak value of 0.5 to 3 parts per billion (ppb) in the early afternoon, and then declined sharply to less than half of the peak value near 05:00 p.m. CST. An inter-comparison between the ID-CIMS and an ion chromatograph/mass spectrometer (ICMS) showed a good agreement between the two HNO3 measurements (R2=0.75). The HNO3 mixing ratio was found to anti-correlate with submicron-sized aerosol nitrate, suggesting that the gas-particle partitioning process was a major factor in determining the gaseous HNO3 concentration. Losses by irreversible reactions with mineral dust and via dry deposition also could be important at this site. Most of the times during the MCMA 2006 field campaign, N2O5 was found to be below the detection limit (about 30 ppt for a 10 s integration time) of the ID-CIMS, because of high NO mixing ratio at the surface (>100 ppb) during the night. An exception occurred on 26 March 2006, when about 40 ppt N2O5 was observed during the late afternoon and early evening hours under cloudy conditions before the build-up of NO at the surface site. The results revealed that during the MCMA-2006 field campaign HNO3 was primarily produced from the reaction of OH with NO2 and regulated by gas/particle transfer and dry deposition. The production of HNO3 from N2O5 hydrolysis during the nighttime was small because of

Ozone, nitric acid, and ammonia air pollution is unhealthy for people and ecosystems in southern Sierra Nevada, California

Science.gov (United States)

R. Cisneros; A. Bytnerowicz; D. Schweizer; S. Zhong; S. Traina; D.H. Bennett

2010-01-01

Two-week average concentrations of ozone (O3), nitric acid vapor (HNO3) and ammonia (NH3) were measured with passive samplers during the 2002 summer season across the central Sierra Nevada Mountains, California, along the San Joaquin River drainage. Elevated concentrations of the pollutants were...

Removal of uranium and gross radioactivity from coal bottom ash by CaCl{sub 2} roasting followed by HNO{sub 3} leaching

Energy Technology Data Exchange (ETDEWEB)

Lei, Xuefei; Qi, Guangxia; Sun, Yinglong; Xu, Hui; Wang, Yi, E-mail: yi_wang@tsinghua.edu.cn

2014-07-15

Highlight: • Roasting the ash with CaCl{sub 2} enhanced the removal of uranium and gross radioactivity. • 87.3% of the total uranium was removed via the optimized roast-leach process. • Nearly 90% of gross α and β radioactivity was removed via the roast-leach process. • Molten CaCl{sub 2} promoted the incorporation of Ca and Al into Si-O matrices in ash. • Radionuclides were removed by the acid decomposition of newly formed silicates. - Abstract: A roast-leach method using CaCl{sub 2} and HNO{sub 3} to remove uranium and gross radioactivity in coal bottom ash was investigated. Heat treatment of the ash with 100% CaCl{sub 2} (900 °C, 2 h) significantly enhanced uranium leachability (>95%) compared with direct acid-leaching (22.6–25.5%). The removal efficiency of uranium and gross radioactivity increased steeply with increasing CaCl{sub 2} content, from 10% to 50%, and a HNO{sub 3} leaching time from 5 min to 1 h, but remained nearly constant or decreased slightly with increasing CaCl{sub 2} dosage >50% or acid-leaching time >1 h. The majority of the uranium (87.3%), gross α (92.9%) and gross β (84.9%) were removed under the optimized roast-leach conditions (50% CaCl{sub 2}, 1 M HNO{sub 3} leaching for 1 h). The mineralogical characteristics of roasted clinker indicated that molten CaCl{sub 2} promoted the incorporation of Ca into silica and silicates and resulted in its progressive susceptibility to acid attack. Uranium and other radionuclides, most likely present in the form of silicates or in association with miscellaneous silicates in the highest density fraction (>2.5 g mL{sup −1}), were probably leached out as the result of the acid decomposition of newly formed “gelatinizing silicates”.

Mechanism of plutonium metal dissolution in HNO3-HF-N2H4 solution

International Nuclear Information System (INIS)

Karraker, D.G.

1985-01-01

An oxidation-reduction balance of the products of the dissolution of plutonium metal and alloys in HNO 3 -HF-N 2 H 4 solution shows that the major reactions during dissolution are the reduction of nitrate to NH 3 , N 2 and N 2 O by the metal, and the oxidation of H free radicals to NH 3 by N 2 H 4 . Reactions between HNO 3 and N 2 H 4 produce varying amounts of HN 3 . The reaction rate is greater for delta-Pu than alpha-Pu, and is increased by higher concentrations of HF and HNO 3 . The low yield of reduced nitrogen species indicates that nitrate is reduced on the metal surface without producing a significant concentration of species that react with N 2 H 4 . It is conjectured that intermediate Pu valences and electron transfer within the metal are involved. 7 refs., 3 tabs

Inhibiting effects of imidazole on copper corrosion in 1 M HNO3 solution

International Nuclear Information System (INIS)

Lee, Woo-Jin

2003-01-01

The present work deals with the inhibiting effects of imidazole on the pure copper (Cu) corrosion in 1 M HNO 3 solution analysing potentiodynamic polarisation curves, potentiostatic anodic current transient, AC impedance spectra and X-ray photoelectron spectra (XPS). By adding imidazole to HNO 3 solution, the polarisation curves showed decrease in the corrosion current and the cathodic current, suggesting that imidazole acts as an effective cathodic inhibitor to Cu corrosion. From the measured anodic current transients, it is inferred that the protective Cu-imidazole complex film is simultaneously formed with the Cu oxide in the presence of imidazole during the early stage of the anodic polarisation. Analysis of the AC impedance spectra revealed that the values of the charge transfer resistance R ct obtained in imidazole-containing HNO 3 solution were greater than that value in imidazole-free one and at the same time steadily increased with immersion time to the constant value. Contrarily, the capacitance value was abruptly lowered from the double layer capacitance C dl to the complex film capacitance C cf in the progress of immersion time. Furthermore, the Warburg coefficient σ value for the ion diffusion through the complex film was observed to increase with immersion time. This means that the Cu(N-OH) complex film becomes thicker during immersion in the HNO 3 solution with imidazole through the inward growth of the N-rich outer layer to the O-rich inner layer, as well validated by XPS. Based upon the experimental results, it is suggested that the Cu corrosion in 1 M HNO 3 solution is efficiently inhibited with the addition of imidazole by retarding both the charge transfer on cathodic sites of the Cu surface in the early stage of immersion time and the subsequent ion diffusion through the steadily growing complex film

New insights in third phase formation in the U(VI)-HNO3, TBP-alkane system

International Nuclear Information System (INIS)

Jensen, M. P.; Chiarizia, R.; Ferraro, J. R.; Borkowski, M.; Nash, K. L.; Thiyagarajan, P.; Littrell, K. C.

2001-01-01

In this work, the system U(VI)-HNO 3 -tributylphosphate (TBP)-n-dodecane has been revisited with the objective of gaining coordination chemistry and structural information on the species that are formed in the organic phase before and after third phase formation. Chemical analyses, spectroscopic and EXAFS data indicate that U(VI) is extracted as the UO 2 (NO 3 ) 2 · 2TBP adduct, while the third phase species has the composition UO 2 (NO 3 ) 2 · 2TBP · HNO 3 . Small-angle neutron scattering (SANS) data reveal the presence in the organic phase, both before and after phase splitting, of ellipsoidal aggregates whose formation seems to depend more on the extraction of HNO 3 than that of U(VI)

Hydrolytic and radiolytic degradation of TBP in TBP.30% V/V-dodecane/UO2(NO3)2.HNO3.H2O systems

International Nuclear Information System (INIS)

Barreta, L.G.

1980-01-01

The hydrolytic and radiolytic degradation of TBP is investigated in systems of TBP 30% V/V-dodecane/H 2 O . HNO 3 . UO 2 (NO 3 ) 2 by gas chromatographic determination of HDBP. No direct relation between the concentration of HDBP formed and the quantity of HNO 3 extracted by the organic phase is observed in the studies of hydrolysis of TBP. The HDBP concentration is seen to increase non-linearly with the concentration of HNO 3 extracted by the organic phase. Radiolytic studies show that for doses greater than 1 Wh/l, the concentration of HDBP formed increases with the dose absorbed by the system. Whith doses smaller than 1 Wh/l and acid concentration greater than 2 M, two distinct patterns of behavior are observed. The concentration of HDBP as a function of the radiation dose absorbed by the system presents a minimum for uranyl nitrate concentrations smaller than 0.9 M; for uranyl nitrate concentrations greater than 1.3 M the concentration of radiolytic HDBP cannot be calculated because the concentration of the hydrolytic HDBP determined is greater than the sum of the experimental concentrations of hydrolytic and radiolytic HDBP. It is known that the dose absorbed by the process solutions during the reprocessing of light water reactor fuel elements is smaller than one Wh/l. Thus, dose rates between zero and one Wh/l should be studied for this system. (Author) [pt

Direct extraction of uranium and plutonium from oxide fuel using TBP-HNO3 complex for super-DIREX process

International Nuclear Information System (INIS)

Miura, S.; Kamiya, M.; Nomura, K.; Koyama, T.; Ogum, S.; Shimada, T.; Mori, Y.; Enokida, Y.

2004-01-01

Super-DIREX is a new reprocessing method which has high economical efficiency. Experimental study of this process was started on the direct extraction of U and Pu from irradiated MOX fuel by the supercritical carbon dioxide (SFCO 2 ) containing TBP-HNO 3 complex. This report describes direct extraction of U and Pu with TBP-HNO 3 complex at atmospheric pressure, as the first test for irradiated fuel, in order to investigate the applicability of SFCO 2 containing TBP-HNO 3 complex. In this test, dependency on dissolution temperature, Pu content, fuel/ TBP-HNO 3 complex ratio and effect of voloxidation were investigated. From these results, TBP-HNO 3 complex was found to be effective in the respect of the recovery of U and Pu. The number of the process step in dissolution and co-extraction is small, and amount of waste can be reduced. It is applicable to the direct extraction in Super-DIREX. (authors)

Foliar loading and metabolic assimilation of dry deposited nitric acid air pollutants by trees

Science.gov (United States)

Pamela E. Padgett; Hillary Cook; Andrzej Bytnerowicz; Robert L. Heath

2009-01-01

Dry deposition of nitric acid vapor (HNO(3)) is a major contributor to eutrophication of natural ecosystems. Although soil fertilization by nitrogen deposition is considered to be the primary pathway for changes in plant nutrient status and shifts in ecological structure, the aerial portion of plants offer many times the surface area in which to...

Observations of total RONO2 over the boreal forest: NOx sinks and HNO3 sources

Directory of Open Access Journals (Sweden)

E. C. Browne

2013-05-01

Full Text Available In contrast with the textbook view of remote chemistry where HNO3 formation is the primary sink of nitrogen oxides, recent theoretical analyses show that formation of RONO2 (ΣANs from isoprene and other terpene precursors is the primary net chemical loss of nitrogen oxides over the remote continents where the concentration of nitrogen oxides is low. This then increases the prominence of questions concerning the chemical lifetime and ultimate fate of ΣANs. We present observations of nitrogen oxides and organic molecules collected over the Canadian boreal forest during the summer which show that ΣANs account for ~20% of total oxidized nitrogen and that their instantaneous production rate is larger than that of HNO3. This confirms the primary role of reactions producing ΣANs as a control over the lifetime of NOx (NOx = NO + NO2 in remote, continental environments. However, HNO3 is generally present in larger concentrations than ΣANs indicating that the atmospheric lifetime of ΣANs is shorter than the HNO3 lifetime. We investigate a range of proposed loss mechanisms that would explain the inferred lifetime of ΣANs finding that in combination with deposition, two processes are consistent with the observations: (1 rapid ozonolysis of isoprene nitrates where at least ~40% of the ozonolysis products release NOx from the carbon backbone and/or (2 hydrolysis of particulate organic nitrates with HNO3 as a product. Implications of these ideas for our understanding of NOx and NOy budget in remote and rural locations are discussed.

Structural and optical properties of vapor-etched porous GaAs

Energy Technology Data Exchange (ETDEWEB)

Smida, A.; Laatar, F. [Photovoltaic Laboratory, Centre for Research and Technology Energy, Tourist Route Soliman, BP 95, 2050 Hammam-Lif (Tunisia); Hassen, M., E-mail: mhdhassen@yahoo.fr [Photovoltaic Laboratory, Centre for Research and Technology Energy, Tourist Route Soliman, BP 95, 2050 Hammam-Lif (Tunisia); Higher Institute of Applied Science and Technology of Sousse, City Taffala (Ibn Khaldun), 4003 Sousse (Tunisia); Ezzaouia, H. [Photovoltaic Laboratory, Centre for Research and Technology Energy, Tourist Route Soliman, BP 95, 2050 Hammam-Lif (Tunisia)

2016-08-15

This paper consists to present first results concerning the structure of porous GaAs layer (por-GaAs-L) prepared by using HF/HNO{sub 3} as acidic solution in vapor etching (VE) method. In order to clarify this method, we detail here its principle and explain how por-GaAs-Ls are formed, taking into account the influencing of the exposure time of the GaAs substrate to the acid vapor. The etched GaAs layers have been investigated by UV–visible and PL analysis. One porous layer was performed to be characterised by Atomic Force Microscopy (AFM), FTIR spectroscopy, and X-Ray Diffraction (XRD). The porous structure was constituted by a nanocrystals with an average size about 6 nm. These nanocrystals were calculated from XRD peak using Scherrer's formula, AFM imaging, and also by using effective mass approximation model from effective band gap. - Highlights: • Porous GaAs layer was prepared by using Vapor etching (VE) method. • Effect of VE duration on the microstructural optical properties of the GaAs substrate • Porous structure of GaAs layer was demonstrated by using SEM and AFM microscopy.

Structural and optical properties of vapor-etched porous GaAs

International Nuclear Information System (INIS)

Smida, A.; Laatar, F.; Hassen, M.; Ezzaouia, H.

2016-01-01

This paper consists to present first results concerning the structure of porous GaAs layer (por-GaAs-L) prepared by using HF/HNO 3 as acidic solution in vapor etching (VE) method. In order to clarify this method, we detail here its principle and explain how por-GaAs-Ls are formed, taking into account the influencing of the exposure time of the GaAs substrate to the acid vapor. The etched GaAs layers have been investigated by UV–visible and PL analysis. One porous layer was performed to be characterised by Atomic Force Microscopy (AFM), FTIR spectroscopy, and X-Ray Diffraction (XRD). The porous structure was constituted by a nanocrystals with an average size about 6 nm. These nanocrystals were calculated from XRD peak using Scherrer's formula, AFM imaging, and also by using effective mass approximation model from effective band gap. - Highlights: • Porous GaAs layer was prepared by using Vapor etching (VE) method. • Effect of VE duration on the microstructural optical properties of the GaAs substrate • Porous structure of GaAs layer was demonstrated by using SEM and AFM microscopy.

Dual vapor extraction on acidic sludge tar at a former refinery

International Nuclear Information System (INIS)

Lear, P.R.; Beall, P.; Townsend, S.

1996-01-01

OHM Remediation Services Corp conducted a pilot-scale demonstration for a novel application of dual vapor extraction technology for the pretreatment of the acid tar sludge material. The acid tar sludge comprised of approximately 60% asphaltene hydrocarbon material, 20% clay, and up to 20% sulfuric acid (H 2 SO 4 ). The liquid layer in the bottom of the pits has a low pH ( 2 ) gas which is released with the sludge material is excavated or handled. The objective of the dual vapor extraction was to remove the SO 2 vapors and liquid layer containing sulfuric acid prior to any further treatment. The dual vapor extraction would reduce the amount of alkaline reagent required for neutralization while eliminating the health and safety concerns. Overall, the DVE pilot demonstration successfully showed that both liquids and vapors could be removed from the acid tar sludge material. The liquid present in the lower portions of the pits will have pH values of 1.0 or less and acidities on the order of 5% H 2 SO 4 . The liquid removed from the acid tar sludge material by a DVE system will have slightly higher pH (∼1.5) and lower alkalinities (∼3% H 2 SO 4 ). The SO 2 concentration in the vapors removed by the DVE system will be variable with initial levels approaching 1,200 ppmv SO 2 . The SO 2 concentration in the vapor phase should decrease with time. A caustic scrubber solution will remove any SO 2 from the vapor phase. After DVE treatment, the acid tar sludge material would have a slightly increased pH and a decreased SO 2 concentration

Interaction of tellurium and tellurium-containing semiconductor compounds with solutions of HI-HNO3-H2O system

International Nuclear Information System (INIS)

Tomashik, V.N.; Sava, A.A.; Tomashik, Z.F.

1994-01-01

As a result of experimental investigations and physical-chemical simulation are established regularities of solution of semiconducting tellurium-containing compounds in HI-HNO 3 -H 2 O systems. In HNO 3 -HI system solutions enriched by HNO 3 are not used for CdTe treatment but HI enriched solution are similar in composition with I 2 -HI solutions. Solution of the given tellurium-containing materials proceeds by a chemical mechanism and is determined by tellurium oxidation with iodine

Characterization of stain etched p-type silicon in aqueous HF solutions containing HNO{sub 3} or KMnO{sub 4}

Energy Technology Data Exchange (ETDEWEB)

Mogoda, A.S., E-mail: awad_mogoda@hotmail.com [Department of Chemistry, Faculty of Science, Cairo University, Giza (Egypt); Ahmad, Y.H.; Badawy, W.A. [Department of Chemistry, Faculty of Science, Cairo University, Giza (Egypt)

2011-04-15

Research highlights: {yields} Stain etching of p-Si in aqueous HF solutions containing HNO{sub 3} or KMnO{sub 4} was investigated. {yields} The electrical conductivity of the etched Si surfaces was measured using impedance technique. {yields} Scanning electron microscope and energy disperse X-ray were used to analyze the etched surfaces. {yields} Etching in aqueous HF solution containing HNO{sub 3} led to formation of a porous silicon layer. {yields} The formation of the porous silicon layer in HF/KMnO{sub 4} was accompanied by deposition of K{sub 2}SiF{sub 6} on the pores surfaces. - Abstract: Stain etching of p-type silicon in hydrofluoric acid solutions containing nitric acid or potassium permanganate as an oxidizing agent has been examined. The effects of etching time, oxidizing agent and HF concentrations on the electrochemical behavior of etched silicon surfaces have been investigated by electrochemical impedance spectroscopy (EIS). An electrical equivalent circuit was used for fitting the impedance data. The morphology and the chemical composition of the etched Si surface were studied using scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) techniques, respectively. A porous silicon layer was formed on Si etched in HF solutions containing HNO{sub 3}, while etching in HF solutions containing KMnO{sub 4} led to the formation of a porous layer and simultaneous deposition of K{sub 2}SiF{sub 6} inside the pores. The thickness of K{sub 2}SiF{sub 6} layer increases with increasing the KMnO{sub 4} concentration and decreases as the concentration of HF increases.

Removal of Procion Red dye from colored effluents using H2SO4-/HNO3-treated avocado shells (Persea americana) as adsorbent.

Science.gov (United States)

Georgin, Jordana; da Silva Marques, Bianca; da Silveira Salla, Julia; Foletto, Edson Luiz; Allasia, Daniel; Dotto, Guilherme Luiz

2018-03-01

The treatment of colored effluents containing Procion Red dye (PR) was investigated using H 2 SO 4 and HNO 3 modified avocado shells (Persea americana) as adsorbents. The adsorbent materials (AS-H 2 SO 4 and AS-HNO 3 ) were properly characterized. The adsorption study was carried out considering the effects of adsorbent dosage and pH. Kinetic, equilibrium, and thermodynamic aspects were also evaluated. Finally, the adsorbents were tested to treat simulated dye house effluents. For both materials, the adsorption was favored using 0.300 g L -1 of adsorbent at pH 6.5, where, more than 90% of PR was removed from the solution. General order model was able to explain the adsorption kinetics for both adsorbents. The Sips model was adequate to represent the isotherm data, being the maximum adsorption capacities of 167.0 and 212.6 mg g -1 for AS-H 2 SO 4 and AS-HNO 3 , respectively. The adsorption processes were thermodynamically spontaneous, favorable (- 17.0 Avocado shells, after a simple acid treatment, can be a low-cost option to treat colored effluents.

Waste acid detoxification and reclamation: Final Phase II report: Summary of distillation and material degradation tests for FY 1987 and FY 1988

International Nuclear Information System (INIS)

Brouns, T.M.; Stewart, T.L.

1988-11-01

The objective of the Waste Acid Detoxification and Reclamation project is to develop processes for reducing the volume, quantity, and toxicity of metal-bearing waste acids. The primary incentives for implementing these types of waste minimization processes are regulatory and economic (that is, to meet requirements in the Resource Conservation and Recovery Act and reduce the cost for treatment, storage, and disposal). Two precipitation processes and a distillation process are being developed to minimize waste from fuel fabrication operations or other metal-finishing operations conducted at US Department of Energy Defense Programs (DOE-DP) facilities. Waste process acids such as (1) HF-HNO 3 etch solutions containing Zr as a major metal impurity, and (2) HNO 3 strip solutions containing Cu as a major metal impurity are detoxified and reclaimed by concurrently precipitating heavy metals and regenerating acid for recycle. Acid from a third waste acid stream generated from chemical milling operations is reclaimed by the use of distillation. This stream comprises HNO 3 and H 2 SO 4 containing U as the major metal impurity. Distillation allows NO 3 /sup /minus// to be displaced by SO 4 /sup /minus/2/ in metal salts; free HNO 3 is then vaporized from the U-bearing sulfate stream. In a downstream precipitation step, uranium can be recovered from the sulfate stream. This report summarizes distillation tests and candidate material degradation tests conducted during FY 1987 and FY 1988

Study on the plutonium extraction and reextraction in radiolytic degraded system 30 % TBP-n-dodecane/HNO3-H2O

International Nuclear Information System (INIS)

Hoffmann, P.M.; Wronska, T.

1980-01-01

The degree of the complexation of plutonium(4) by the products of radiolysis of the system 30 % TBP-n-dodecane/HNO 3 -H 2 O as a function of radiation dose and concentration of nitric acid has been studied. The special method of calculation based on extraction equilibria was used. The retention of plutonium in the organic phase after single reductive reextraction has been determined. (author)

Structural Characteristics of Homogeneous Hydrophobic Ionic Liquid-HNO3-H2O Ternary System: Experimental Studies and Molecular Dynamics Simulations.

Science.gov (United States)

Fu, Jing; Yang, Y Isaac; Zhang, Jun; Chen, Qingde; Shen, Xinghai; Gao, Yi Qin

2016-06-16

The solubility of water in the hydrophobic ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C2mim][NTf2]) increases significantly in the presence of HNO3. [C2mim][NTf2] is completely miscible with HNO3 but immiscible with water. The triangular phase diagram of the ternary system [C2mim][NTf2]-HNO3-H2O was determined at 300.1 K. The homogeneous [C2mim][NTf2]-HNO3-H2O phase is thermodynamically stable, while it can be separated into two phases with an increase of water content. Experiments (electrospray ionization mass spectrometry, Fourier transform infrared spectrometry, and (1)H-nuclear magnetic resonance spectrometry) and molecular dynamics simulations were carried out to investigate the interaction between [C2mim][NTf2], HNO3, and water in the homogeneous phase. It was found that NO3(-) ions interact with both C2mim(+) and water via H-bonding and act as a "bridge" to induce a large amount of water to be dissolved in the hydrophobic IL phase. This confirms that the complexes [C2mim-NTf2-C2mim](+) and [NTf2-C2mim-NTf2](-) exist in the homogeneous [C2mim][NTf2]-HNO3-H2O system at the concentration of HNO3 up to 27.01 wt % and of water as high as 20.74 wt %.

Modeling of Pu(IV) extraction and HNO3 speciation in nuclear fuel reprocessing

International Nuclear Information System (INIS)

De-Sio, S.

2012-01-01

The PUREX process is a solvent extraction method dedicated to the reprocessing of irradiated nuclear fuel in order to recover pure uranium and plutonium from aqueous solutions of concentrated nitric acid. The tri-n-butylphosphate (TBP) is used as the extractant in the organic phase. The aim of this thesis work was to improve the modeling of liquid-liquid extraction media in nuclear fuel reprocessing. First, Raman and 14 N NMR measurements, coupled with theoretical calculations based on simple solutions theory and BIMSA modeling, were performed in order to get a better understanding of nitric acid dissociation in binary and ternary solutions. Then, Pu(IV) speciation in TBP after extraction from low nitric acid concentrations was investigated by EXAFS and vis-NIR spectroscopies. We were able to show evidence of the extraction of Pu(IV) hydrolyzed species into the organic phase. A new structural study was conducted on An(VI)/TBP and An(IV)/TBP complexes by coupling EXAFS measurements with DFT calculations. Finally, extraction isotherms modeling was performed on the Pu(IV)/HNO 3 /H 2 O/TBP 30%/dodecane system (with Pu at tracer scale) by taking into account deviation from ideal behaviour in both organic and aqueous phases. The best modeling was obtained when considering three plutonium (IV) complexes in the organic phase: Pu(OH) 2 (NO 3 ) 2 (TBP) 2 , Pu(NO 3 ) 4 (TBP) 2 and Pu(NO 3 ) 4 (TBP) 3 . (author) [fr

Numerical simulation of extraction behavior of major components in the CMPO-TBP-HNO3 system

International Nuclear Information System (INIS)

Takanashi, M.; Koma, Y.; Koyama, T.; Funasaka, H.

2000-01-01

A numerical simulation code was developed in order to find the optimum condition for separation and the recovery of TRU (TRansUranium) elements in the octyl(phenyl)-N,N-di-isobutyl-carbamoyl-methyl-phosphine oxide (CMPO) - tri-butyl phosphate (TBP) - HNO 3 solvent extraction system. This code is able to predict the extraction behavior of americium and europium in the system containing many components. Calculations of concentration profiles of americium and lanthanides were carried out for a counter current experiment with laboratory scale mixer-settlers. The calculated profiles were in agreement with the experimental ones. The effect of oxalic acid was also included in the calculation and was discussed. (authors)

Simulation of technetium extraction behavior in UO2 (NO3)2-TcO4--HNO3-H2O/TBP-kerosene system

International Nuclear Information System (INIS)

Zhang Chunlong; He Hui; Chen Yanxin; Tang Hongbin

2012-01-01

By comparing and analyzing lots of reported data of technetium with the computing results, a modification function P(c 0 (U), t) was introduced to the existing distribution coefficient model of technetium, and a new mathematical model for simulating technetium extraction behavior in the system of UO 2 (NO 3 ) 2 -TcO 4 -HNO 3 -H 2 O/TBP- kerosene was established, as well as a computer program. The reliability of the program was verified by 179 sets of distribution coefficient data, and the results were found to agree well with experimental data. By comparing the reported data of technetium with the computing results, an evaluation was made to test the performance of the revised model. It turned out that the calculation results of the new model were more reliable than that of the one reported previously. The revised model and program can be the foundation to simulating technetium extraction behavior in the system of UO 2 (NO 3 ) 2 - TcO 4 - -HNO 3 -H 2 O/TBP-kerosene with the temperature scope from 10 to 60℃, U concentration from 0 to 280 g/L, and nitric acid concentration from 0.1 to 5 mol/L. (authors)

Determination of total fluoride in HF/HNO3/H2SiF6 etch solutions by new potentiometric titration methods.

Science.gov (United States)

Weinreich, Wenke; Acker, Jörg; Gräber, Iris

2007-03-30

In the photovoltaic industry the etching of silicon in HF/HNO(3) solutions is a decisive process for cleaning wafer surfaces or to produce certain surface morphologies like polishing or texturization. With regard to cost efficiency, a maximal utilisation of etch baths in combination with highest quality and accuracy is strived. To provide an etch bath control realised by a replenishment with concentrated acids the main constituents of these HF/HNO(3) etch solutions including the reaction product H(2)SiF(6) have to be analysed. Two new methods for the determination of the total fluoride content in an acidic etch solution based on the precipitation titration with La(NO(3))(3) are presented within this paper. The first method bases on the proper choice of the reaction conditions, since free fluoride ions have to be liberated from HF and H(2)SiF(6) at the same time to be detected by a fluoride ion-selective electrode (F-ISE). Therefore, the sample is adjusted to a pH of 8 for total cleavage of the SiF(6)(2-) anion and titrated in absence of buffers. In a second method, the titration with La(NO(3))(3) is followed by a change of the pH-value using a HF resistant glass-electrode. Both methods provide consistent values, whereas the analysis is fast and accurate, and thus, applicable for industrial process control.

Ozone, nitric acid, and ammonia air pollution is unhealthy for people and ecosystems in southern Sierra Nevada, California

Energy Technology Data Exchange (ETDEWEB)

Cisneros, Ricardo, E-mail: rcisneros@fs.fed.u [USDA Forest Service, Pacific Southwest Region, 1600 Tollhouse Road, Clovis, CA 93611 (United States); Bytnerowicz, Andrzej, E-mail: abytnerowicz@fs.fed.u [USDA Forest Service, Pacific Southwest Research Station, 4955 Canyon Crest Dr., Riverside, CA 92507 (United States); Schweizer, Donald, E-mail: dschweizer@fs.fed.u [USDA Forest Service, Pacific Southwest Region, 1600 Tollhouse Road, Clovis, CA 93611 (United States); Zhong, Sharon, E-mail: zhongs@msu.ed [Department of Geography, Michigan State University, 116 Geography Building East, Lansing, MI 48824-1117 (United States); Traina, Samuel, E-mail: straina@ucmerced.ed [Environmental Systems Graduate Group, University of California Merced, 5200 North Lake Road, Merced, CA 95343 (United States); Bennett, Deborah H., E-mail: dhbennett@ucdavis.ed [Department of Public Health Sciences, University of California Davis, One Shields Avenue, TB 169 Davis, CA 95616 (United States)

2010-10-15

Two-week average concentrations of ozone (O{sub 3}), nitric acid vapor (HNO{sub 3}) and ammonia (NH{sub 3}) were measured with passive samplers during the 2002 summer season across the central Sierra Nevada Mountains, California, along the San Joaquin River drainage. Elevated concentrations of the pollutants were determined with seasonal means for individual sites ranging between 62 and 88 ppb for O{sub 3}, 1.0-3.8 {mu}g m{sup -3} for HNO{sub 3}, and 2.6-5.2 {mu}g m{sup -3} for NH{sub 3}. Calculated O{sub 3} exposure indices were very high, reaching SUM00-191 ppm h, SUM60-151 ppm h, and W126-124 ppm h. Calculated nitrogen (N) dry deposition ranged from 1.4 to 15 kg N ha{sup -1} for maximum values, and 0.4-8 kg N ha{sup -1} for minimum values; potentially exceeding Critical Loads (CL) for nutritional N. The U.S., California, and European 8 h O{sub 3} human health standards were exceeded during 104, 108, and 114 days respectively, indicating high risk to humans from ambient O{sub 3}. - Ozone concentrations remained unchanged while those of nitric acid vapor and ammonia decreased along the river drainage crossing the Sierra Nevada Mountains.

Ozone, nitric acid, and ammonia air pollution is unhealthy for people and ecosystems in southern Sierra Nevada, California

International Nuclear Information System (INIS)

Cisneros, Ricardo; Bytnerowicz, Andrzej; Schweizer, Donald; Zhong, Sharon; Traina, Samuel; Bennett, Deborah H.

2010-01-01

Two-week average concentrations of ozone (O 3 ), nitric acid vapor (HNO 3 ) and ammonia (NH 3 ) were measured with passive samplers during the 2002 summer season across the central Sierra Nevada Mountains, California, along the San Joaquin River drainage. Elevated concentrations of the pollutants were determined with seasonal means for individual sites ranging between 62 and 88 ppb for O 3 , 1.0-3.8 μg m -3 for HNO 3 , and 2.6-5.2 μg m -3 for NH 3 . Calculated O 3 exposure indices were very high, reaching SUM00-191 ppm h, SUM60-151 ppm h, and W126-124 ppm h. Calculated nitrogen (N) dry deposition ranged from 1.4 to 15 kg N ha -1 for maximum values, and 0.4-8 kg N ha -1 for minimum values; potentially exceeding Critical Loads (CL) for nutritional N. The U.S., California, and European 8 h O 3 human health standards were exceeded during 104, 108, and 114 days respectively, indicating high risk to humans from ambient O 3 . - Ozone concentrations remained unchanged while those of nitric acid vapor and ammonia decreased along the river drainage crossing the Sierra Nevada Mountains.

Development of acid-resistant HEPA filter components

International Nuclear Information System (INIS)

Terada, K.; Woodard, R.W.; Buttedahl, O.I.

1981-01-01

Laboratory and in-service tests of various HEPA filter media and separators were conducted to establish their relative resistances to HNO 3 -HF vapors. Filter medium of glass fiber with Nomex additive and aluminum separators with an epoxy-vinyl coating have performed quite well in the acid environment in the laboratory, and in prototype-filters placed in service in a plenum at Rocky Flats. Proprietary filters with new design and/or components were also tested in service with generally good results

Optimization of HNO3 leaching of copper from old AMD Athlon processors using response surface methodology.

Science.gov (United States)

Javed, Umair; Farooq, Robina; Shehzad, Farrukh; Khan, Zakir

2018-04-01

The present study investigates the optimization of HNO 3 leaching of Cu from old AMD Athlon processors under the effect of nitric acid concentration (%), temperature (°C) and ultrasonic power (W). The optimization study is carried out using response surface methodology with central composite rotatable design (CCRD). The ANOVA study concludes that the second degree polynomial model is fitted well to the fifteen experimental runs based on p-value (0.003), R 2 (0.97) and Adj-R 2 (0.914). The study shows that the temperature is the most significant process variable to the leaching concentration of Cu followed by nitric acid concentration. However, ultrasound power shows no significant impact on the leaching concentration. The optimum conditions were found to be 20% nitric acid concentration, 48.89 °C temperature and 5.52 W ultrasound power for attaining maximum concentration of 97.916 mg/l for Cu leaching in solution. Copyright © 2018 Elsevier Ltd. All rights reserved.

VOLTAMMETRIC BEHAVIOR OF SOME STEELS IN AQUEOUS SOLUTIONS OF HNO3

Directory of Open Access Journals (Sweden)

Gheorghe Nemtoi

2011-06-01

Full Text Available The corrosion process of some steels immersed in HNO3 solutions of different concentrations by means of voltammetric measurements was investigated. For different values of the corrosion potential, or of the contact time: solid steel-aggressive medium, several equations of the type: I = f (E were proposed, only for linear domains of the voltammograms.

The effect of fatty acid surfactants on the uptake of nitric acid to deliquesced NaCl aerosol

Directory of Open Access Journals (Sweden)

M. Ammann

2008-09-01

Full Text Available Surface active organic compounds have been observed in marine boundary layer aerosol. Here, we investigate the effect such surfactants have on the uptake of nitric acid (HNO₃, an important removal reaction of nitrogen oxides in the marine boundary layer. The uptake of gaseous HNO₃ on deliquesced NaCl aerosol was measured in a flow reactor using HNO₃ labelled with the short-lived radioactive isotope ¹³N. The uptake coefficient γ on pure deliquesced NaCl aerosol was γ=0.5±0.2 at 60% relative humidity and 30 ppb HNO₃(g. The uptake coefficient was reduced by a factor of 5–50 when the aerosol was coated with saturated linear fatty acids with carbon chain lengths of 18 and 15 atoms in monolayer quantities. In contrast, neither shorter saturated linear fatty acids with 12 and 9 carbon atoms, nor coatings with the unsaturated oleic acid (C18, cis-double bond had a detectable effect on the rate of HNO₃ uptake. It is concluded that it is the structure of the monolayers formed, which determines their resistance towards HNO₃ uptake. Fatty acids (C18 and C15, which form a highly ordered film in the so-called liquid condensed state, represent a significant barrier towards HNO₃ uptake, while monolayers of shorter-chain fatty acids (C9, C12 and of the unsaturated oleic acid form a less ordered film in the liquid expanded state and do not hinder the uptake. Similarly, high contents of humic acids in the aerosol, a structurally inhomogeneous, quite water soluble mixture of oxidised high molecular weight organic compounds did not affect HNO₃ uptake. As surfactant films on naturally occurring aerosol are expected to be less structured due to their chemical inhomogeneity, it is likely that their inhibitory effect on HNO₃ uptake is smaller than that observed here for the C15 and C18 fatty acid monolayers.

Waste acid detoxification and reclamation

International Nuclear Information System (INIS)

Brouns, T.M.; Stewart, T.L.

1988-01-01

Economically feasible processes that reduce the volume, quantity, and toxicity of metal-bearing waste acids by reclaiming, reusing, and recycling spent acids and metal salts are being developed and demonstrated. The acids used in the demonstrations are generated during metal-finishing operations used in nuclear fuel fabrication; HF-HNO 3 , HNO 3 , and HNO 3 -H 2 SO 4 wastes result from Zr etching, Cu stripping, and chemical milling of U. At discharge, wastes contain high concentrations of acid and one major metal impurity. The waste minimization process used to reclaim acid from these three streams incorporates three processes for acid regeneration and reclamation. Normally, HNO 3 remains in the bottoms when an aqueous acid solution is distilled; however, in the presence of H 2 SO 4 , HNO 3 will distill to the overhead stream. In this process, nitrates and fluorides present as free acid and metal salts can be reclaimed as acid for recycle to the metal-finishing processes. Uranium present in the chemical milling solution can be economically recovered from distillation bottoms and refined. Using acid distillation, the volume of chemical milling solution discharged as waste can be reduced by as much as 60% depending on the H 2 SO 4 concentration. A payback period of 2.2 years has been estimated for this process. The development and demonstration of precipitation and distillation processes for detoxification and reclamation of waste acid is supported by the US Department of Energy's Hazardous Waste Remedial Actions Program (HAZWRAP)

Impact of the new HNO3-forming channel of the HO2+NO reaction on tropospheric HNO3, NOx, HOx and ozone

Directory of Open Access Journals (Sweden)

A. Kukui

2008-07-01

Full Text Available We have studied the impact of the recently observed reaction NO+HO2→HNO3 on atmospheric chemistry. A pressure and temperature-dependent parameterisation of this minor channel of the NO+HO2→NO2+OH reaction has been included in both a 2-D stratosphere-troposphere model and a 3-D tropospheric chemical transport model (CTM. Significant effects on the nitrogen species and hydroxyl radical concentrations are found throughout the troposphere, with the largest percentage changes occurring in the tropical upper troposphere (UT. Including the reaction leads to a reduction in NOx everywhere in the troposphere, with the largest decrease of 25% in the tropical and Southern Hemisphere UT. The tropical UT also has a corresponding large increase in HNO3 of 25%. OH decreases throughout the troposphere with the largest reduction of over 20% in the tropical UT. The mean global decrease in OH is around 13%, which is very large compared to the impact that typical photochemical revisions have on this modelled quantity. This OH decrease leads to an increase in CH4 lifetime of 5%. Due to the impact of decreased NOx on the OH:HO2 partitioning, modelled HO2 actually increases in the tropical UT on including the new reaction. The impact on tropospheric ozone is a decrease in the range 5 to 12%, with the largest impact in the tropics and Southern Hemisphere. Comparison with observations shows that in the region of largest changes, i.e. the tropical UT, the inclusion of the new reaction tends to degrade the model agreement. Elsewhere the model comparisons are not able to critically assess the impact of including this reaction. Only small changes are calculated in the minor species distributions in the stratosphere.

Physiological responses of lichens to factorial fumigations with nitric acid and ozone

International Nuclear Information System (INIS)

Riddell, J.; Padgett, P.E.; Nash, T.H.

2012-01-01

This paper addresses the effects of gaseous nitric acid (HNO 3 ) and ozone (O 3 ), two important air pollutants, on six lichen species with different morphological, ecological, and biological characteristics. The treatment chambers were set up in a factorial design consisting of control chambers, chambers fumigated with HNO 3 , with O 3 , and with HNO 3 and O 3 , together. Each species showed a different sensitivity to the fumigations, reflecting the physiological variation among species. Our results clearly indicate that HNO 3 is a strong phytotoxin to many lichens, and that O 3 alone has little effect on the measured parameters. The combined fumigation effects of HNO 3 and O 3 were not significantly different from HNO 3 alone. - Highlights: ► We fumigated 6 lichen species with factorial combinations of nitric acid (HNO 3 ) and ozone (O 3 ). ► Some species were highly sensitive to HNO 3 while others were tolerant. ► No species responded significantly to O 3 . ► The combined fumigation effects of HNO 3 and O 3 were not significantly different from HNO 3 alone. ► HNO 3 may play an important role in lichen community composition in areas with high HNO 3 pollution. - Nitric acid can be highly toxic to lichens through several physiological mechanisms. Ozone is relatively non-toxic to fumigated lichens.

Extraction and separation of Am and rare earth elements in HNO3 solution with P507-sulphonating kerosene

International Nuclear Information System (INIS)

Li Zhenhu; Jiao Rongzhou; Zhu Yongjun

1994-01-01

A study has been made of the extraction equilibrium of Am(III) and rare earth elements (III) in HNO 3 solution with P507-sulphonating kerosene. It has been found that this equilibrium depends on saponification ratio of P507, feed acidity, metal concentration as well as phase ratio. The extraction ability in order is La< Ce< Am< Pr< Nd< Sm. The model of distribution ratio has been founded. The agreement for calculated and experimental values of distribution ratio is fairly good. These values can be used to design the extraction and separation process of Am and rare earth elements

Equilibrium and kinetics of co-extraction of U(VI) and HNO3 using tri-n-butyl phosphate and tri-iso-amyl phosphate in paraffin

International Nuclear Information System (INIS)

Das, Diptendu; Juvekar, V.A.; Biswas, Sujoy; Roy, S.B.; Bhattacharya, R.

2014-01-01

Tri-n-butyl phosphate (TBP) is versatile solvent for recovery of actinides as it is cheaper and the extracted actinides can be stripped from the loaded organic phase using plain water. However there are inherent problems associated TBP such as i) formation of the third phase ii) high solubility in aqueous phase iii) radiolytic hydrolysis at high radiation environment and iv) high propensity for extraction of mineral acids. The last mentioned property makes it less suitable for liquid emulsion membrane (LEM) extraction where acid transport to the strip phase drastically reduces extraction efficiency. Therefore there is need to replace TBP with an extractant which has lesser propensity for acid extraction. Many researcher reported Tri-iso-amyl phosphate (TiAP) as an alternative extractant which can sustain high radiation environment without chemical/radiative degradation. However there are no studies available on co-extraction of U(VI) and mineral acids by TiAP. In this research paper equilibrium and kinetics of co-extraction of U(VI) and HNO 3 from nitric acid medium into a hydrocarbon phase (paraffin) using Tri n- butyl phosphate (TBP), Tri-iso-amyl phosphate (TiAP) has been studied. Relative rates of extraction of uranium(VI) and HNO 3 by TiAP and TBP were measured simultaneously using bulk-liquid membrane (BLM) system. Study reveals although TiAP is less efficient in extracting U(IV), than TBP, it transfers lesser quantity of nitric acid to organic phase. Hence TiAP is more suitable as a carrier for LEM extraction than TBP

Structure-property relationships in halogenbenzoic acids: Thermodynamics of sublimation, fusion, vaporization and solubility.

Science.gov (United States)

Zherikova, Kseniya V; Svetlov, Aleksey A; Kuratieva, Natalia V; Verevkin, Sergey P

2016-10-01

Temperature dependences of vapor pressures for 2-, 3-, and 4-bromobenzoic acid, as well as for five isomeric bromo-methylbenzoic acids were studied by the transpiration method. Melting temperatures and enthalpies of fusion for all isomeric bromo-methylbenzoic acids and 4-bromobenzoic acid were measured with a DSC. The molar enthalpies of sublimation and vaporization were derived. These data together with results available in the literature were collected and checked for internal consistency using a group-additivity procedure and results from X-ray structural diffraction studies. Specific (hydrogen bonding) interactions in the liquid and in the crystal phase of halogenbenzoic acids were quantified based on experimental values of vaporization and sublimation enthalpies. Structure-property correlations of solubilities of halogenobenzoic acids with sublimation pressures and sublimation enthalpies were developed and solubilities of bromo-benzoic acids were estimated. These new results resolve much of the ambiguity in the available thermochemical and solubility data on bromobenzoic acids. The approach based on structure property correlations can be applied for the assessment of water solubility of sparingly soluble drugs. Copyright © 2016 Elsevier Ltd. All rights reserved.

Global CO emission estimates inferred from assimilation of MOPITT and IASI CO data, together with observations of O3, NO2, HNO3, and HCHO.

Science.gov (United States)

Zhang, X.; Jones, D. B. A.; Keller, M.; Jiang, Z.; Bourassa, A. E.; Degenstein, D. A.; Clerbaux, C.; Pierre-Francois, C.

2017-12-01

Atmospheric carbon monoxide (CO) emissions estimated from inverse modeling analyses exhibit large uncertainties, due, in part, to discrepancies in the tropospheric chemistry in atmospheric models. We attempt to reduce the uncertainties in CO emission estimates by constraining the modeled abundance of ozone (O3), nitrogen dioxide (NO2), nitric acid (HNO3), and formaldehyde (HCHO), which are constituents that play a key role in tropospheric chemistry. Using the GEOS-Chem four-dimensional variational (4D-Var) data assimilation system, we estimate CO emissions by assimilating observations of CO from the Measurement of Pollution In the Troposphere (MOPITT) and the Infrared Atmospheric Sounding Interferometer (IASI), together with observations of O3 from the Optical Spectrograph and InfraRed Imager System (OSIRIS) and IASI, NO2 and HCHO from the Ozone Monitoring Instrument (OMI), and HNO3 from the Microwave Limb Sounder (MLS). Our experiments evaluate the inferred CO emission estimates from major anthropogenic, biomass burning and biogenic sources. Moreover, we also infer surface emissions of nitrogen oxides (NOx = NO + NO2) and isoprene. Our results reveal that this multiple species chemical data assimilation produces a chemical consistent state that effectively adjusts the CO-O3-OH coupling in the model. The O3-induced changes in OH are particularly large in the tropics. Overall, our analysis results in a better constrained tropospheric chemical state.

Fate of aliphatic compounds in nitric acid processing solutions

International Nuclear Information System (INIS)

Clark, W.E.; Howerton, W.B.

1975-01-01

The reaction of hyperazeotropic iodic acid-saturated nitric acid with short chain aliphatic iodides, nitrates, and acids was studied in order to determine the conditions for complete removal of organic materials from nitric acid systems. The aliphatic iodides are converted to the nitrates and the nitrates in strong HNO 3 are extensively converted into CO 2 and acids. The aliphatic acids are rather stable; acetic acid was unattacked by boiling in 20M HNO 3 and n-butyric acid was 80 percent unattacked. The dibasic acids oxalic and malonic are extensively attacked, but succinic acid is relatively stable. A wet oxidation method is successful in destroying acetic acid in 5 to 8M HNO 3 . (U.S.)

Extractive distillation of nitric acid using the two-pot concept

International Nuclear Information System (INIS)

Counce, R.M.; Groenier, W.S.; Holland, W.D.; Jubin, R.T.; North, E.D.; Thompson, L.E. Jr.; Hebble, T.L.

1982-12-01

Experiments have confirmed the validity of a novel design for a nitric acid concentration system for use in shielded nuclear fuel reprocessing plants. Current plans for producing the scrub solution for the IODOX process require the concentration and recycle of low strength ( 3 ) 2 as the solvent and features two pots: an extractive distillation pot in which a concentrated acid product is obtained by contacting the acid feed with the solvent and a solvent recovery pot in which the solvent is dehydrated and recovered for recycle. In these experiments, a concentrated product of 89 wt % nitric acid was produced from azeotropic feed. The available vapor-liquid equilibria data for the Mg(NO 3 ) 2 -HNO 3 -H 2 O system has been empirically correlated, and a design methodology has been developed for the two-pot extractive distillation process

Kinetics, mechanism, and stoicheiometry of the oxidation of hydroxylamine by nitric acid

International Nuclear Information System (INIS)

Pembridge, J.R.; Stedman, G.

1979-01-01

Hydroxylamine is oxidised by nitric acid to form dinitrogen monoxide and nitrous acid, the proportions varying with reaction conditions. (The chemistry of hydroxylamine in nitric acid is of potential technological interest, since it has been proposed as a reagent for the reduction of Pu(IV) to Pu(III).) The yield [HNO 2 ]infinity/ [NH 3 OH + ] 0 is a maximum at ca. 4 to 5 mol dm -3 HNO 3 , and is also a function of the hydroxylamine concentration. In 5 mol dm -3 HNO 3 the limiting yield is ca. 0.85 at very low initial hydroxylamine concentrations, but decreases towards zero at higher values of [NH 3 OH + ] 0 . Reaction is only observed at sufficiently high nitric acid concentrations; at 25 0 C the cut-off point is ca. 2.5 mol dm -3 HNO 3 . The reaction is characterised by an induction period, followed by a rapid autocatalytic process. Addition of nitrite eliminates the induction period, while addition of nitrite scavengers completely prevents any reaction. Nitrous acid is an essential catalyst for the reaction, and the initial rate of reaction obeys the equation d[HNO 2 ]/dt = V 0 = k[HNO 2 ][NH 3 OH + ]. Isotopic experiments, using 15 N-enriched hydroxylamine show that virtually all of the N 2 O arises from reaction between HNO 2 and hydroxylamine. The mechanism suggested involves oxidation of un-protonated hydroxylamine by N 2 O 4 to form the nitroxyl diradical HNO; this is then further oxidised to HNO 2 , which reacts with hydroxylamine to form N 2 O. (author)

Revising the retrieval technique of a long-term stratospheric HNO{sub 3} data set. From a constrained matrix inversion to the optimal estimation algorithm

Energy Technology Data Exchange (ETDEWEB)

Fiorucci, I.; Muscari, G. [Istituto Nazionale di Geofisica e Vulcanologia, Rome (Italy); De Zafra, R.L. [State Univ. of New York, Stony Brook, NY (United States). Dept. of Physics and Astronomy

2011-07-01

The Ground-Based Millimeter-wave Spectrometer (GBMS) was designed and built at the State University of New York at Stony Brook in the early 1990s and since then has carried out many measurement campaigns of stratospheric O{sub 3}, HNO{sub 3}, CO and N{sub 2}O at polar and mid-latitudes. Its HNO{sub 3} data set shed light on HNO{sub 3} annual cycles over the Antarctic continent and contributed to the validation of both generations of the satellite-based JPL Microwave Limb Sounder (MLS). Following the increasing need for long-term data sets of stratospheric constituents, we resolved to establish a long-term GMBS observation site at the Arctic station of Thule (76.5 N, 68.8 W), Greenland, beginning in January 2009, in order to track the long- and short-term interactions between the changing climate and the seasonal processes tied to the ozone depletion phenomenon. Furthermore, we updated the retrieval algorithm adapting the Optimal Estimation (OE) method to GBMS spectral data in order to conform to the standard of the Network for the Detection of Atmospheric Composition Change (NDACC) microwave group, and to provide our retrievals with a set of averaging kernels that allow more straightforward comparisons with other data sets. The new OE algorithm was applied to GBMS HNO{sub 3} data sets from 1993 South Pole observations to date, in order to produce HNO{sub 3} version 2 (v2) profiles. A sample of results obtained at Antarctic latitudes in fall and winter and at mid-latitudes is shown here. In most conditions, v2 inversions show a sensitivity (i.e., sum of column elements of the averaging kernel matrix) of 100{+-}20% from 20 to 45 km altitude, with somewhat worse (better) sensitivity in the Antarctic winter lower (upper) stratosphere. The 1{sigma} uncertainty on HNO{sub 3} v2 mixing ratio vertical profiles depends on altitude and is estimated at {proportional_to}15% or 0.3 ppbv, whichever is larger. Comparisons of v2 with former (v1) GBMS HNO{sub 3} vertical profiles

Atmospheric acidity measurements on allegheny mountain and the origins of ambient acidity in the Northeastern United States

Science.gov (United States)

Pierson, William R.; Brachaczek, Wanda W.; Gorse, Robert A.; Japar, Steven M.; Norbeck, Joseph M.; Keeler, Gerald J.

Atmospheric acidity as HNO 3(g), SO 2(g), and aerosol H + was measured on Allegheny Mountain and Laurel Hill in southwest Pennsylvania in August 1983. The aerosol H + appeared to represent the net after H 2SO 4 reaction with NH 3(g). The resulting H +/SO 42- ratio depended on SO 42- concentration, approaching that of H 2SO 4 at the highest SO 42- concentrations. The atmosphere was acidic; the average concentrations of HNO 3 (78 nmole m -3) and aerosol H + (205 nmole m -3), NH 4+ (172 nmole m -3) and SO 42- (201 nmole m -3), and the dearth of NH 3( 2, with one 10-h period averaging 263 and 844 nmolem -3 for HNO 3 and aerosol H +, respectively. SO 2 added another 900 nmole m -3 (average) of potential H + acidity. HNO 3 and aerosol H + episodes were concurrent, on 7-8 day cycles, unrelated to SO 2 which existed more in short-lived bursts of apparently more local origin. NOx was sporadic like SO 2. Laurel and Allegheny, separated by 35.5 km, were essentially identical in aerosol SO 42-, and in aerosol H +, less so in HNO 3 and especially less so in SO 2; apparently, chemistry involving HNO 3 and aerosol H + or SO 42- was slow compared to inter-site transport times (1-2 h). From growth of bscat and decline of SO 2 during one instance of inter-site transport, daytime rate coefficients for SO 2 oxidation and SO 2 dry deposition were inferred to have been, respectively, ~ 0.05 and ⩽ 0.1 h -1. HNO 3 declined at night. Aerosol H + and SO 42- showed no significant diurnal variation, and O 3 showed very little; these observations, together with high PAN/NO x ratios, indicate that regional transport rather than local chemistry is governing. The O 3 concentration (average 56 ppb or 2178 nmolem -3) connotes an oxidizing atmosphere conducive to acid formation. Highest atmospheric acidity was associated with (1) slow westerly winds traversing westward SO 2 source areas, (2) local stagnation, or (3) regional transport around to the back side of a high pressure system. Low acidity

Nitric Acid and Water Extraction by T2EHDGA in n -Dodecane

Energy Technology Data Exchange (ETDEWEB)

Campbell, Emily L. [Pacific Northwest National Laboratory, Richland, Washington, USA; Chemistry Department, Washington State University, Pullman, Washington, USA; Holfeltz, Vanessa E. [Pacific Northwest National Laboratory, Richland, Washington, USA; School of Nuclear Science and Engineering, Oregon State University, Corvallis, OR; Hall, Gabriel B. [Pacific Northwest National Laboratory, Richland, Washington, USA; Nash, Kenneth L. [Chemistry Department, Washington State University, Pullman, Washington, USA; Lumetta, Gregg J. [Pacific Northwest National Laboratory, Richland, Washington, USA; Levitskaia, Tatiana G. [Pacific Northwest National Laboratory, Richland, Washington, USA

2017-11-10

Liquid-liquid distribution behavior of nitric acid (HNO3) and water by a diglycolamide ligand, N,N,N',N'-tetra-2-ethylhexyldiglycolamide (T2EHDGA) into n-dodecane diluent was investigated. Spectroscopic FTIR and NMR characterization of the organic extraction solutions indicate T2EHDGA carbonyl coordinates HNO3 and progressively aggregates at high acid conditions. Water extraction increases in the presence of HNO3. The experimentally observed distribution of HNO3 was modeled using the computer program, SXLSQI. The results indicated that the formation of two organic phase species—HNO3·T2EHDGA and (HNO3)2·T2EHDGA—satisfactory describes the acid transport behavior. Temperature dependent solvent extraction studies allowed for determination of thermodynamic extraction constants and ΔH and ΔS parameters for the corresponding extractive processes.

Synergistic Effect of L-Methionine and KI on Copper Corrosion Inhibition in HNO3 (1M

Directory of Open Access Journals (Sweden)

Amel SEDIK

2014-05-01

Full Text Available L-Methionine (L-Met efficiency as a non-toxic corrosion inhibitor for copper in 1M HNO3 has been studied by using electrochemical impedance spectroscopy (EIS and potentiodynamic polarization. Copper corrosion rate significant decrease was observed in the presence of L-Met at 10-4M. The Obtained Results from potentiodynamic polarization and impedance measurements are in good agreement. L-Methionine adsorption on copper surface follows Langmuir isotherm. L-Met free energy adsorption on copper (-30 KJ mol-1 reveals an inhibition strong physical adsorption on copper surface. In order to evaluate the L-Met effect, L-Met and iodide ion’synergistic effect was used to prevent copper corrosion in nitric acid. It was found that inhibitor efficiency (IE reached 98.27 % in 1M solution containing 10-4M L-Met and 10- 3 M KI. The synergistic effect was attributed to iodide ions adsorption on copper surface, which facilitated the L-Met adsorption and an inhibitive film formation.

Corrosion of stainless steels and nickel-base alloys in solutions of nitric acid and hydrofluoric acid

International Nuclear Information System (INIS)

Horn, E.M.; Renner, M.

1992-01-01

Reactions involving nitric acid may always result in the contamination of this acid with fluorides. In highly concentrted nitric acid, the presence of small amounts of HF will substantially reduce the corrosion of metallic materials. Mixtures consisting of hydrofluoric acid and hypo-azeotropic nitric acid on the other hand will strongly attack: the metal loss will markedly increase with increasing HNO 3 and HF concentrations as well as with rising temperatures. The investigation covered 12 stainless steel grades and nickel-base alloys. With constant HNO 3 content, corrosion rates will rise linearly when increasing the HF concentration. With constant HF concentration (0,25 M), corrosion rates will increase rapidly with increasing nitric acid concentration (from 0.3 M to 14.8 M). This can best be described by superimposing a linear function and a hyperbolic function that is reflecting the change in the HNO 3 content. Alloys containing as much chromium as possible (up to 46 wt.%) will exhibit the best corrosion resistance. Alloy NiCr30FeMo (Hastelloy alloy G-30) proved to be well suitable in this investigation. (orig.) [de

Computational Chemical Kinetics for the Reaction of Criegee Intermediate CH2OO with HNO3 and Its Catalytic Conversion to OH and HCO.

Science.gov (United States)

Raghunath, P; Lee, Yuan-Pern; Lin, M C

2017-05-25

The kinetics and mechanisms for the reaction of the Criegee intermediate CH 2 OO with HNO 3 and the unimolecular decomposition of its reaction product CH 2 (O)NO 3 are important in atmospheric chemistry. The potential-energy profile of the reactions predicted with the CCSD(T)/aug-cc-pVTZ//B3LYP/aug-cc-pVTZ method shows that the initial association yields a prereaction complex that isomerizes by H migration to yield excited intermediate nitrooxymethyl hydroperoxide NO 3 CH 2 OOH* with internal energy ∼44 kcal mol -1 . A fragmentation of this excited intermediate produces CH 2 (O)NO 3 + OH with its transition state located 5.0 kcal mol -1 below that of the reactants. Further decomposition of CH 2 (O)NO 3 produces HCO + HNO 3 , forming a catalytic cycle for destruction of CH 2 OO by HNO 3 . The rate coefficients and product-branching ratios were calculated in the temperature range 250-700 K at pressure 20-760 Torr (N 2 ) using the variational-transition-state and Rice-Ramsperger-Kassel-Marcus (RRKM) theories. The predicted total rate coefficient for reaction CH 2 OO + HNO 3 at 295 K, 5.1 × 10 -10 cm 3 molecule -1 s -1 , agrees satisfactorily with the experimental value, (5.4 ± 1.0) × 10 -10 cm 3 molecule -1 s -1 . The predicted branching ratios at 295 K are 0.21 for the formation of NO 3 CH 2 OOH and 0.79 for CH 2 (O)NO 3 + OH at a pressure of 40 Torr (N 2 ), and 0.79 for the formation of NO 3 CH 2 OOH and 0.21 for CH 2 (O)NO 3 + OH at 760 Torr (N 2 ). This new catalytic conversion of CH 2 OO to HCO + OH by HNO 3 might have significant impact on atmospheric chemistry.

Separation of 15N by isotopic exchange in NO, NO2-HNO3 system under pressure

International Nuclear Information System (INIS)

Axente, D.; Baldea, A.; Teaca, C.; Horga, R.; Abrudean, M.

1998-01-01

One of the most used method for production of 15 N with 99% at. concentration is the isotopic exchange between gaseous nitrogen oxides and HNO 3 solution 10M: ( 15 NO, 15 NO 2 ) g + H 14 NO 3,l = ( 14 NO, 14 NO 2 ) g + H 15 NO 3,l . The isotopic exchange is characterized by an elemental separation factor α=1.055 at 25 deg. C and atmospheric pressure. Recently, kinetics data pointed to the linear dependence of the exchange rate 15 N/ 14 N(R) on the nitrogen oxide pressure with a rate law R = k[HNO 3 ] 2 · [N 2 O 3 ]. In this work, the influence of the nitrogen oxide pressure on the 15 N separation efficiency was determined by the use of a laboratory equipment with a separation column pack of Helipack type, with dimensions 1.8 mm x 1.8 mm x 0.2 mm. The increase of nitrogen oxide pressure led to a better isotopic transfer between the two counter-flow phases in the column pack. The HETP (Height Equivalent to a Theoretical Plate) determined for a 3.14 ml ·cm -2 · min -1 load is equal to that obtained at atmospheric pressure for a two times lower load. The operation of the equipment for isotopic separation of 15 N at 1.8 atm instead of atmospheric pressure allows doubling the HNO 3 10 M load of the column and consequently, doubling the production rate. A better performance of the separation process at higher pressure is essential for the industrial production of 15 N isotope which is used for the production of uranium nitride in FBR type reactors. (authors)

Effect of hydrofluoric acid on acid decomposition mixtures for determining iron and other metallic elements in green vegetables

International Nuclear Information System (INIS)

Dogbe, S.A.; Afful, S.; Debrah, C.

2007-01-01

The efficiency of acid mixtures, HNO 3 - HCI0 4 -HF, HNO 3 - HCI - HF, HNO 3 - HCIO 4 and HNO 3 - HCI in the decomposition of four edible green vegetables, Gboma (Solanum macrocarpon), Aleefu (Amaranttius hibiridus), Shoeley (Hibiscus sabdariffa) and Ademe (Corchorus olitorius), for flame Atomic Absorption Spectrometer analysis of Fe, Mn, Mg, Cu, Zn and Ca was studied. The concentrations of Fe were higher (120.61 -710.10 mg/kg), while the values of Cu were lower (2.31 - 4.84 mg/kg) in all the samples. The values of concentration for Fe were more reproducible when HF was included in the decomposition mixtures. There were no significant differences in the concentrations of the other elements when HF was included in the acid mixture as compared to the acid mixtures without HF. Therefore, the inclusion of HF in the acid decomposition mixtures would ensure total and precise estimation of Fe in plant materials, but not critical for analysis of Mn, Mg, Cu, Zn and Ca. Performance of the decomposition procedures was verified by applying the methods to analyse Standard Reference Material IAEA-V-10 Hay Powder. (au)

Vapor pressures and standard molar enthalpies, entropies, and Gibbs free energies of sublimation of 2,4- and 3,4-dinitrobenzoic acids

International Nuclear Information System (INIS)

Vecchio, Stefano; Brunetti, Bruno

2009-01-01

The vapor pressures of the solid and liquid 2,4- and 3,4-dinitrobenzoic acids were determined by torsion-effusion and thermogravimetry under both isothermal and non-isothermal conditions, respectively. From the temperature dependence of vapor pressure derived by the experimental torsion-effusion and thermogravimetry data the molar enthalpies of sublimation Δ cr g H m 0 ( ) and vaporization Δ l g H m 0 ( ) were determined, respectively, at the middle of the respective temperature intervals. The melting temperatures and the molar enthalpies of fusion of these compounds were measured by d.s.c. Finally, the results obtained by all the methods proposed were corrected at the reference temperature of 298.15 K using the estimated heat capacity differences between gas and liquid for vaporization experiments and the estimated heat capacity differences between gas and solid for sublimation experiments. Therefore, the averages of the standard (p o = 0.1 MPa) molar enthalpies, entropies and Gibbs free energies of sublimation at 298.15 K, have been derived.

Characterization of condensed phase nitric acid particles formed in the gas phase

Institute of Scientific and Technical Information of China (English)

Long Jia; Yongfu Xu

2011-01-01

The formation of nitric acid hydrates has been observed in a chamber during the dark reaction of NO2 with O3 in the presence of air.The size of condensed phase nitric acid was measured to be 40-100 nm and 20-65 nm at relative humidity (RH) ≤ 5％ and RH = 67％ under our experimental conditions, respectively.The nitric acid particles were collected on the glass fiber membrane and their chemical compositions were analyzed by infrared spectrum.The main components of nitric acid hydrates in particles are HNO3·3H2O and NO3-·xH2O (x≥ 4) at low RH, whereas at high RH HNO3·H2O, HNO3·2H2O, HNO3·3H2O and NO3-·xH2O (x≥ 4) all exist in the condensed phase.At high RH HNO3·xH2O (x ≤ 3) collected on the glass fiber membrane is greatly increased, while NO3-·xH2O (x ≥4) decreased, compared with low RH.To the best of our knowledge, this is the first time to report that condensed phase nitric acid can be generated in the gas phase at room temperature.

Temperature dependences of saturated vapor pressure and the enthalpy of vaporization of n-pentyl esters of dicarboxylic acids

Science.gov (United States)

Portnova, S. V.; Krasnykh, E. L.; Levanova, S. V.

2016-05-01

The saturated vapor pressures and enthalpies of vaporization of n-pentyl esters of linear C2-C6 dicarboxylic acids are determined by the transpiration method in the temperature range of 309.2-361.2 K. The dependences of enthalpies of vaporization on the number of carbon atoms in the molecule and on the retention indices have been determined. The predictive capabilities of the existing calculation schemes for estimation of enthalpy of vaporization of the studied compounds have been analyzed.

Effects of prior cold work on corrosion and corrosive wear of copper in HNO3 and NaCl solutions

International Nuclear Information System (INIS)

Yin Songbo; Li, D.Y.

2005-01-01

Effects of prior cold work on corrosion and corrosive wear behavior of copper in 0.1 M HNO 3 and 3.5% NaCl solutions, respectively, were investigated using electrochemical tests, electron work function measurements, and sliding corrosive wear tests with and without cathodic protection. Optical microscope and SEM were employed to examine the microstructure and worn surfaces. It was shown that, in general, the prior cold work raised the corrosion rate, but the effect differed in different corrosive media. In both the solutions, pure mechanical wear decreased with an increase in cold work. The prior cold work had a significant influence on the corrosive wear of copper, depending on the corrosive solution and the applied load. In the 0.1 M HNO 3 solution, the ratio of the wear loss caused by corrosion-wear synergism to the total wear loss increased with the cold work and became saturated when the cold work reached a certain level. In the 3.5% NaCl solution, however, this ratio decreased initially and then became relatively stable with respect to the cold work. It was observed that wear of copper in the 3.5% NaCl solution was larger than that in 0.1 M HNO 3 solution, although copper showed lower corrosion rate in the former solution. The experimental observations and the possible mechanisms involved are discussed

Nitrogen isotope exchange between nitric oxide and nitric acid

International Nuclear Information System (INIS)

Axente, D.; Abrudean, M.; Baldea, A.

1996-01-01

The rate of nitrogen isotope exchange between NO and HNO 3 has been measured as a function of nitric acid concentration of 1.5-4M x 1 -1 . The exchange rate law is shown to be R=k[HNO 3 ] 2 [N 2 O 3 ] and the measured activation energy is E=67.78 kJ x M -1 (16.2 kcal x M -1 ). It is concluded that N 2 O 3 participates in 15 N/ 14 N exchange between NO and HNO 3 at nitric acid concentrations higher than 1.5M x 1 -1 . (author). 7 refs., 3 figs., 4 tabs

Anodic galvanostatic polarization of AA2024-T3 aircraft alloy in conventional mineral acids

Energy Technology Data Exchange (ETDEWEB)

Kozhukharov, S., E-mail: stephko1980@abv.bg [Department of Chemical Sciences, University of Chemical Technology and Metallurgy, 8 “Kliment Okhridski” Blvd, 1756, Sofia (Bulgaria); Girginov, Ch. [Department of Chemical Sciences, University of Chemical Technology and Metallurgy, 8 “Kliment Okhridski” Blvd, 1756, Sofia (Bulgaria); Avramova, I. [Institute of General and Inorganic Chemistry, Bulgarian Academy of Science, 11 “Georgi Bonchev” Str., 1113, Sofia (Bulgaria); Machkova, M. [Department of Chemical Sciences, University of Chemical Technology and Metallurgy, 8 “Kliment Okhridski” Blvd, 1756, Sofia (Bulgaria)

2016-09-01

The present study is devoted to the determination of the impact of the anodization of AA2024-T3 alloys in HCl, HNO{sub 3}, H{sub 2}SO{sub 4} or H{sub 3}PO{sub 4} on the samples’ surface morphology and properties. Subsequent systematic assessments were performed by Scanning Electron Microscopy (SEM), Energy Dispersion X-Ray Spectroscopy (EDX) and X-ray Photoelectron Spectroscopy (XPS). These observations were combined with Linear Voltammetry (LVA) and Electrochemical Impedance Spectroscopy (EIS) after 48 and 168 h of exposure to a 3.5% NaCl model corrosive medium. The main result is, that completely different effects were observed in accordance to the acid used. It was established that the monoprotonic acids have a deep destructive effect due to dissolution of the alloy components, whereas the polyprotonic ones possess either indistinguishable influence, or surface film formation. - Highlights: • AA2024 was polarized anodically in 15%{sub wt} acid solutions at 15 mA cm{sup −2} for 2 h. • Four mineral acids were selected for investigation: HCl, HNO{sub 3}, H{sub 2}SO{sub 4} and H{sub 3}PO{sub 4}. • SEM, EDX and XPS were applied for morphological description. • Electrochemical characterizations were performed by EIS and linear voltammetry. • The acid used predetermines completely different interaction with the AA2024 alloy.

Facilitated transport of HNO3 through a supported liquid membrane containing a tertiary amine as carrier

International Nuclear Information System (INIS)

Cianetti, C.; Danesi, P.R.

1983-01-01

The facilitated transport of HNO 3 through a supported liquid membrane consisting of a porous polypropylene film containing a solution of trilaurylamine in diethylbenzene as carrier was studied as a function of the stirring speed of the aqueous solutions and the membrane composition. A physico-chemical model which takes into account diffusion through an aqueous boundary layer, a fast interfacial chemical reaction leading to the formation of a membrane soluble alkylammonium salt and diffusion through the membrane was proposed. In this way, equations were derived which describe how composition changes, occurring in the course of the permeation process, influence the membrane permeability. The experimental data were quantitatively explained by the derived equations. The results indicate that the monomeric form of the trilaurylammonium nitrate salt is the species which is mainly responsible for the acid transport through the membrane. The diffusion coefficient of the permeating species and the order of magnitude of the thickness of the aqueous boundary layer were evaluated. 8 figures

Mathematical modeling of the radiation-chemical behavior of neptunium in HNO3. Equilibrium states

International Nuclear Information System (INIS)

Vladimirova, M.V.

1995-01-01

A mathematical model of the radiation-chemical behavior of neptunium is presented for a wide range of α-and γ-irradiation doses. Equations determining the equilibrium concentrations of NP(IV), Np(V), and Np(VI) are derived for various concentrations of HNO 3 and dose rates of the ionizing irradiation. The rate constants of the reactions NP(IV) + OH, Np(IV) + NO 3 , Np(V) + NO 2 , Np(V) + H, Np(IV), and Np(V) + Np(V) are obtained by the mathematical modeling

Co-precipitation of plutonium(IV) and americium(III) from nitric acid-oxalic acid solutions with bismuth oxalate

International Nuclear Information System (INIS)

Pius, I.C.; Noronha, D.M.; Chaudhury, Satyajeet

2017-01-01

Co-precipitation of plutonium and americium from nitric acid-oxalic acid solutions with bismuth oxalate has been investigated for the removal of these long lived α-active nuclides from waste solutions. Effect of concentration of bismuth and oxalic acid on the co-precipitation of Pu(IV) from 3 M HNO_3 has been investigated. Similar experiments were also carried out from 3.75 M HNO_3 on co-precipitation of Am(III) to optimize the conditions of precipitation. Strong co-precipitation of Pu(IV) and Am(III) with bismuth oxalate indicate feasibility of treatment of plutonium and americium bearing waste solutions. (author)

Nitric acid titration in the presence of UO2(NO3)2, Th(NO3)4, U(NO3)4 or Zr(NO3)4

International Nuclear Information System (INIS)

Nakashima, T.; Lieser, K.H.

1986-01-01

Procedures are described for titration of HNO 3 in presence of UO 2 2+ , Th 4+ , U 4+ and Zr 4+ without formation of interfering precipitates. In the first step the hydrolysable ions are masked by addition of complexing agents and in the second step the acid is titrated by NaOH as usual. (orig.)

Zirconium distribution in the system HNO3-H2O-TBP-diluent

International Nuclear Information System (INIS)

Shu, J.; Araujo, B.F. de.

1984-01-01

The extraction behaviour of zirconium in TBP/diluent-HNO 3 -H 2 O systems is studied in order to increase the uranium decontamination factor by adjusting the extraction conditions so that zirconium extraction is kept at a minimum. Equilibrium diagram, TBP concentration, aqueous: organic phases ratio, salting-out effects and uranium loading in the organic phase were the main factors studied. All the experiments have been carried out with zirconium in the 10 -2 - 10 -3 M concentration range. The extractant degradation products influence upon zirconium behaviour was also verified. With the data obtained it was possible to introduce some modifications in the standard Purex flowsheet with the increase of the decontamination of uranium product from zirconium. (Author) [pt

Observations of HNO3, ΣAN, ΣPN and NO2 fluxes: evidence for rapid HOx chemistry within a pine forest canopy

Directory of Open Access Journals (Sweden)

D. K. Farmer

2008-07-01

Full Text Available Measurements of exchange of reactive nitrogen oxides between the atmosphere and a ponderosa pine forest in the Sierra Nevada Mountains are reported. During winter, we observe upward fluxes of NO2, and downward fluxes of total peroxy and peroxy acyl nitrates (ΣPNs, total gas and particle phase alkyl and multifunctional alkyl nitrates (ΣANs(g+p, and the sum of gaseous HNO3 and semi-volatile NO3− particles (HNO3(g+p. We use calculations of the vertical profile and flux of NO, partially constrained by observations, to show that net midday ΣNOyi fluxes in winter are –4.9 ppt m s−1. The signs and magnitudes of these wintertime individual and ΣNOyi fluxes are in the range of prior measurements. In contrast, during summer, we observe downward fluxes only of ΣANs(g+p, and upward fluxes of HNO3(g+p, ΣPNs and NO2 with signs and magnitudes that are unlike most, if not all, previous observations and analyses of fluxes of individual nitrogen oxides. The results imply that the mechanisms contributing to NOy fluxes, at least at this site, are much more complex than previously recognized. We show that the observations of upward fluxes of HNO3(g+p and σPNs during summer are consistent with oxidation of NO2 and acetaldehyde by an OH x residence time of 1.1×1010 molec OH cm−3 s, corresponding to 3 to 16×107 molecules cm−3 OH within the forest canopy for a 420 to 70 s canopy residence time. We show that ΣAN(g+p fluxes are consistent with this range in OH if the reaction of OH with ΣANs produces either HNO3 or NO2 with a 6–30% yield. Calculations of NO fluxes constrained by the NO2 observations and the inferred OH indicate that NOx fluxes are downward into the canopy because of the substantial conversion of NOx to HNO3 and σPNs in the canopy. Even so, we derive that NOx emission fluxes of ~15 ng(N m−2 s−1 at midday during summer are required to balance the NOx and NOy flux budgets. These fluxes are partly explained by estimates of soil

Improvement of microwave-assisted digestion of milk powder with diluted nitric acid using oxygen as auxiliary reagent

Energy Technology Data Exchange (ETDEWEB)

Bizzi, Cezar A. [Departamento de Quimica, Universidade Federal de Santa Maria, 97105-900, Santa Maria, RS (Brazil); Instituto Nacional de Ciencia e Tecnologia de Bioanalitica, Campinas, SP (Brazil); Barin, Juliano S. [Departamento de Tecnologia e Ciencia dos Alimentos, Universidade Federal de Santa Maria, 97105-900, Santa Maria, RS (Brazil); Garcia, Edivaldo E. [Departamento de Quimica, Universidade Estadual de Maringa, 87100-900, Maringa, PR (Brazil); Nobrega, Joaquim A. [Departamento de Quimica, Universidade Federal de Sao Carlos, 13565-905, Sao Carlos, SP (Brazil); Dressler, Valderi L. [Departamento de Quimica, Universidade Federal de Santa Maria, 97105-900, Santa Maria, RS (Brazil); Instituto Nacional de Ciencia e Tecnologia de Bioanalitica, Campinas, SP (Brazil); Flores, Erico M.M., E-mail: ericommf@gmail.com [Departamento de Quimica, Universidade Federal de Santa Maria, 97105-900, Santa Maria, RS (Brazil); Instituto Nacional de Ciencia e Tecnologia de Bioanalitica, Campinas, SP (Brazil)

2011-05-15

The feasibility of using diluted HNO{sub 3} solutions under oxygen pressure for decomposition of whole and non-fat milk powders and whey powder samples has been evaluated. Digestion efficiency was evaluated by determining the carbon content in solution (digests) and the determination of Ca, Cd, Cu, Fe, K, Mg, Mn, Mo, Na, Pb and Zn was performed by inductively coupled plasma optical emission spectrometry and Hg by chemical vapor generation coupled to inductively coupled plasma mass spectrometry. Samples (up to 500 mg) were digested using HNO{sub 3} solutions (1 to 14 mol L{sup -1}) and the effect of oxygen pressure was evaluated between 2.5 and 20 bar. It was possible to perform the digestion of 500 mg of milk powder using 2 mol L{sup -1} HNO{sub 3} with oxygen pressure ranging from 7.5 to 20 bar with resultant carbon content in digests lower than 1700 mg L{sup -1}. Using optimized conditions, less than 0.86 mL of concentrated nitric acid (14 mol L{sup -1}) was enough to digest 500 mg of sample. The accuracy was evaluated by determination of metal concentrations in certified reference materials, which presented an agreement better than 95% (Student's t test, P < 0.05) for all the analytes.

The oxidation of uranium(IV) ions by nitrous acid in 30% tri-butyl phosphate

International Nuclear Information System (INIS)

Koltunov, V.S.; Marchenko, V.I.; Savilova, O.A.; Dvoeglazov, K.N.; Taylor, R.J.

2004-01-01

The kinetics of the oxidation of U(IV) ions by nitrous acid in a 30% TBP solution have been determined. The rate equation was found to be: - d[U(IV)] / dt = k 2a [U(IV)][HNO 2 ][HNO 3 ][H 2 O] / [HNO 3 ] 2 + β 3 [HNO 3 ][H 2 O] + β 4 [H 2 O] 2 , where, k 2a = 0.405 ± 0.055 M -1 min -1 at 55 C (β 3 ∼ 0.08; β 4 ∼ 0.007) and the activation energy was E = 112 ± 17 kJ mol -1 . The reaction mechanism appeared to involve interaction with the 1 st hydrolysis product of U(IV)-UOH 3+ . The data is compared with a previous study of the nitric acid oxidation of U(IV) in 30% TBP. This reaction is autocatalytic due to the formation of nitrous acid during the reaction. The kinetics of the decomposition of HNO 2 in 30% TBP (in the absence of U(IV)) have also been reported. (orig.)

Potentiodynamic polarization studies of bulk amorphous alloy Zr57Cu15.4Ni12.6Al10Nb5 and Zr59Cu20Ni8Al10Ti3 in aqueous HNO3 media

International Nuclear Information System (INIS)

Sharma, Poonam; Dhawan, Anil; Jayraj, J.; Kamachi Mudali, U.

2013-01-01

The potentiodynamic polarization studies were carried out on Zr based bulk amorphous alloy Zr 57 Cu 15.4 Ni 12.6 Al 10 Nb 5 and Zr 59 Cu 20 Ni 8 Al 10 Ti 3 in solutions of 1 M, 6 M and 11.5 M HNO 3 aqueous media at room temperature. As received specimens of Zr 57 Cu 15.4 Ni 12.6 Al 10 Nb 5 (5 mm diameter rod) and Zr 59 Cu 20 Ni 8 Al 10 Ti 3 (3 mm diameter rod) were polished with SiC paper before testing them for potentiodynamic polarization studies. The amorphous nature of the specimens was checked by X-ray diffraction. The bulk amorphous alloy Zr 59 Cu 20 Ni 8 Al 10 Ti 3 shows the better corrosion resistance than Zr 57 Cu 15.4 Ni 12.6 Al 10 Nb 5 alloy in the aqueous HNO 3 media as the value of the corrosion current density (I corr ) for Zr 57 Cu 15.4 Ni 12.6 Al 10 Nb 5 alloy were found to be more than Zr 59 Cu 20 Ni 8 Al 10 Ti 3 alloy in aqueous HNO 3 media. The improved corrosion resistance of Zr 59 Cu 20 Ni 8 Al 10 Ti 3 alloy is possibly due to the presence of Ti and formation of TiO 2 during anodic oxidation. Both Zr based bulk amorphous alloys shows wider passive range at lower concentration of nitric acid and the passive region gets narrowed down with the increase in concentration. A comparison of data obtained from both the Zr-based bulk amorphous alloys is made and results are discussed in the paper. (author)

Atmospheric measurements of gas-phase HNO3 and SO2 using chemical ionization mass spectrometry during the MINATROC field campaign 2000 on Monte Cimone

Directory of Open Access Journals (Sweden)

M. Hanke

2003-01-01

Full Text Available The EU-project MINATROC (MINeral dust And TROpospheric Chemistry aims at enabling an estimation of the influence of mineral dust, a major, but to date largely ignored component of tropospheric aerosol, on tropospheric oxidant cycles. Within the scope of this project continuous atmospheric measurements of gas-phase HNO3 and SO2 were conducted in June and July 2000 at the CNR WMO station, situated on Monte Cimone (MTC (44°11' N --10°42' E, 2165 m asl, Italy. African air transporting dust is occasionally advected over the Mediterranean Sea to the site, thus mineral aerosol emitted from Africa will encounter polluted air masses and provide ideal conditions to study their interactions. HNO3 and SO2 were measured with an improved CIMS (chemical ionization mass spectrometry system for ground-based measurements that was developed and built at MPI-K Heidelberg. Since HNO3  is a very sticky compound special care was paid for the air-sampling and background-measurement system. Complete data sets could be obtained before, during and after major dust intrusions. For the first time these measurements might provide a strong observational indication of efficient uptake of gas-phase HNO3 by atmospheric mineral-dust aerosol particles.

Vapor pressure data for fatty acids obtained using an adaptation of the DSC technique

International Nuclear Information System (INIS)

Matricarde Falleiro, Rafael M.; Akisawa Silva, Luciana Y.; Meirelles, Antonio J.A.; Krähenbühl, Maria A.

2012-01-01

Highlights: ► Vapor pressure data of fatty acids were measured by Differential Scanning Calorimetry. ► The DSC technique is especially advantageous for expensive chemicals. ► High heating rate was used for measuring the vapor pressure data. ► Antoine constants were obtained for the selected fatty acids. - Abstract: The vapor pressure data for lauric (C 12:0 ), myristic (C 14:0 ), palmitic (C 16:0 ), stearic (C 18:0 ) and oleic (C 18:1 ) acids were obtained using Differential Scanning Calorimetry (DSC). The adjustments made in the experimental procedure included the use of a small sphere (tungsten carbide) placed over the pinhole of the crucible (diameter of 0.8 mm), making it possible to use a faster heating rate than that of the standard method and reducing the experimental time. The measurements were made in the pressure range from 1333 to 9333 Pa, using small sample quantities of fatty acids (3–5 mg) at a heating rate of 25 K min −1 . The results showed the effectiveness of the technique under study, as evidenced by the low temperature deviations in relation to the data reported in the literature. The Antoine constants were fitted to the experimental data whose values are shown in Table 5.

Studies on inorganic exchangers - polyantimonic acid

International Nuclear Information System (INIS)

Murthy, T.S.; Balasubramanian, K.R.; Ananthakrishnan, M.; Ramani, K.S.; Varma, R.N.

1976-01-01

From the detailed experimental investigations carried out, it may be mentioned that the inorganic exchanger polyantimonic acid could be used for effectively separating strontium from fission product waste solutions free from caesium and zirconium at acidities of the order of 2M or so. After thorough washing of the column with 2M HNO 3 acid to remove any residual activity unadsorbed, the strontium can be eluted with a mixture of 1M AgNO 3 +6M HNO 3 at room temperature. The column after regeneration and conditioning can be used for further adsorption and elution up to a maximum of 6 cycles without much deterioration in column characteristics. (author)

Extraction of trivalent actinides and lanthanides from nitric acid solutions by ion flotation

International Nuclear Information System (INIS)

Mezhov, E.H.; Samatov, A.V.; Troyanovskiy, L.V.

1992-01-01

To determine whether the deep extraction of trivalent actinides from liquid active waste is feasible, the authors made a detailed investigation into the ion flotation of europium (as a simulator of americium) and americium from nitric acid solutions by using as an SAS precipitant either lauril phosphoric acid (LPA) to reprocess 0.1-0.7 M HNO 3 or diphosphine dioxides (PO) for 1-5 M HNO 3 . In all instances the extent of metal removal increases with floto-reagent expenditure. When the floto-reagent excess required for full precipitation is reached, the extraction of the metals under study is high, viz., 97-98% from 0.1 M HNO 3 with LPA and ∼75% from 3-3.5 M HNO 3 with PO per one flotation operation

Acid extraction by supported liquid membranes containing basic carriers

International Nuclear Information System (INIS)

Danesi, P.R.; Cianetti, C.; Horwitz, E.P.

1983-01-01

The extraction of HNO 3 (nitric acid) from aqueous solutions by permeation through a number of supported liquid membranes containing basic carriers dissolved in diethylbenzene has been studied. The results have shown that the best permeations are obtained with long chain aliphatic amines (TLA, Primene JM-T) followed by TOPO (trioctylphosphine oxide) and then by other monofunctional and bifunctional organophosphorous basic carriers. The influence of an aliphatic diluent on the permeability of HNO 3 through a supported liquid membrane containing TLA as carrier was also investigated. In this case the permeability to HNO 3 decreases as a result of the lower diffusion coefficient of the acid-carrier complex in the more vicous aliphatic solvent. 4 figures

The Effects of Nitroxyl (HNO) on H2O2 Metabolism and Possible Mechanisms of HNO Signaling

OpenAIRE

Jackson, Matthew I.; Fields, Hannah F.; Lujan, Timothy S.; Cantrell, Megan M.; Lin, Joseph; Fukuto, Jon M.

2013-01-01

Nitroxyl (HNO) possesses unique and potentially important biological/physiological activity that is currently mechanistically ill-defined. Previous work has shown that the likely biological targets for HNO are thiol proteins, oxidized metalloproteins (i.e. ferric heme proteins) and, most likely, selenoproteins. Interestingly, these are the same classes of proteins that interact with H2O2. In fact, these classes of proteins not only react with H2O2, and thus potentially responsible for the sig...

McCabe thiele diagram for tetraoctyl diglycolamide (TODGA)-NPH-Nd(III)-HNO3 system

International Nuclear Information System (INIS)

Ansari, S.A.; Prabhu, D.R.; Gujar, R.B.; Murali, M.S.; Manchanda, V.K.

2007-01-01

Preparatory studies were carried out to set up the mixer settler runs for the partitioning of actinides from simulated high level waste solution using 0.1M N,N,N',N'-tetraoctyl diglycolamide and 0.5M dihexyl octanamide dissolved in NPH. McCabe-Thiele diagram suggested that three stages each of extraction and stripping were sufficient for complete extraction and stripping of Nd from SHLW solution containing 0.6g/L lanthanides at 3.12M HNO 3 . Parameters such as loading, stripping, number of stages required for complete extraction and stripping as well as reusability of the extractant were evaluated. (author)

Investigation of the vaporization of boric acid by transpiration thermogravimetry and knudsen effusion mass spectrometry.

Science.gov (United States)

Balasubramanian, R; Lakshmi Narasimhan, T S; Viswanathan, R; Nalini, S

2008-11-06

The vaporization of H3BO3(s) was studied by using a commercial thermogravimetric apparatus and a Knudsen effusion mass spectrometer. The thermogravimetric measurements involved use of argon as the carrier gas for vapor transport and derivation of vapor pressures of H3BO3(g) in the temperature range 315-352 K through many flow dependence and temperature dependence runs. The vapor pressures as well as the enthalpy of sublimation obtained in this study represent the first results from measurements at low temperatures that are in accord with the previously reported near-classical transpiration measurements (by Stackelberg et al. 70 years ago) at higher temperatures (382-413 K with steam as the carrier gas). The KEMS measurements performed for the first time on boric acid showed H3BO3(g) as the principal vapor species with no meaningful information discernible on H2O(g) though. The thermodynamic parameters, both p(H3BO3) and Delta sub H degrees m(H3BO3,g), deduced from KEMS results in the temperature range 295-342 K are in excellent agreement with the transpiration results lending further credibility to the latter. All this information points toward congruent vaporization at the H3BO3 composition in the H2O-B2O3 binary system. The vapor pressures obtained from transpiration (this study and that of Stackelberg et al.) as well as from KEMS measurements are combined to recommend the following: log [p(H3BO3)/Pa]=-(5199+/-74)/(T/K)+(15.65+/-0.23), valid for T=295-413 K; and Delta sub H degrees m=98.3+/-9.5 kJ mol (-1) at T=298 K for H3BO3(s)=H3BO3(g).

Determination of Water Vapor Pressure Over Corrosive Chemicals Versus Temperature Using Raman Spectroscopy as Exemplified with 85.5% Phosphoric Acid

DEFF Research Database (Denmark)

Rodier, Marion; Li, Qingfeng; Berg, Rolf W.

2016-01-01

A method to determine the water vapor pressure over a corrosive substance was developed and tested with 85.5 ± 0.4% phosphoric acid. The water vapor pressure was obtained at a range of temperatures from ∼25 ℃ to ∼200 ℃ using Raman spectrometry. The acid was placed in an ampoule and sealed...... with a reference gas (either hydrogen or methane) at a known pressure (typically ∼0.5 bar). By comparing the Raman signals from the water vapor and the references, the water pressure was determined as a function of temperature. A considerable amount of data on the vapor pressure of phosphoric acid are available...... in the literature, to which our results could successfully be compared. A record value of the vapor pressure, 3.40 bar, was determined at 210 ℃. The method required a determination of the precise Raman scattering ratios between the substance, water, and the used reference gas, hydrogen or methane. In our case...

Rate constants of the equilibrium reactions SO⨪4 + HNO3 ⇄ HSO-4 + NO3 and SO⨪4 + NO-3 ⇄ SO2-4 + NO3

DEFF Research Database (Denmark)

Løgager, T.; Sehested, K.; Holcman, J.

1993-01-01

Rate constants of the following equilibrium reactions were determined by pulse radiolysis at high solute concentrations: SO4.- + HNO, half arrow right over half arrow left HSO4- + NO3. [k(f) = (2.7 +/- 0.5) x 10(6) M-1 s-1, k(r) = (5.6 +/- 1.0) x 10(3) M-1 s-1] and SO4.- + NO3- half arrow right...

Properties of concentrated plutonium nitrate solutions

International Nuclear Information System (INIS)

Gray, J.H.; Swanson, J.L.

1978-01-01

Selected properties were measured for solutions containing about 500 and 700 g/l plutonium (IV) in 4--5M nitric acid: density, viscosity, vapor pressure, boiling point, radiolytic gas (H 2 ) evolution rates, and corrosion rate on Ti and 304L stainless steel. Pu solubility was determined to be 550 to 800 g/l in 2.5 to 7M HNO 3 at ambient temperature and 820 to 860 g/l in 3M HNO 3 at 50 0 C

Vertical Distribution of NO, NO(2), and HNO(3) as Derived from Stratospheric Absorption Infrared Spectra.

Science.gov (United States)

Fontanella, J C; Girard, A; Gramont, L; Louisnard, N

1975-04-01

This paper is devoted to the results concerning NO, NO(2), and HNO(3) obtained during airborne experiments performed in June-July 1973 on Concorde 001. The altitude of flight was about 16 km. Results concerning NO are, within the accuracy of measurement, in agreement with results of a previousspectrometric balloonborne experiment conducted jointly by IASB and ONERA (14 May 1973). Nitric oxide is concentrated in stratospheric layers clearly above the flight altitude. Integrated amount of NO along the optical path is (4 +/- 1.5) x 10(16) mol cm(-2) for a solar elevation varying from +2 degrees above the horizontal plane to -1 degrees . A value of 6 x 10(8) mol cm(-3) may be given as an upper limit for the local concentration at the flight altitude. Thereis no significant difference in the integrated amount observed at sunset and sunrise. Measured value of NO(2) local concentration at 15.5 km is (1.1 +/- 0.2) x 10(9) mol cm(-3), in sunset conditions. This value is not greatly modified between 15 km and 30 km. Measured value of HNO(3). This value increases with altitude between 15 km and 20 km. The local concentration is maximum at 20 km. The measured value is (2 +/- 1) x 10(10) mol cm(-3) at 20 km. It seems that local concentration decreases rapidly above 20 km.

Effect of Gold (Au) Doping on the Surface of CeO2 Materials Surface Gas Sensor to NH3, CO and HNO3 Detection Sensitivity

International Nuclear Information System (INIS)

Sayono; Tjipto Sujitno; Agus Santoso; Sunardi

2002-01-01

Research on the effect of various dose and energy of gold ions (1.2 x 10 16 ion/cm 2 , 40 keV; 4.4 x 10 16 ion/cm 2 , 60 keV and 4.6 x 10 16 ion/cm 2 , 80 keV) implanted into CeO 2 thin layer gas sensor has been carried out using ion accelerator. The effect such as their resistance and sensitivity for various temperature and gas sensor such as NH 3 , CO and HNO 3 has been done. It was found that the best resistance and sensitivity was achieved at ion dose 1.2 x 10 16 ion/cm 2 and 40 keV. At this conditions, the resistance was 2.22 MΩ and sensitivity was (70.3 ± 8.38)% for NH 3 ; (45 ± 6.78)% for CO and (30.3 ± 5.5)% for HNO 3 gas, at the sensor temperature of 325 o C and concentration of 4800 ppm. (author)

Vapor-liquid equilibria for nitric acid-water and plutonium nitrate-nitric acid-water solutions

International Nuclear Information System (INIS)

Maimoni, A.

1980-01-01

The liquid-vapor equilibrium data for nitric acid and nitric acid-plutnonium nitrate-water solutions were examined to develop correlations covering the range of conditions encountered in nuclear fuel reprocessing. The scanty available data for plutonium nitrate solutions are of poor quality but allow an order of magnitude estimate to be made. A formal thermodynamic analysis was attempted initially but was not successful due to the poor quality of the data as well as the complex chemical equilibria involved in the nitric acid and in the plutonium nitrate solutions. Thus, while there was no difficulty in correlating activity coefficients for nitric acid solutions over relatively narrow temperature ranges, attempts to extend the correlations over the range 25 0 C to the boiling point were not successful. The available data were then analyzed using empirical correlations from which normal boiling points and relative volatilities can be obtained over the concentration ranges 0 to 700 g/l Pu, 0 to 13 M nitric acid. Activity coefficients are required, however, if estimates of individual component vapor pressures are needed. The required ternary activity coefficients can be approximated from the correlations

Vapor pressure data for fatty acids obtained using an adaptation of the DSC technique

Energy Technology Data Exchange (ETDEWEB)

Matricarde Falleiro, Rafael M. [LPT, Departamento de Processos Quimicos (DPQ), Faculdade de Engenharia Quimica, Universidade de Campinas (UNICAMP), 13083-852 Campinas - SP (Brazil); Akisawa Silva, Luciana Y. [Departamento de Ciencias Exatas e da Terra, Universidade Federal de Sao Paulo (UNIFESP), 09972-270 Diadema - SP (Brazil); Meirelles, Antonio J.A. [EXTRAE, Departamento de Engenharia de Alimentos (DEA), Faculdade de Engenharia de Alimentos, Universidade de Campinas (UNICAMP), 13083-862 Campinas - SP (Brazil); Kraehenbuehl, Maria A., E-mail: mak@feq.unicamp.br [LPT, Departamento de Processos Quimicos (DPQ), Faculdade de Engenharia Quimica, Universidade de Campinas (UNICAMP), 13083-852 Campinas - SP (Brazil)

2012-11-10

Highlights: Black-Right-Pointing-Pointer Vapor pressure data of fatty acids were measured by Differential Scanning Calorimetry. Black-Right-Pointing-Pointer The DSC technique is especially advantageous for expensive chemicals. Black-Right-Pointing-Pointer High heating rate was used for measuring the vapor pressure data. Black-Right-Pointing-Pointer Antoine constants were obtained for the selected fatty acids. - Abstract: The vapor pressure data for lauric (C{sub 12:0}), myristic (C{sub 14:0}), palmitic (C{sub 16:0}), stearic (C{sub 18:0}) and oleic (C{sub 18:1}) acids were obtained using Differential Scanning Calorimetry (DSC). The adjustments made in the experimental procedure included the use of a small sphere (tungsten carbide) placed over the pinhole of the crucible (diameter of 0.8 mm), making it possible to use a faster heating rate than that of the standard method and reducing the experimental time. The measurements were made in the pressure range from 1333 to 9333 Pa, using small sample quantities of fatty acids (3-5 mg) at a heating rate of 25 K min{sup -1}. The results showed the effectiveness of the technique under study, as evidenced by the low temperature deviations in relation to the data reported in the literature. The Antoine constants were fitted to the experimental data whose values are shown in Table 5.

2-Mercaptopyrimidine as an effective inhibitor for the corrosion of cold rolled steel in HNO_3 solution

International Nuclear Information System (INIS)

Li, Xianghong; Deng, Shuduan; Lin, Tong; Xie, Xiaoguang; Du, Guanben

2017-01-01

Highlights: • MP acts an effective inhibitor in HNO_3, but other pyrimidine derivatives are poor. • MP is a mixed inhibitor, while mainly retards anodic reaction. • EIS exhibit depressed capacitive loops whose diameters are increased with MP. • The most active adsorption site is S atom for any MP molecular form. • The adsorptive order is thiol-MP < thione-MP < p-thiol-MP < p-thione-MP. - Abstract: The inhibition effect of five pyrimidine derivatives (2-chloropyrimidine, 2-hydroxypyrimidine, 2-bromopyrimidine, 2-aminopyrimidine, 2-mercaptopyrimidine) on the corrosion of cold rolled steel (CRS) in 0.1 M HNO_3 solution was comparatively examined. 2-Mercaptopyrimidine (MP) was found to be an effective inhibitor with the inhibition efficiency as high as 99.1% at a low concentration 0.50 mM. But other four pyrimidine derivatives exhibited poor inhibitive ability. The addition of MP caused both anodic and cathodic curves to low current densities, and was found to significantly strengthen the impedance. Quantum chemical calculation and molecular dynamic simulation were performed to theoretically investigate the adsorption mechanism.

Thermal degradation kinetics of polylactic acid/acid fabricated cellulose nanocrystal based bionanocomposites.

Science.gov (United States)

Monika; Dhar, Prodyut; Katiyar, Vimal

2017-11-01

Cellulose nanocrystals (CNC) are fabricated from filter paper (as cellulosic source) by acid hydrolysis using different acids such as sulphuric (H 2 SO 4 ), phosphoric (H 3 PO 4 ), hydrochloric (HCl) and nitric (HNO 3 ) acid. The resulting acid derived CNC are melt mixed with Polylactic acid (PLA) using extruder at 180°C. Thermogravimetric (TGA) result shows that increase in 10% and 50% weight loss (T 10 , T 50 ) temperature for PLA-CNC film fabricated with HNO 3 , H 3 PO 4 and HCl derived CNC have improved thermal stability in comparison to H 2 SO 4 -CNC. Nonisothermal kinetic studies are carried out with modified-Coats-Redfern (C-R), Ozawa-Flynn-Wall (OFW) and Kissinger method to predict the kinetic and thermodynamic parameters. Subsequently prediction of these parameter leads to the proposal of thermal induced degradation mechanism of nanocomposites using Criado method. The distribution of E a calculated from OFW model are (PLA-H 3 PO 4 -CNC: 125-139 kJmol -1 ), (PLA-HNO 3 -CNC: 126-145 kJmol -1 ), (PLA-H 2 SO 4 -CNC: 102-123 kJmol -1 ) and (PLA-HCl-CNC: 140-182 kJmol -1 ). This difference among E a for the decomposition of PLA-CNC bionanocomposite is probably due to various acids used in this study. The E a calculated by these two methods are found in consonance with that observed from Kissinger method. Further, hyphenated TG-Fourier transform infrared spectroscopy (FTIR) result shows that gaseous products such as CO 2 , CO, lactide, aldehydes and other compounds are given off during the thermal degradation of PLA-CNC nanocomposite. Copyright © 2017 Elsevier B.V. All rights reserved.

Contribution to the study of the redox couple Np(VI)/Np(V) in the presence of uranium(VI) in solutions of nitric acid and nitrous acid; Contribution a l'etude du comportement redox du couple Np(VI)/Np(V) en presence d'uranium VI dans les solutions constituees d'acide nitrique et d'acide nitreux

Energy Technology Data Exchange (ETDEWEB)

Arpigny, S. [CEA Marcoule, Dept. de Radiochimie et Procedes, DRP, 30 (France)

2001-07-01

The redox behavior of the Np(VI)/Np(V) couple was the subject of a spectrometric study of the Np(VI) reduction reaction in nitric acid solutions (4 to 5 M) containing variable concentrations (1.5 to 3.5 x 10{sup -3} M) of nitrous acid. A low nitrous acid concentration and a high nitric acid concentration were found to favor the stabilization of Np(VI). The stoichiometric coefficients of nitrous acid and nitric acid in the Np(VI) reduction reaction were determined thermodynamically, although only the reaction order with respect to HNO{sub 2} could be calculated from a kinetic analysis. Adding nitrate ions to a HNO{sub 3}/HNO{sub 2} solution enhanced the stability of neptunium at oxidation state +VI, but also increased the reduction rate. When uranium(VI) was added to the HNO{sub 3}/HNO{sub 2} solutions, the total quantity of neptunium at oxidation state +V (either free or as a Np(V)-U(VI) complex) remained practically unchanged, as did the Np(VI) reduction rate. The electrochemical behavior of the Np(VI)/Np(V) couple was investigated in a weak acidic medium by voltammetry with an ultra-micro-electrode (UME). The oxidation wave limiting current variation was a linear function of the Np(V) concentration when a gold UME was used, but not with a platinum UME; the reduction wave limiting current variation versus the Np(V) concentration was linear with either gold or platinum UMEs. The presence of the Np(V)-U(VI) complex in the neptunium solutions was characterized by a shift in the normal apparent potential of the Np(VI)/Np(V) couple toward anodic potentials consistent with the previously determined values of the complexation constants. (author)

The oxidation of hydroxylamine by nitric and nitrous acids in the presence of technetium (VII)

International Nuclear Information System (INIS)

Koltunov, V.S.; Gomonova, T.V.; Savilova, O.A.; Zhuravleva, G.I.

2000-01-01

The oxidation of hydroxylamine by nitric acid in the presence of technetium ions at temperatures above ∝60 C is an autocatalytic process comprising an induction period and then a catalysed reaction involving HNO 2 , which has accumulated in the solution. Tc ions have no appreciable effect on the reaction rate, which is governed only by the nitric and nitrous acid oxidation reactions of hydroxylamine, but the presence of Tc ions does extend the initial induction period. The rate of hydroxylamine oxidation by HNO 3 in the presence of HNO 2 , that is, after the induction period, was found to be: -d[NH 3 OH + ]/dt = k[NH 3 OH + ][HNO 2 ][HNO 3 ] 3.5 where k = 120 ± 10 l 4.5 mol -4.5 min -1 at T = 80 C, μ = 2 and [H + ] ≤ 2 M. Under these conditions, the reaction apparently has a high activation energy of 160-180 kJ mol -1 . At low temperatures (20-40 C) hydroxylamine is effectively stable in solutions of HNO 3 up to concentrations of ∝2 M, whether or not Tc(VII) ions are present. Tc(V) was also observed to form at least one complex on reduction with excess hydroxylamine with an absorption maximum between 467 and 480 nm dependent on the solution acidity. (orig.)

Phase transition and luminescence properties from vapor etched silicon

International Nuclear Information System (INIS)

Aouida, S.; Saadoun, M.; Ben Saad, K.; Bessais, B.

2006-01-01

In this work, we present a study on the structure and photoluminescence (PL) properties of a non-conventional ammonium hexafluorosilicate (NH 4 ) 2 SiF 6 (white powder) obtained from HNO 3 /HF chemical vapor etching (CVE) of silicon wafers. The CVE method leads either to the formation of luminescent Porous Silicon (PS) or SiO x /Si-containing (NH 4 ) 2 SiF 6 depending on the experimental conditions. At specific conditions (i.e., HNO 3 / HF volume ratio > 1 / 4), the CVE technique can generate instead of PS, a (NH 4 ) 2 SiF 6 phase where SiO x /Si particles are embedded. The (NH 4 ) 2 SiF 6 marketed powder is not luminescent, while that obtained from silicon vapor-etching presents a noticeable intense and stable photoluminescence (PL), which was found to have mainly two shoulders at 1.98 and 2.1 eV. Two processes have been proposed to explain this PL property. First, the visible luminescence around 1.98 eV would come from silicon nanoparticles embedded in the powder, having a distribution size that does not allow SiO x species to influence their own PL. Second, the PL shoulder around 2.1 eV would originate from small silicon nanoparticles trapped in SiO x features, leading to oxide related states that may trap electrons or excitons, depending on the silicon nanoparticle size, wherein radiative recombination occurs. The PL shoulder could become broader at low temperatures suggesting the existence of radiative recombination in SiO x related defects

On the identification of complexing radiolysis products in the Purex system. (20%TBP - Dodecane - HNO3)

International Nuclear Information System (INIS)

Becker, R.; Baumgartner, F.; Steiglitz, L.

1978-09-01

The lifetime of the extraction system TBP Dodecane-aqueous HNO. In the Purex process is limited by radiolytic and hydrolytic decomposition of the extracting and diluting agent which is indicated by an increased retention of fission products, especially zirconium. In this work, the radiolytically formed complexing agents responsible for this are enriched (molecular distillation) and separated in several fractions by liquid chromatography. The chemical composition of these fractions was identified by a combination of gas chromatography and mass spectrometry, supplemented by infra-red spectroscopy. As for doubtful complexing agents, they are mainly long-chain phosphoric acid esters, and, to a lesser extent, the existence of polycarbonyl compounds is suspected. The high molecular weight components of the phosphate ester fraction could be separated by gas chromatography and identified as oligomeric phosphate esters. (author)

Studies on the decomposition of oxalic acid by nitric acid in presence of catalysts

International Nuclear Information System (INIS)

Noronha, D.M.; Pius, I.C.; Chaudhury, S.

2015-01-01

Impure Plutonium oxalate generated from the recovery of plutonium from waste solutions may require further purification via anion exchange. Conventionally, plutonium oxalate is converted to oxide in a furnace and the oxide is dissolved in Conc. HNO 3 containing HF and purified by anion exchange route. Studies initiated on the decomposition of oxalic acid with Conc. HNO 3 to facilitate direct dissolution of plutonium oxalate and quantitative destruction of oxalate are discussed in this paper. (author)

Dissolution kinetics of metal coating in HNO3-scCO2 micro-emulsion using QCM

International Nuclear Information System (INIS)

Ju, Min Su; Koh, Moon Sung; Park, Kwang Heon; Kim, Hak Won; Kim, Hong Doo

2005-01-01

technique expands its application area to pressurized fluids such as liquids and supercritical CO 2 . In this study, we made a HNO 3 -scCO 2 microemulsion to remove a film from a contaminated metal surface. F-AOT and Proline surfactant-1 were used as a surfactant. HNO 3 was used as a acid solution for dissolution Cu coating. As a setting for experimental conditions, we analyzed the film removal characteristics of Cu and Ni coated QCM

Electrochemical mechanism of uranium mononitride dissolution in aqueous solutions of nitric acid

Energy Technology Data Exchange (ETDEWEB)

Ershov, Boris G. [Russian Academy of Sciences, Moscow (Russian Federation). Frumkin Inst. of Physical Chemistry and Electrochemistry

2017-09-01

It was shown that the dissolution of UN with metallic conduction follows an electrochemical mechanism when it proceeds in contact with an electrically conductive medium (HNO{sub 3} solution). According to this mechanism, the oxidation of UN (at the anode) passes an electron into the UN matrix, which is a conductor, and can then reduce nitric acid in a parallel reaction a short distance away at another exposed surface of the UN (at the cathode). As a result, the reduction of HNO{sub 3} affords NO and NO{sub 2}, while oxidation of uranium mononitride affords NH{sub 3}, N{sub 2}, and N{sub 2}O. The occurrence of these two separate processes accounts for the composition and yields of the products formed from UN and HNO{sub 3} as well as for the nitrogen isotope distribution between them when UN and HNO{sub 3} were labeled with {sup 14} N or {sup 15}N. A mathematical equation describing the dependence of N{sub 2} and N{sub 2}O yields on HNO{sub 3} concentration was derived. It was also shown that the calculated value of standard electromotive force of the galvanic pair formed on the UN surface during its dissolution in HNO{sub 3} is high enough to initiate and support the electrochemical mechanism of its dissolution in nitric acid.

Catalytic reduction of NH4NO3 by NO. Effects of solid acids and implications for low temperature DeNOx processes

International Nuclear Information System (INIS)

Savara, Aditya; Li, Mei-Jun; Sachtler, Wolfgang M.H.; Weitz, Eric

2008-01-01

Ammonium nitrate is thermally stable below 250 C and could potentially deactivate low temperature NO x reduction catalysts by blocking active sites. It is shown that NO reduces neat NH 4 NO 3 above its 170 C melting point, while acidic solids catalyze this reaction even at temperatures below 100 C. NO 2 , a product of the reduction, can dimerize and then dissociate in molten NH 4 NO 3 to NO + + NO 3 - , and may be stabilized within the melt as either an adduct or as HNO 2 formed from the hydrolysis of NO + or N 2 O 4 . The other product of reduction, NH 4 NO 2 , readily decomposes at ≤100 C to N 2 and H 2 O, the desired end products of DeNO x catalysis. A mechanism for the acid catalyzed reduction of NH 4 NO 3 by NO is proposed, with HNO 3 as an intermediate. These findings indicate that the use of acidic catalysts or promoters in DeNO x systems could help mitigate catalyst deactivation at low operating temperatures (<150 C). (author)

Effect of HNO3-cerium(IV) decontamination on stainless steel canister materials

International Nuclear Information System (INIS)

Westerman, R.E.; Mackey, D.B.

1991-01-01

Stainless steel canisters will be filled with vitrified radioactive waste at the West Valley Demonstration Project (WVDP), West Valley, NY. After they are filled, the sealed canisters will be decontaminated by immersion in a HNO 3 -Ce(IV) solution, which will remove the oxide film and a small amount of metal from the surface of the canisters. Studies were undertaken in support of waste form qualification activities to determine the effect of this decontamination treatment on the legibility of the weld-bead canister identification label, and to determine whether this decontamination treatment could induce stress-corrosion cracking (SCC) in the AISI 304L stainless steel (SS) canister material. Neither the label legibility nor the canister integrity with regard to SCC were found to be prejudiced by the simulated decontamination treatment

Physiological responses of lichens to factorial fumigations with nitric acid and ozone

Science.gov (United States)

J. Riddell; P.E. Padgett; T. Nash

2012-01-01

This paper addresses the effects of gaseous nitric acid (HNO3) and ozone (O3), two important air pollutants, on six lichen species with different morphological, ecological, and biological characteristics. The treatment chambers were set up in a factorial design consisting of control chambers, chambers fumigated with HNO

Postdoc Proposal

Energy Technology Data Exchange (ETDEWEB)

Dorhout, Jacquelyn Marie [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2017-11-21

The goal of this project is to determine whether variables such as the molarity of nitric acid (HNO₃), temperature, and surface characteristics of uranium materials have an effect on the fractionation of ¹⁵N between the solution and vapor phases.

Electrochemical corrosion behavior of acid treated strip cast AM50 and AZX310 magnesium alloys in 3.5 wt.% NaCl solution

Directory of Open Access Journals (Sweden)

Srinivasan Arthanari

2017-09-01

Full Text Available The influence of acid treatments on the surface morphology and electrochemical corrosion behavior of strip-cast AM50 and AZX310 alloys have been studied in the present investigation. The alloys were acid treated using H3PO4 (AT-1, HF (AT-2 and HNO3 (AT-3 for different treatment durations viz., 60, 300 and 600 s. The acid treatments produced a surface layer consisting of corresponding magnesium salts of the acids and were confirmed from the X-ray diffraction (XRD, scanning electron microscopy (SEM and energy dispersive X-ray analysis (EDAX. AT-1 treatment produced cracked and network porous morphology for AM50 and AZX310 alloys respectively and AT-3 treatment exhibited dense creaked surface layer formation while AT-2 does not produce any significant change in the morphology. Polarization studies revealed that, the acid treatment significantly altered the corrosion process by altering anodic and cathodic reaction rates of AM50 and AZX310 alloys. The HNO3 (AT-3 treatment was effective compared to other treatments to control the corrosion rate in the studied treatment conditions. The surface morphology and chemical composition of surface layer produced during the treatment was correlated to explain the corrosion results.

Validation of HNO3, ClONO2, and N2O5 from the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS

Directory of Open Access Journals (Sweden)

P. Raspollini

2008-07-01

Full Text Available The Atmospheric Chemistry Experiment (ACE satellite was launched on 12 August 2003. Its two instruments measure vertical profiles of over 30 atmospheric trace gases by analyzing solar occultation spectra in the ultraviolet/visible and infrared wavelength regions. The reservoir gases HNO3, ClONO2, and N2O5 are three of the key species provided by the primary instrument, the ACE Fourier Transform Spectrometer (ACE-FTS. This paper describes the ACE-FTS version 2.2 data products, including the N2O5 update, for the three species and presents validation comparisons with available observations. We have compared volume mixing ratio (VMR profiles of HNO3, ClONO2, and N2O5 with measurements by other satellite instruments (SMR, MLS, MIPAS, aircraft measurements (ASUR, and single balloon-flights (SPIRALE, FIRS-2. Partial columns of HNO3 and ClONO2 were also compared with measurements by ground-based Fourier Transform Infrared (FTIR spectrometers. Overall the quality of the ACE-FTS v2.2 HNO3 VMR profiles is good from 18 to 35 km. For the statistical satellite comparisons, the mean absolute differences are generally within ±1 ppbv ±20% from 18 to 35 km. For MIPAS and MLS comparisons only, mean relative differences lie within±10% between 10 and 36 km. ACE-FTS HNO3 partial columns (~15–30 km show a slight negative bias of −1.3% relative to the ground-based FTIRs at latitudes ranging from 77.8° S–76.5° N. Good agreement between ACE-FTS ClONO2 and MIPAS, using the Institut für Meteorologie und Klimaforschung and Instituto de Astrofísica de Andalucía (IMK-IAA data processor is seen. Mean absolute differences are typically within ±0.01 ppbv between 16 and 27 km and less than +0.09 ppbv between 27 and 34 km. The ClONO2 partial column comparisons show varying degrees of agreement, depending on the location and the quality of the FTIR measurements. Good agreement was found for the comparisons with the midlatitude Jungfraujoch partial columns for which

Corrosion mechanism of Z3 CN18.10 stainless steel in the presence of nitric acid condensates

International Nuclear Information System (INIS)

Balbaud, Fanny

1998-01-01

In installations handling concentrated boiling nitric acid, a severe intergranular corrosion can sometimes occur in condensation zones constituted of non-sensitized Z3 CN 18.10 stainless steel. Corrosion tests in reactors and in a specific loop, CIRCE, allowed to specify the conditions of occurrence of this type of corrosion and showed the similitude with the corrosion in non-renewed liquid nitric acid: the specific parameters linked to the condensate phase are the high ratio metallic surface area to volume of condensate and the low renewing rate which induce a concentration of oxidation products of the metal and of reduction products of nitric acid. The initiation of the intergranular corrosion is attributed to the increase in the reduction rate of nitric acid by an autocatalytic mechanism which was demonstrated by electrochemical measurements on platinum and on stainless steel. The reduction mechanism involves a charge transfer step where nitrous acid, the electro-active species, is reduced into nitrogen monoxide and a chemical regeneration reaction of nitrous acid. The thermodynamic study led to a representation of the chemical and electrochemical properties of nitric acid. This study allowed also to determine the Gibbs free energy of formation of nitrous acid in solution in concentrated nitric acid at 100 deg. C. The diagram, constructed in coordinates log(P O 2 ) / [-log(P HNO 3 )] or E eXperimental / [-log(P HNO 3 )], shows that the final reduction product of nitric acid depends on the concentration of nitric acid: at 100 deg. C, NO is obtained for concentrations lower than 8 mol.L -1 and NO 2 is obtained for higher concentrations. All these results allowed to propose a corrosion mechanism of Z3 CN 18.10 stainless steel in the presence of nitric acid condensates. [fr

Manipulating the Morphology of P3HT–PCBM Bulk Heterojunction Blends with Solvent Vapor Annealing

KAUST Repository

Verploegen, Eric; Miller, Chad E.; Schmidt, Kristin; Bao, Zhenan; Toney, Michael F.

2012-01-01

Using grazing incidence X-ray scattering, we observe the effects of solvent vapors upon the morphology of poly(3-hexylthiophene)-phenyl-C 61-butyric acid methyl ester (P3HT-PCBM) bulk heterojunction thin film blends in real time; allowing us to observe morphological rearrangements that occur during this process as a function of solvent. We detail the swelling of the P3HT crystallites upon the introduction of solvent and the resulting changes in the P3HT crystallite morphology. We also demonstrate the ability for tetrahydrofuran vapor to induce crystallinity in PCBM domains. Additionally, we measure the nanoscale phase segregated domain size as a function of solvent vapor annealing and correlate this to the changes observed in the crystallite morphology of each component. Finally, we discuss the implications of the morphological changes induced by solvent vapor annealing on the device properties of BHJ solar cells. © 2012 American Chemical Society.

Manipulating the Morphology of P3HT–PCBM Bulk Heterojunction Blends with Solvent Vapor Annealing

KAUST Repository

Verploegen, Eric

2012-10-23

Using grazing incidence X-ray scattering, we observe the effects of solvent vapors upon the morphology of poly(3-hexylthiophene)-phenyl-C 61-butyric acid methyl ester (P3HT-PCBM) bulk heterojunction thin film blends in real time; allowing us to observe morphological rearrangements that occur during this process as a function of solvent. We detail the swelling of the P3HT crystallites upon the introduction of solvent and the resulting changes in the P3HT crystallite morphology. We also demonstrate the ability for tetrahydrofuran vapor to induce crystallinity in PCBM domains. Additionally, we measure the nanoscale phase segregated domain size as a function of solvent vapor annealing and correlate this to the changes observed in the crystallite morphology of each component. Finally, we discuss the implications of the morphological changes induced by solvent vapor annealing on the device properties of BHJ solar cells. © 2012 American Chemical Society.

Study on mechanism for oxidation of N,N-dimethylhydroxylamine by nitrous acid

International Nuclear Information System (INIS)

Li Gaoliang; He Hui

2011-01-01

The oxidation of N,N-dimethylhydroxylamine (DMHAN) by nitrous acid is investigated in perchloric acid and nitric acid medium, respectively. The effects of H + , DMHAN, ionic strength and temperature on the reaction are studied. The rate equation in perchloric acid medium has been determined to be -d[HNO 2 ]/dt = k[DMHAN][HNO 2 ], where k = 12.8 ± 1.0 (mol/L) -1 min -1 when the temperature is 18.5 deg C and the ionic strength is 0.73 mol/L with an activation energy about 41.5 kJ mol -1 . The reaction becomes complicated when it is performed in nitric acid medium. When the molarity of HNO 3 is higher than 1.0 mol/L, nitrous acid will be produced via the reaction between nitric acid and DMHAN. The reaction products are analyzed and the reaction mechanism is discussed in this paper. (author)

Vaporization, fusion and sublimation enthalpies of the dicarboxylic acids from C4 to C14 and C16

International Nuclear Information System (INIS)

Roux, Maria Victoria; Temprado, Manuel; Chickos, James S.

2005-01-01

The fusion enthalpies of the series butanedioic acid through to tetradecanedioic acid and hexadecanedioic acids have been measured by DSC. In addition to fusion, a number of solid-solid phase transitions have also been detected in these diacids. The vaporization enthalpies of these compounds have been measured by correlation gas chromatography using the vaporization enthalpies of butanedioic, hexanedioic and decanedioic acids as standards. The vaporization enthalpies of the diacids from C 4 to C 10 correlated linearly with the number of methylene groups present. Above C 10 , the vaporization enthalpies of C 11 -C 14 and C 16 begin to deviate from linearity. The vaporization enthalpies for these compounds are dependent on the temperature of the GC column used. Similar departure from linearity has also been observed previously in the sublimation enthalpies for these compounds. The results are discussed in terms of formation of a cyclic intramolecular hydrogen bonded network in the gas phase similar to the bimolecular association observed in smaller mono-carboxylic acids at ambient temperatures

Vapor condensation device

International Nuclear Information System (INIS)

Sakurai, Manabu; Hirayama, Fumio; Kurosawa, Setsumi; Yoshikawa, Jun; Hosaka, Seiichi.

1992-01-01

The present invention enables to separate and remove 14 C as CO 3 - ions without condensation in a vapor condensation can of a nuclear facility. That is, the vapor condensation device of the nuclear facility comprises (1) a spray pipe for spraying an acidic aqueous solution to the evaporation surface of an evaporation section, (2) a spray pump for sending the acidic aqueous solution to the spray pipe, (3) a tank for storing the acidic aqueous solution, (4) a pH sensor for detecting pH of the evaporation section, (5) a pH control section for controlling the spray pump, depending on the result of the detection of the pH sensor. With such a constitution, the pH of liquid wastes on the vaporization surface is controlled to 7 by spraying an aqueous solution of dilute sulfuric acid to the evaporation surface, thereby enabling to increase the transfer rate of 14 C to condensates to 60 to 70%. If 14 C is separated and removed as a CO 2 gas from the evaporation surface, the pH of the liquid wastes returns to the alkaline range of 9 to 10 and the liquid wastes are returned to a heating section. The amount of spraying the aqueous solution of dilute sulfuric acid can be controlled till the pH is reduced to 5. (I.S.)

Effect of simulated acid rain (sar) on some morphochemical aspects of mash (vigna mungo l.)

International Nuclear Information System (INIS)

Imran, H.A.; Hussain, M.; Hussain, S.

2014-01-01

The studies were conducted to evaluate the effect of simulated acid rain (SAR) at early plant growth on some morphochemical characters of two varieties of Mash (Vigna mungo L.) namely Mash 97 and Var. 95009. Different pH values were made by using H/sub 2/SO/sub 4/, HNO/sub 3/, and combination of both. The data revealed that low pH (3.5) of either sulphuric acid or the combination of H/sub 2/SO/sub 4/ and HNO/sub 3/ affected more severely at all parameters including number of leaves, shoot: root ratio, water contents of shoot and Potassium ion concentration. Whereas for a few parameters like plant height and number of branches the simulated acid rain of solution of pH 4.5 and 3.5 by using HNO/sub 3/ proved a bit better for plant growth, the root length was increased in case of SAR of solution of pH 3.5 by using H/sub 2/SO/sub 4/+HNO/sub 3/. Foliar application of SAR of solution of pH greater than 4.5 showed some improvement in crop growth due to fertilizer effect of solution's components. (author)

Blue-shifted and red-shifted hydrogen bonds: Theoretical study of the CH3CHO· · ·HNO complexes

Science.gov (United States)

Yang, Yong; Zhang, Weijun; Gao, Xiaoming

The blue-shifted and red-shifted H-bonds have been studied in complexes CH3CHO?HNO. At the MP2/6-31G(d), MP2/6-31+G(d,p) MP2/6-311++G(d,p), B3LYP/6-31G(d), B3LYP/6-31+G(d,p) and B3LYP/6-311++G(d,p) levels, the geometric structures and vibrational frequencies of complexes CH3CHO?HNO are calculated by both standard and CP-corrected methods, respectively. Complex A exhibits simultaneously red-shifted C bond H?O and blue-shifted N bond H?O H-bonds. Complex B possesses simultaneously two blue-shifted H-bonds: C bond H?O and N bond H?O. From NBO analysis, it becomes evident that the red-shifted C bond H?O H-bond can be explained on the basis of the two opposite effects: hyperconjugation and rehybridization. The blue-shifted C bond H?O H-bond is a result of conjunct C bond H bond strengthening effects of the hyperconjugation and the rehybridization due to existence of the significant electron density redistribution effect. For the blue-shifted N bond H?O H-bonds, the hyperconjugation is inhibited due to existence of the electron density redistribution effect. The large blue shift of the N bond H stretching frequency is observed because the rehybridization dominates the hyperconjugation.

Effects of etchants in the transfer of chemical vapor deposited graphene

Science.gov (United States)

Wang, M.; Yang, E. H.; Vajtai, R.; Kono, J.; Ajayan, P. M.

2018-05-01

The quality of graphene can be strongly modified during the transfer process following chemical vapor deposition (CVD) growth. Here, we transferred CVD-grown graphene from a copper foil to a SiO2/Si substrate using wet etching with four different etchants: HNO3, FeCl3, (NH4)2S2O8, and a commercial copper etchant. We then compared the quality of graphene after the transfer process in terms of surface modifications, pollutions (residues and contaminations), and electrical properties (mobility and density). Our tests and analyses showed that the commercial copper etchant provides the best structural integrity, the least amount of residues, and the smallest doping carrier concentration.

Thermometric titration of acids in pyridine.

Science.gov (United States)

Vidal, R; Mukherjee, L M

1974-04-01

Thermometric titration of HClO(4), HI, HNO(3), HBr, picric acid o-nitrobenzoic acid, 2,4- and 2,5-dinitrophenol, acetic acid and benzoic acid have been attempted in pyridine as solvent, using 1,3-diphenylguanidine as the base. Except in the case of 2,5-dinitrophenol, acetic acid and benzoic acid, the results are, in general, reasonably satisfactory. The approximate molar heats of neutralization have been calculated.

Three millimeter molecular line observations in Sagittarius B2. 1: Full synthesis mapping study of HNO, CCS, and HC(13)CCN

Science.gov (United States)

Kuan, Yi-Jehng; Snyder, Lewis E.

1994-01-01

We present the first full synthesis maps of the small molecules HNO, CCS, and HC(13)CCN in Sgr B2. We have observed the 3.8 mm continuum, the HNO J(sub K(sub -1)K(sub 1)) = 1(sub O1)-0(sub OO), the CCS J(sub N) = 7(sub 6)-6(sub 5), and the HC(13)CCN J = 9-8 transitions in the core of the Sgr B2 molecular cloud, using the Berkeley Illinois Maryland Association (BIMA) millimeter array and the NRAO 12 m telescope. We have found that HNO exists in five major gas clumps in the Sgr B2 region, which we have labeled HNO(N), HNO(NW), HNO(E), HNO(M), and HNO(S). Of particular interest is HNO(M), a major molecular gas concentration approximately 15 sec west of Sgr B2(M) in a region of young star formation. HNO is found to be closely associated with the ionized gas and might be depleted around bright H II complexes. In general, the peak intensity of the HNO emission is found to be offset from the peak of the continuum emission. We found evidence for some chemical differentiation among the three species, HNO, CCS, and HC(13)CCN, but the abundance ratios are in fair agreement with theoretical models. Two unidentified lines, U81420 and U81518, were observed, and a previously unknown compact dust source was detected. Our HNO data indicate the presence of a rotating approximately (2.2-4.4) x 10(exp 3)solar mass gas envelope surrounding Sgr B2(N), a possible bipolar gas outflow in HNO(M), and possibly a large (approximately 4.2 x 10(exp 4)solar mass) extended rotating disk associated with HNO(S). In addition, the CCS and HC(13)CCN data approximately outline the extended component of Sgr B2 and clearly show that the southern continuum source Sgr B2(S) is actually a major molecular source as well. Consequently, the kinematics of the Sgr B2 molecular cloud is quite complex, but in moving from the northwest to south, the LSR velocity generally changes from 79 to 46 km/s.

Effects of HCl and HNO3 on the oxidation of toluene to benzaldehyde by H2O2 over TS-1 modified with Al in aqueous phase

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Paricha Pongjirawat

2014-09-01

Full Text Available This research studies effects of HCl and HNO3 in aqueous solution on the oxidation reaction between toluene and hydrogen peroxide to benzaldehyde over titanium silicalite-1 catalyst modified with Al. The reaction was carried out at reaction temperature 120°C in a pressurized autoclave reactor. The research found that the addition of HCl and HNO3 not only increases the concentration of toluene in the aqueous phase but also increases the formation of benzaldehyde as main product in the reaction.

The effect of γ-ray irradiation on the adsorption properties and chemical stability of AMP/SiO2 towards Cs(I) in HNO3 solution

International Nuclear Information System (INIS)

Xiaoxia Zhang; Yan Wu; Yuezhou Wei; Guangxi University, Nanning

2016-01-01

Silica based ammonium molybdophosphate (AMP/SiO 2 ) adsorbent was used to remove Cs(I) from HNO 3 solution. The adsorbent with different absorbed dose (0-300 kGy) was characteristed by X-ray power diffraction. The adsorption data against different γ-ray absorbed doses were analyzed by the Langmuir isotherm. The adsorption capacity decreased slightly from 23.22 to 22.37 mg/g with the increase of the absorbed dose. The breakthrough properties of Cs(I) were conducted using column packed with AMP/SiO 2 before and after irradiation. The chemical stability of AMP/SiO 2 at 300 kGy absorbed dose in 3 mol/L (M) HNO 3 was excellent. (author)

Chemistry of some metals and fluorides in pure nitric acid and high density red fuming nitric acid

International Nuclear Information System (INIS)

Moharum, A.A.M.

1982-10-01

The work presented in this thesis is partly concerned with the reactions of some metals (Bi, U, V) with 100% HNO 3 and the mixture of composition ca. 56 wt% HNO 3 - 44 wt% N 2 O 4 , known as High Density Acid (HDA). Both bismuth and uranium react to give solid products formulated as 'mixed adducts' of Bi(NO 3 ) 3 or UO 2 (NO 3 ) 2 with N 2 O 4 and H 2 O. Vibrational spectroscopy shows these compounds to be nitrosonium nitrato-complexes. X-ray powder diffraction data are presented for the bismuth products. On the other hand, both the solid and solution products obtained by the reaction of vanadium with 100% HNO 3 and HDA, were found to be linear chain V-O polymeric species in which the vanadium atom is co-ordinated to at least four oxygen atoms. Vibrational spectroscopy and X-ray powder diffraction results are reported. 51 V and 14 N n.m.r. spectroscopic studies of V/100% HNO 3 solution are presented. The reactions of BF 3 with 100% HNO 3 and HDA, at low concentrations of BF 3 , were investigated mainly by 11 B and 19 F n.m.r. spectroscopy at room temperature and lower temperatures. The reactions of HDA solutions of aluminium with HF are also reported. The results are discussed. (author)

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

Science.gov (United States)

Myers, R. Thomas

1983-01-01

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

A Recent History of HNO (Nitroxyl) Chemistry, Pharmacology and Therapeutic Potential.

Science.gov (United States)

Fukuto, Jon M

2018-06-02

Due to the excitement surrounding the discovery of nitric oxide (NO) as an endogenously generated signaling molecule, numerous other nitrogen oxides were also investigated as possible physiological mediators. Among these was nitroxyl (HNO). Over the past 25 years or so, a significant amount of work by this lab and many others has discovered that HNO possesses unique chemical properties and important pharmacological utility. Indeed, the pharmacological potential for HNO as a treatment for heart failure, among other uses, has garnered this curious molecule tremendous recent attention. This review thus summarizes the events that led to this recent attention as well as pose remaining questions that are important to answer with regards to understanding the chemistry and biology of HNO. This article is protected by copyright. All rights reserved.

A wet effluent denuder/mist-chamber coupled to ion chromatography for the continuous measurement of atmospheric HONO, HNO{sub 3}, NO{sub 3}{sup -} and SO{sub 4}{sup 2-}.

Energy Technology Data Exchange (ETDEWEB)

Zellweger, C.; Baltensperger, U. [Paul Scherrer Inst. (PSI), Villigen (Switzerland); Hofer, P. [EMPA, Duebendorf (Switzerland)

1997-09-01

A denuder/mist chamber system has been developed for the continuous automated measurement of low level concentrations of HONO, HNO{sub 3} as well as of NO{sub 3}{sup -} and SO{sub 4}{sup 2-}. (author) 2 figs., 1 ref.

Nitric Acid-Treated Carbon Fibers with Enhanced Hydrophilicity for Candida tropicalis Immobilization in Xylitol Fermentation

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Le Wang

2016-03-01

Full Text Available Nitric acid (HNO3-treated carbon fiber (CF rich in hydrophilic groups was applied as a cell-immobilized carrier for xylitol fermentation. Using scanning electron microscopy, we characterized the morphology of the HNO3-treated CF. Additionally, we evaluated the immobilized efficiency (IE of Candida tropicalis and xylitol fermentation yield by investigating the surface properties of nitric acid treated CF, specifically, the acidic group content, zero charge point, degree of moisture and contact angle. We found that adhesion is the major mechanism for cell immobilization and that it is greatly affected by the hydrophilic–hydrophilic surface properties. In our experiments, we found 3 hto be the optimal time for treating CF with nitric acid, resulting in an improved IE of Candida tropicalis of 0.98 g∙g−1 and the highest xylitol yield and volumetric productivity (70.13% and 1.22 g∙L−1∙h−1, respectively. The HNO3-treated CF represents a promising method for preparing biocompatible biocarriers for multi-batch fermentation.

Properties of TiO2 prepared by acid treatment of BaTiO3

International Nuclear Information System (INIS)

Okada, Kiyoshi; Yanagisawa, Tomoki; Kameshima, Yoshikazu; Nakajima, Akira

2007-01-01

TiO 3 powders were prepared by acid treatment of BaTiO 3 and their properties were investigated. The BaTiO 3 powder was subjected to HNO 3 in concentrations ranging from 10 -3 to 8 M at 90 deg. C for 0.5-6 h. Dissolution of BaTiO 3 and precipitation of TiO 2 occurred at acid concentrations of 2-5 M. BaTiO 3 dissolves completely to form a clear solution at reaction times of 0.5-1 h, but a rutile precipitate is formed after 2 h of acid treatment. By contrast, anatase is precipitated by adjusting the pH of the clear solution to 2-3 using NaOH or NH 4 OH solution. The rutile crystals were small and rod-shaped, consisting of many small coherent domains connected by grain boundaries with small inclination angles and edge dislocations, giving them a high specific surface area (S BET ). With increasing HNO 3 concentration, the S BET value increased from 100 to 170 m 2 /g while the crystallite size decreased from 25 to 11 nm. The anatase crystals obtained here were very small equi-axial particles with a smaller crystallite size than the rutile and S BET values of about 270 m 2 /g (higher than the rutile samples). The photocatalytic activity of these TiO 2 was determined from the decomposition rate of Methylene Blue under ultraviolet irradiation. Higher decomposition rates were obtained with larger crystallite sizes resulting from heat treatment. The maximum decomposition rates were obtained in samples heated at 500-600 deg. C. The photocatalytic activity of the TiO 2 was found to depend more strongly on the sample crystallite size than on S BET

Acidity of vapor plume from cooling tower mixed with flue gases emitted from coal-fired power plant.

Science.gov (United States)

Hlawiczka, Stanislaw; Korszun, Katarzyna; Fudala, Janina

2016-06-01

Acidity of products resulting from the reaction of flue gas components emitted from a coal-fired power plant with water contained in a vapor plume from a wet cooling tower was analyzed in a close vicinity of a power plant (710 m from the stack and 315 m from the cooling tower). Samples of this mixture were collected using a precipitation funnel where components of the mixed plumes were discharged from the atmosphere with the rainfall. To identify situations when the precipitation occurred at the same time as the wind directed the mixed vapor and flue gas plumes above the precipitation funnel, an ultrasound anemometer designed for 3D measurements of the wind field located near the funnel was used. Precipitation samples of extremely high acidity were identified - about 5% of samples collected during 12 months showed the acidity below pH=3 and the lowest recorded pH was 1.4. During the measurement period the value of pH characterizing the background acidity of the precipitation was about 6. The main outcome of this study was to demonstrate a very high, and so far completely underestimated, potential of occurrence of episodes of extremely acid depositions in the immediate vicinity of a coal-fired power plant. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis of Patchouli Biochar Cr2O3 Composite Using Double Acid Oxidators for Paracetamol Adsorption

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Tutik Setianingsih

2018-01-01

Full Text Available Composite built by patchouli biochar and metal oxide, Cr2O3, is a potential material for remediation of contaminated wasterwater. Oxidation of biochar using acid or salt oxidators can improve its surface polar functional groups. This treatment may be able to increase impregnation of metal cation (as salt before calcination to form its oxide. In this research, 3 types of oxidators were used to oxidize the biochar before impregnation with purpose to study its influence toward physichochemistry and adsorption performance of the composite. Preparation of the composite included 3 steps, including preparation of biochar by pyrolisis of patchouli biomass using ZnCl2 activator at 450 oC, oxidation of the biochar using 3 different oxidators (H2SO4-HNO3, H3PO4-HNO3, H2O2–HNO3 at 60 oC, impregnation of the oxidized biochar using CrCl3 followed by calcination process to form biochar–Cr2O3 composite at 600 oC. Characterization using X-ray diffraction indicated that the composite containes the Cr2O3 structure. FTIR spectrophotometry characterization indicates the different content of C=O, C-O, and –OH on the composite surface. SEM images shows irregular micro ball shapes. EDX characterization indicates the different Cr content in the composite with same sequence with FTIR absorbances of both C-O and –OH. Adsorption of paracetamol indicates effect of Cr2O3 showing the same sequence of both.

On the Growth of Ternary System HNO3/H2SO4/H2O Aerosol Particles in the Stratosphere

Science.gov (United States)

Hamill, Patrick; Tabazadeh, A.; Kinne, S.; Toon, O. B.; Turco, R. P.

1996-01-01

We present a study of the growth of ternary solution (nitric acid, sulfuric acid and water) droplets in the stratosphere. The growth mechanism is hetero-molecular condensation in which the particle is assumed to be in equilibrium with environmental water vapor. Model results are in reasonable agreement with the averaged extinction ratio obtained by the SAM II satellite system.

Mass spectrometric study of Nd2S3 vaporization

International Nuclear Information System (INIS)

Fenochka, B.V.

1987-01-01

The authors conduct a mass-spectrometric study of neodymium(III) sulfide vaporization. The chemical composition of the samples was stoichiometric and the samples were vaporized from tantalum effusion cells. When the vapor over Nd 2 S 3 is ionized by electrons the mass spectra shows monovalent cations of Nd, S, NdS, and NdO. The enthalpy of vaporization if Nd atoms from Nd 2 S 3 at average experimental temperatures and the standard enthalpy of reaction is shown. Also presented is the enthalpy of vaporization of NdS molecules from Nd 2 S 3 at average experimental temperatures and the standard enthalpy of reaction

On the ability of chemical transport models to simulate the vertical structure of the N2O, NO2 and HNO3 species in the mid-latitude stratosphere

Directory of Open Access Journals (Sweden)

G. Berthet

2006-01-01

Full Text Available In this paper we study the impact of the modelling of N2O on the simulation of NO2 and HNO3 by comparing in situ vertical profiles measured at mid-latitudes with the results of the Reprobus 3-D CTM (Three-dimensional Chemical Transport Model computed with the kinetic parameters from the JPL recommendation in 2002. The analysis of the measured in situ profile of N2O shows particular features indicating different air mass origins. The measured N2O, NO2 and HNO3 profiles are not satisfyingly reproduced by the CTM when computed using the current 6-hourly ECMWF operational analysis. Improving the simulation of N2O transport allows us to calculate quantities of NO2 and HNO3 in reasonable agreement with observations. This is achieved using 3-hourly winds obtained from ECMWF forecasts. The best agreement is obtained by constraining a one-dimensional version of the model with the observed N2O. This study shows that the modelling of the NOy partitioning with better accuracy relies at least on a correct simulation of N2O and thus of total NOy.

Extracting properties of N,N,N'N'-tetraalkyl-2 alkyl propane -1,3 diamides

International Nuclear Information System (INIS)

Nigond, L.

1992-01-01

N,N,N',N'-tetraalkyl -2 alkyl propane -1,3 diamides (RR'NCO) 2 CHR'' are investigated in the aim to separate actinides from nuclear wastes. N,N'-dimethyl N,N'-dibutyl tetradecylmalonamide (DMDBTDMA) was selected. This molecule can extract trivalent actinides in aliphatic diluents. Americium extraction is faster than iron extraction, hydrolytic degradation and solubility in aqueous phase are satisfactory. In non acidic media, diamides form aggregates, the size of which is function of diluent and diamide concentration. Extraction equilibria of HNO 3 , UO 2 2+ , Pu 4+ , Am 3+ and Fe 3+ are investigated.Four complexes are formed with nitric acid: L 2 HNO 3 , LHNO 3 , L 2 (HNO 3 ) 2 and L(HNO 3 ) 3 with L=DMDBTDMA. UO 2 2+ and Pu 4+ extraction takes place via the formation of neutral complexes: LUO 2 (NO 3 ) 2 , LPu(NO 3 ) 4 and L 2 Pu(NO 3 ) 4 for any nitric acid concentration. Am 3+ extraction takes place via the formation of LAm(NO 3 ) 3 and L 2 Am(NO 3 ) 3 for low nitric acid concentration and L x H y Am(NO 3 ) 3+y at higher acidity. Fe 3+ extraction involves anionic complexes L x HFe(NO 3 ) 4 for any acid concentration. In the presence of metallic cations, two kinds of interactions are observed: in the inner sphere of the metal diamide-metal ion complexation and in the outer sphere diamide-metallic complex interaction. The malonamide DMDBTDMA can be used to separate (III), (IV) and (VI) actinides from radioactive wastes

Determination of mercury in rice by cold vapor atomic fluorescence spectrometry after microwave-assisted digestion

Energy Technology Data Exchange (ETDEWEB)

Silva, Maria Jose da [Department of Analytical Chemistry, Edificio de Investigacion, University of Valencia, 50 Dr. Moliner Street, E-46100 Burjassot, Valencia (Spain); Departamento de Quimica Fundamental, Universidade Federal de Pernambuco, Cidade Universitaria, 50740-550 Recife, PE (Brazil); Paim, Ana Paula S. [Departamento de Quimica Fundamental, Universidade Federal de Pernambuco, Cidade Universitaria, 50740-550 Recife, PE (Brazil); Pimentel, Maria Fernanda [Departamento de Engenharia Quimica, Universidade Federal de Pernambuco, Recife, PE (Brazil); Cervera, M. Luisa, E-mail: m.luisa.cervera@uv.es [Department of Analytical Chemistry, Edificio de Investigacion, University of Valencia, 50 Dr. Moliner Street, E-46100 Burjassot, Valencia (Spain); Guardia, Miguel de la [Department of Analytical Chemistry, Edificio de Investigacion, University of Valencia, 50 Dr. Moliner Street, E-46100 Burjassot, Valencia (Spain)

2010-05-14

A cold vapor atomic fluorescence spectrometry method (CV-AFS) has been developed for the determination of Hg in rice samples at a few ng g{sup -1} concentration level. The method is based on the previous digestion of samples in a microwave oven with HNO{sub 3} and H{sub 2}O{sub 2} followed by dilution with water containing KBr/KBrO{sub 3} and hydroxylamine and reduction with SnCl{sub 2} in HCl using external calibration. The matrix interferences and the effect of nitrogen oxide vapors have been evaluated and the method validated using a certified reference material. The limit of detection of the method was 0.9 ng g{sup -1} with a recovery percentage of 95 {+-} 4% at an added concentration of 5 ng g{sup -1}. The concentration level of Hg found in 24 natural rice samples from different origin ranged between 1.3 and 7.8 ng g{sup -1}.

Iron catalyzed conversion of NO into nitrosonium (NO+) and nitroxyl (HNO/NO-) species.

Science.gov (United States)

Stojanović, Srdjan; Stanić, Dragana; Nikolić, Milan; Spasić, Mihailo; Niketić, Vesna

2004-11-01

The conversion of NO into its congeners, nitrosonium (NO+) and nitroxyl (HNO/NO-) species, has important consequences in NO metabolism. Dinitrosyl iron complex (DNIC) combined with thiol ligands was shown to catalyze the conversion of NO into NO+, resulting in the synthesis of S-nitrosothiols (RSNO) both in vitro and in vivo. The formation mechanism of DNIC was proposed to involve the intermediate release of nitroxyl. Since the detection of hydroxylamine (as the product of a rapid reaction of HNO/NO- with thiols) is taken as the evidence for nitroxyl generation, we examined the formation of hydroxylamine, RSNO, and nitrite (the product of a rapid reaction of NO+ with water) in neutral solutions containing iron ions and thiols exposed to NO under anaerobic conditions. Hydroxylamine was detected in NO treated solutions of iron ions in the presence of cysteine, but not glutathione (GSH). The addition of urate, a major "free" iron-binding agent in humans, to solutions of GSH and iron ions, and the subsequent treatment of these solutions with NO increased the synthesis of GSNO and resulted in the formation of hydroxylamine. This caused a loss of urate and yielded a novel nitrosative/nitration product. GSH attenuated the urate decomposition to such a degree that it could be reflected as the function of GSH:urate. Results described here contribute to the understanding of the role of iron ions in catalyzing the conversion of NO into HNO/NO- and point to the role of uric acid not previously described.

A contribution to the study of the extraction of mineral acids and of actinide (IV) and (VI) cations by N,N-dialkylamides

International Nuclear Information System (INIS)

Condamines, N.

1990-03-01

N,N-dialkylamides are alternate extractants to tributylphosphate, TBP, for the actinides separation in nuclear fuel reprocessing. N,N-di (2-ethyl hexyl) butyramide and N,N-di (2 ethyl hexyl) isobutyramide are selected for their sufficient extraction and partition ability towards actinides (IV) and (VI) without coextracting fission products. Mechanisms of HNO 3 , UO 2 2+ , Pu 4+ , Th 4+ are investigated. Nitric acid extraction is due to the competitive formation of the species (HNO 3 )L 2 , (HNO 3 )L, (HNO 3 ) 2 L (L: DOBA or DOiBA). An hydrogen bond is the driving force of the transfer. For low acidity media, amides are neutral extractants. Physical interactions, between free ligand and metallic complex, arise for high amide concentrations. Taking into account the non-ideality of the organic medium by a hard spheres mixture model, we estimate that such interactions are far from negligible and very specific to the amide group. Unlike TBP, when increasing acidity, amides behave as anionic extractants. DOBA and DOiBA appear to be satisfactory extractants for fuel reprocessing [fr

The Consistency of Isotopologues of Ambient Atmospheric Nitric Acid in Passively Collected Samples

Science.gov (United States)

Bell, M. D.; Sickman, J. O.; Bytnerowicz, A.; Padgett, P.; Allen, E. B.

2012-12-01

Anthropogenic sources of nitrogen oxides have previously been shown to have distinctive isotopic signatures of oxygen and nitrogen. Nylon filters are currently used in passive sampling arrays to measure ambient atmospheric nitric acid concentrations and estimate deposition rates. This experiment measured the ability of nylon filters to consistently collect isotopologues of atmospheric nitric acid in the same ratios as they are present in the atmosphere. Samplers were deployed in continuous stirred tank reactors (CSTR) and at field sites across a nitrogen deposition gradient in Southern California. Filters were exposed over a four week period with individual filters being subjected to 1-4 week exposure times. Extracted nitric acid were measured for δ18O and δ15N ratios and compared for consistency based on length of exposure and amount of HNO3 collected. Filters within the CSTRs collected HNO3 at a consistent rate in both high and low concentration chambers. After two weeks of exposure, the mean δ18O values were within 0.5‰ of the δ18O of the source HNO3 solution. The mean of all weekly exposures were within 0.5‰ of the δ15N of the source solution, but after three weeks, the mean δ15N of adsorbed HNO3 was within 0.2‰. As the length of the exposure increased, the variability of measured delta values decreased for both elements. The field samplers collected HNO3 consistent with previously measured values along a deposition gradient. The mean δ18O at high deposition sites was 52.2‰ compared to 35.7‰ at the low deposition sites. Mean δ15N values were similar at all sites across the deposition gradient. Due to precipitation events occurring during the exposure period, the δ15N and δ18O of nitric acid were highly variable at all field sites. At single sites, changes in δ15N and δ18O were negatively correlated, consistent with two-sourcing mixing dynamics, but the slope of the regressions differed between high and low deposition sites. Anthropogenic

Variation in isotopologues of atmospheric nitric acid in passively collected samples along an air pollution gradient in southern California

Science.gov (United States)

Michael D. Bell; James O. Sickman; Andrzej Bytnerowicz; Pamela E. Padgett; Edith B. Allen

2014-01-01

The sources and oxidation pathways of atmospheric nitric acid (HNO3) can be evaluated using the isotopic signatures of oxygen (O) and nitrogen (N). This study evaluated the ability of Nylasorb nylon filters to passively collect unbiased isotopologues of atmospheric HNO3 under controlled and field conditions. Filters...

Reaction Kinetics of Monomethylhydrazine With Nitrous Acid in Perchloric Acid Solution

International Nuclear Information System (INIS)

Wei Yan; Wang Hui; Pan Yongjun; Cong Haifeng; Jiao Haiyang; Jia Yongfen; Zheng Weifang

2009-01-01

The oxidation of monomethylhydrazine (MMH) by nitrous acid was researched in perchloric acid solution with spectrophotometry. The rate equation has been determined as follows: -dc (HNO 2 ) /dt= kc (H + ) 0.9 c (MMH) 1.1 c (HNO 2 ), k is (46.0 ± 2.7) L 2 / (mol 2 · s) with the initial perchlorate concentration of 0.50 mol/L at the temperature of 4.5 degree C. The corresponding activation energy of the reaction is (42.4 ± 0.1) kJ/mol. The results indicate that oxidation of mono-methylhydrazine (MMH) by nitrous acid is fast. The higher concentration of MMH can accelerate the reduction process of nitrous acid. Higher acidity can also speed up the reduction of nitrous acid. (authors)

Thermochemistry of 1,3-diethylbarbituric and 1,3-diethyl-2-thiobarbituric acids: Experimental and computational study

International Nuclear Information System (INIS)

Notario, Rafael; Roux, María Victoria; Ros, Francisco; Emel’yanenko, Vladimir N.; Zaitsau, Dzmitry H.; Verevkin, Sergey P.

2014-01-01

Highlights: • Enthalpies of formation in condensed phase have been obtained. • Enthalpy of vaporization of 1,3-diethylbarbituric acid has been determined. • Enthalpy of sublimation of 1,3-diethyl-2-thiobarbituric acid has been determined. • Gas-phase enthalpies of formation have been obtained. • Gas-phase enthalpies of formation have been calculated at G3 and G4 levels. - Abstract: This paper reports an experimental and computational thermochemical study on two barbituric acid derivatives, viz. 1,3-diethylbarbituric acid and 1,3-diethyl-2-thiobarbituric acid. Values of standard molar enthalpies of formation in the gas phase at T = 298.15 K have been derived from experiment. Energies of combustion were measured by the static bomb combustion calorimetry in the case of 1,3-diethylbarbituric acid, and the rotating-bomb combustion calorimetry in the case of 1,3-diethyl-2-thiobarbituric acid. From the combustion energies, standard molar enthalpies of formation in the crystalline state at T = 298.15 K were calculated. The enthalpy of vaporization of 1,3-diethylbarbituric acid and enthalpy of sublimation of 1,3-diethyl-2-thiobarbituric acid were determined using the transpiration method. Combining calorimetric and transpiration results, values of −(611.9 ± 2.0) kJ · mol −1 and −(343.8 ± 2.2) kJ · mol −1 for the gas-phase enthalpies of formation at T = 298.15 K of 1,3-diethylbarbituric and 1,3-diethyl-2-thiobarbituric acids, respectively, were derived. Theoretical calculations at the G3 and G4 levels were performed, and a study of the molecular structure of the compounds has been carried out. Calculated enthalpies of formation were in very good agreement with the experimental values

Influence of gas-particle partitioning on ammonia and nitric acid fluxes above a deciduous forest in the Midwestern USA

DEFF Research Database (Denmark)

Hansen, Kristina; Sørensen, Lise Lotte; Hornsby, Karen E.

to bi-directionality of the flux, and the dynamics of the chemical gas/aerosol equilibrium of NH3 and HNO3 (or other atmospheric acids) with aerosol-phase ammonium (NH4+) and nitrate (NO3-). NH3 and HNO3 are both very reactive and typically exhibit higher deposition velocities than aerosol NH4...... diffusion denuders with detection by florescence and half-hourly flux measurements are calculated. HNO3 REA system is based on gas capture on sodium chloride (NaCl) coated denuders with subsequent analysis by ion-chromatography, and the resulting fluxes have a resolution of 3-4 hours. CO2 fluxes...

Characterisation of aggregation of tributylphosphate molecules in organic solvent

International Nuclear Information System (INIS)

Mandin, C.; Martinet, L.; Zemb, Th.; Berthon, L.; Madic, Ch.

2000-01-01

This report presents a structural study of the aggregates formed with the organic phases of the extractant tri-n-butyl phosphate, used in the industrial PUREX process (Plutonium and Uranium Extraction; liquid-liquid solvent extraction) for the treatment of high radioactive waste. Combined Small Angle X-ray Scattering and Small Angle Neutron Scattering show that organic TBP solutions (in equilibrium with acid solutions) are organised in oligomeric aggregates. The influence of various parameters such as HNO 3 or TBP concentrations, diluent or acid natures, does not seem to modify the aggregate shape and size, whereas the interactions are modified. Moreover the aggregates disappear under high temperatures, whereas the attractive interactions between them increase at low temperatures. The 'drop weight' method gives the critical micellar concentration values of TBP in case of H 2 O or HNO 3 extractions (H 2 O: 0.48 M; HNO 3 2M: 0.65 M; at 21 deg C). Furthermore, the measures at different acid concentrations show that the c.m.c. varies with the acidity. The more acid the aqueous phase is, the smaller is the entropy in the system because of the numerous negative charges, i.e. the harder the micellization occurs, so the higher the c.m.c. value is. The sticky sphere model proposed by Baxter, can be used to model successfully small reverse micelles of the organic TBP phases. The aggregation number would be 4±1 (water extraction) and 5±1(HNO 3 2M extraction). These values are also given by vapor pressure measurements. (authors)

Problem of air pollution

Energy Technology Data Exchange (ETDEWEB)

Berge, H

1964-01-01

The effects of air pollutants on plants are dependent on and modified by climatic, orographic, edaphic, and biotic factors; the synergism of pollutants; and differences in the sensitivity of individual plants and species. Sulfur dioxide and fluorine are the most dangerous pollutants for plants, but ammonia, hydrogen sulfide, nitrogen oxides, nitric acid, chlorine, hydrochloric acid, bromine, iodine, hydrocyanic acid, ethylene, carbon monoxide, hydrocarbons, mercaptans, asphalt and tar vapors, mercury, and selenium can also inflict damage. Young leaves, sensitive to H/sub 2/S, nitrogen oxides, Cl, HCl, HCN, mercaptans, Hg, and sulfuric acid, are more resistant to SO/sub 2/, gaseous F compounds, ethylene, and selenium than older leaves. Damage is most serious when pollutants enter leaves simultaneously or alternately through epidermis and stomata. The yellow-to-brown coloration of leaves is usually a result of the precipitation of tanning. Plasmolysis is caused by SO/sub 2/, gaseous F compounds, ammonia, nitrogen oxides, HNO/sub 3/, Br, asphalt and tar vapors, while photosynthesis is stimulated by traces of ammonia, HNO/sub 3/, and saturated hydrocarbons. Increased transpiration due to SO/sub 2/ and HCl and elevated permeability and osmosis due to SO/sub 2/ were observed. 9 references, 12 figures, 1 table.

Features of molybdenum disulfide interaction with nitric acid

International Nuclear Information System (INIS)

Chursanov, Yu.V.; Potashnikov, Yu.M.; Rumyantsev, V.K.

1987-01-01

Experiments on studying composition of products of molybdenite concentrate (MoS 2 ) oxidation by HNO 3 solutions were conducted. Molybdenite oxidation was conducted in a glass temperature controlled vessel in absence of oxygen. It was shown that nitrogen (2) oxide represented the final product of molybdenite interaction with nitric acid. The process was accompanied as well by separation of NO 2 and HNO 2 under dynamic conditions, and nitrogen (4) oxide acted as catalyst of oxidation at that

A contribution to the study of the extraction of mineral acids and of actinide (IV) and (VI) cations by N,N-dialkylamides; Contribution a l'etude de l'extraction d'acides mineraux et de cations actinides aux degres d'oxydation (IV) et (VI) par des N,N-dialkylamides

Energy Technology Data Exchange (ETDEWEB)

Condamines, N

1990-03-15

N,N-dialkylamides are alternate extractants to tributylphosphate, TBP, for the actinides separation in nuclear fuel reprocessing. N,N-di (2-ethyl hexyl) butyramide and N,N-di (2 ethyl hexyl) isobutyramide are selected for their sufficient extraction and partition ability towards actinides (IV) and (VI) without coextracting fission products. Mechanisms of HNO{sub 3}, UO{sub 2}{sup 2+}, Pu{sup 4+}, Th{sup 4+} are investigated. Nitric acid extraction is due to the competitive formation of the species (HNO{sub 3})L{sub 2}, (HNO{sub 3})L, (HNO{sub 3}){sub 2}L (L: DOBA or DOiBA). An hydrogen bond is the driving force of the transfer. For low acidity media, amides are neutral extractants. Physical interactions, between free ligand and metallic complex, arise for high amide concentrations. Taking into account the non-ideality of the organic medium by a hard spheres mixture model, we estimate that such interactions are far from negligible and very specific to the amide group. Unlike TBP, when increasing acidity, amides behave as anionic extractants. DOBA and DOiBA appear to be satisfactory extractants for fuel reprocessing.

Determination of the distribution coefficient of 46 elements on tin dioxide in 0.1N HNO3-acetone media

International Nuclear Information System (INIS)

Jaffrezic-Renault, N.

1977-01-01

The use of radioactive indicators for the determination of the distribution coefficients of 46 elements on SnO 2 in 0.1N HNO 3 -acetone media is described. The determination has been carried out in static conditions: labelled element solution has been agitated with SnO 2 for two hours; the elements have been labelled with radioisotopes generally obtained by (n, γ) reaction, by irradiating a part of the used salt in EL 3 or OSIRIS reactor in the C.E.N. Saclay (France). Results show that the elements may be classified into several groups, according to their oxidation state. (T.I.)

Study of oxalic acid effect on equilibrium and kinetics of isotopic exchange between penta- and hexavalent neptunium in nitric acid solutions

International Nuclear Information System (INIS)

Nikitenko, S.I.; Ionnikova, N.I.

1989-01-01

Spectrophotometry at 25 deg C and ionic force μ=1.0 mol/l (KNO 3 +HNO 3 ) was used to show that at HNO 3 concentration 0.1-1.0 mol/l H 2 C 2 O 4 introduction to nitric acid solutions of Np 5+ in the presence of nitrite-ion resulted in the shift of equilibrium between Np 5+ and Np 6+ to the side of Np 6+ accumulation. The presence of H 2 C 2 O 4 at HNO 3 concentration > 1.0 mol/l doesn't affect the equilibrium position. The values of nominal equilibrium constant at different HNO 3 and H 2 C 2 O 4 concentrations were calculated. It was found that isotope exchange ( 239 Np/ 237 Np) between Np 5+ and Np 6+ in oxalate solutions proceeded more slowly than in oxalate absence. Rate constants of isotope exchange calculated at 9 deg C, μ=1.0 mol/l (KNO 3 ), H 2 C 2 O 4 concentration 0.01 mol/l and pH=2.2 and 3.5 are equal to 0.49x10 3 and 0.67x10 2 l/mol·min respectively. Mechanism of isotope exchange including electron transport between Np 5+ and Np 6+ oxalate complexes is suggested

Materials development for thermochemical cycles: sulfuric acid vaporizer. Semiannual technical report, October 1, 1977--March 31, 1978

International Nuclear Information System (INIS)

Krikorian, O.H.

1978-01-01

Installation of a sulfuric acid corrosion test facility has been completed and is described. The facility is to be used for testing of potential materials for containment and heat exchange of a sulfuric acid vaporizer at temperatures up to 725 0 K and boiling pressures of >20 atm (2 MPa). Materials that are ready for test are Duriron, Durichlor 51, single crystal Si, hot-pressed Si 3 N 4 (Noralide NC-132), and hot-pressed SiC (Crystar HD-435), and tests are expected to get underway in April pending Hazards Control approval

Thermal hazard assessment of TMCH mixed with inorganic acids

Directory of Open Access Journals (Sweden)

Yeh Chi-Tang

2018-01-01

Full Text Available 1,1-Bis(tert-butylperoxy-3,3,5-trimethylcyclohexane (TMCH is a typical peroxide with two peroxy groups that may runaway and/or explode due to mixing with inorganic acids, such as HCl, HNO3, H2SO4, or H3PO4. In this study, reactivities of TMCH mixed with the above inorganic acids were assessed by differential scanning calorimetry (DSC. Furthermore, data obtained by DSC, such as exothermic onset temperature (T0, maximum temperature (Tmax, and heat of decomposition (ΔHd could be employed to acquire thermal safety parameters. Moreover, thermal activity monitor III (TAM III was employed to investigate the thermal hazards while storing or transporting TMCH and TMCH mixed with four types of commonly used inorganic acids, here as HCl, HNO3, H2SO4, or H3PO4 under isothermal conditions. Mixing TMCH with those inorganic acids resulted in higherΔHd except H3PO4, and mixing TMCH with HCl clearly decreased T0. Therefore, the phenomena of mixing those incompatible materials with TMCH can be concluded as the worst cases in terms of contamination hazards during storage and transportation of TMCH.

Anion exchange separation of the light lanthanoids with nitric acid-methyl alcohol mixed media at elevated temperature

International Nuclear Information System (INIS)

Usuda, S.; Magara, M.

1987-01-01

Anion exchange chromatography with nitric acid-methyl alcohol mixed media at elevated temperature was applied to mutual separation of the light lanthanoids, La, Ce, Pr, Nd and Pm. The individual elements could be effectively separated from each other, main fission products and actinoids with 0.01M HNO 3 -90% CH 3 OH or 0.5M HNO 3 -80% CH 3 OH eluent at 90 deg C. (author) 14 refs.; 3 tables

New mechanism for autocatalytic decomposition of H2CO3 in the vapor phase.

Science.gov (United States)

Ghoshal, Sourav; Hazra, Montu K

2014-04-03

In this article, we present high level ab initio calculations investigating the energetics of a new autocatalytic decomposition mechanism for carbonic acid (H2CO3) in the vapor phase. The calculation have been performed at the MP2 level of theory in conjunction with aug-cc-pVDZ, aug-cc-pVTZ, and 6-311++G(3df,3pd) basis sets as well as at the CCSD(T)/aug-cc-pVTZ level. The present study suggests that this new decomposition mechanism is effectively a near-barrierless process at room temperature and makes vapor phase of H2CO3 unstable even in the absence of water molecules. Our calculation at the MP2/aug-cc-pVTZ level predicts that the effective barrier, defined as the difference between the zero-point vibrational energy (ZPE) corrected energy of the transition state and the total energy of the isolated starting reactants in terms of bimolecular encounters, is nearly zero for the autocatalytic decomposition mechanism. The results at the CCSD(T)/aug-cc-pVTZ level of calculations suggest that the effective barrier, as defined above, is sensitive to some extent to the levels of calculations used, nevertheless, we find that the effective barrier height predicted at the CCSD(T)/aug-cc-pVTZ level is very small or in other words the autocatalytic decomposition mechanism presented in this work is a near-barrierless process as mentioned above. Thus, we suggest that this new autocatalytic decomposition mechanism has to be considered as the primary mechanism for the decomposition of carbonic acid, especially at its source, where the vapor phase concentration of H2CO3 molecules reaches its highest levels.

Basic and Acidic Leaching of Sludge from Melton Valley Storage Tank W-25

Energy Technology Data Exchange (ETDEWEB)

Collins, J.L., Egan, B.Z., Beahm, E.C., Chase, C.W., Anderson, K.K.

1997-10-01

Bench-scale leaching tests were conducted with samples of tank waste sludge from the Melton Valley Storage Tank (MVST) Facility at Oak Ridge National Laboratory (ORNL) to evaluate separation technology processes for use in concentrating the radionuclides and reducing the volume of waste for final disposal. This paper discusses the hot cell apparatus, the characterization of the sludge, the leaching methodology, and the results obtained from a variety of basic and acidic leaching tests of samples of sludge at ambient temperature. Basic leaching tests were also conducted at 75 and 95 deg C. The major alpha-,gamma., and beta-emitting radionuclides in the centrifuged, wet sludge solids were {sup 137}Cs, {sup 60}Co, {sup 154}Eu, {sup 241}Am, {sup 244}Cm {sup 90}Sr, Pu, U, and Th. The other major metals (in addition to the U and Th) and anions were Na, Ca, Al, K, Mg, NO{sub 3}{sup -},CO{sub 3}{sup 2-}, OH{sup -}, and O{sup 2-} organic carbon content was 3.0 +/- 1.0%. The pH was 13. A surprising result was that about 93% of the {sup 137}Cs in the centrifuged, wet sludge solids was bound in the solids and could not be solubilized by basic leaching at ambient temperature and 75 deg C. However, the solubility of the {sup 137}Cs was enhanced by heating the sludge to 95 deg C. In one of the tests,about 42% of the {sup 137}Cs was removed by leaching with 6.3 M NaOH at 95 deg C.Removing {sup 137}Cs from the W-25 sludge with nitric acid was a slow process. About 13% of the {sup 137}Cs was removed in 16 h with 3.0 M HNO{sub 3}. Only 22% of the {sup 137}Cs was removed in 117 h usi 6.0 M HNO{sub 3}. Successive leaching of sludge solids with 0.5 M, 3.0 M, 3.0 M; and 6.0 M HNO{sub 3} for a total mixing time of 558 h removed 84% of the {sup 137}Cs. The use of caustic leaching prior to HNO{sub 3} leaching, and the use of HF with HNO{sub 3} in acidic leaching, increased the rate of {sup 137}Cs dissolution. Gel formation proved to be one of the biggest problems associated with HNO{sub 3

Basic and Acidic Leaching of Sludge from Melton Valley Storage Tank W-25

International Nuclear Information System (INIS)

Collins, J.L.; Egan, B.Z.; Beahm, E.C.; Chase, C.W.; Anderson, K.K.

1997-10-01

Bench-scale leaching tests were conducted with samples of tank waste sludge from the Melton Valley Storage Tank (MVST) Facility at Oak Ridge National Laboratory (ORNL) to evaluate separation technology processes for use in concentrating the radionuclides and reducing the volume of waste for final disposal. This paper discusses the hot cell apparatus, the characterization of the sludge, the leaching methodology, and the results obtained from a variety of basic and acidic leaching tests of samples of sludge at ambient temperature. Basic leaching tests were also conducted at 75 and 95 deg C. The major alpha-,gamma., and beta-emitting radionuclides in the centrifuged, wet sludge solids were 137 Cs, 60 Co, 154 Eu, 241 Am, 244 Cm 90 Sr, Pu, U, and Th. The other major metals (in addition to the U and Th) and anions were Na, Ca, Al, K, Mg, NO 3 - ,CO 3 2- , OH - , and O 2- organic carbon content was 3.0 +/- 1.0%. The pH was 13. A surprising result was that about 93% of the 137 Cs in the centrifuged, wet sludge solids was bound in the solids and could not be solubilized by basic leaching at ambient temperature and 75 deg C. However, the solubility of the 137 Cs was enhanced by heating the sludge to 95 deg C. In one of the tests,about 42% of the 137 Cs was removed by leaching with 6.3 M NaOH at 95 deg C.Removing 137 Cs from the W-25 sludge with nitric acid was a slow process. About 13% of the 137 Cs was removed in 16 h with 3.0 M HNO 3 . Only 22% of the 137 Cs was removed in 117 h usi 6.0 M HNO 3 . Successive leaching of sludge solids with 0.5 M, 3.0 M, 3.0 M; and 6.0 M HNO 3 for a total mixing time of 558 h removed 84% of the 137 Cs. The use of caustic leaching prior to HNO 3 leaching, and the use of HF with HNO 3 in acidic leaching, increased the rate of 137 Cs dissolution. Gel formation proved to be one of the biggest problems associated with HNO 3 leaching of the W-25 sludge

Experimental determination of the (vapor + liquid) equilibrium data of binary mixtures of fatty acids by differential scanning calorimetry

International Nuclear Information System (INIS)

Matricarde Falleiro, Rafael M.; Meirelles, Antonio J.A.; Kraehenbuehl, Maria A.

2010-01-01

(Vapor + liquid) equilibrium (VLE) data for three binary mixtures of saturated fatty acids were obtained by differential scanning calorimetry (DSC). However, changes in the calorimeter pressure cell and the use of hermetic pans with holes (φ = 250 mm) in the lids were necessary to make it possible to apply this analytical technique, obtaining accurate results with smaller samples and shorter operational times. The systems evaluated in this study were: myristic acid (C 14:0 ) + palmitic acid (C 16:0 ), myristic acid (C 14:0 ) + stearic acid (C 18:0 ), and palmitic acid (C 16:0 ) + stearic acid (C 18:0 ), all measured at 50 mm Hg and with mole fractions between 0.0 and 1.0 in relation to the most volatile component of each diagram. The fugacity coefficients for the components in the vapor phase were calculated using the Hayden and O'Connell method [J.G. Hayden, J.P. O'Connell, Ind. Eng. Chem. Process Design Develop. 14 (3) (1975) 209-216] and the activity coefficients for the liquid phase were correlated with the traditional g E models (NRTL [H. Renon, J.M. Prausnitz, Aiche J. 14 (1968) 135-144], UNIQUAC [D.S. Abrams, J.M. Prausnitz, Aiche J. 21 (1975) 116-128], and Wilson [J.M. Prausnitz, N.L. Linchtenthaler, E.G. Azevedo, Molecular Thermodynamics of Fluid-phase Equilibria, River-Prentice Hall, Upper Saddle, 1999]). The sets of parameters were then compared in order to determine which adjustments best represented the VLE.

Correlation of vapor - liquid equilibrium data for acetic acid - isopropanol - water - isopropyl acetate mixtures

Directory of Open Access Journals (Sweden)

B. A. Mandagarán

2006-03-01

Full Text Available A correlation procedure for the prediction of vapor - liquid equilibrium of acetic acid - isopropanol - water - isopropyl acetate mixtures has been developed. It is based on the NRTL model for predicting liquid activity coefficients, and on the Hayden-O'Connell second virial coefficients for predicting the vapor phase of systems containing association components. When compared with experimental data the correlation shows a good agreement for binary and ternary data. The correlation also shows good prediction for reactive quaternary data.

A theoretical investigation of gaseous absorption by water droplets from SO2-HNO3-NH3-CO2-HCl mixtures

Science.gov (United States)

Adewuyi, Y. G.; Carmichael, G. R.

1982-01-01

A physical-chemical model is developed and used to investigate gaseous absorption by water droplets from trace gas mixtures. The model is an extension of that of Carmichael and Peters (1979) and includes the simultaneous absorption of SO2, NH3, HNO3, CO2, and HCl. Gas phase depletion is also considered. Presented results demonstrate that the absorption behavior of raindrops is strongly dependent on drop size, fall distance, trace gas concentrations, and the chemical and physical properties of the constituents of the mixture. In addition, when gas phase depletion is considered, the absorption rates and equilibrium values are also dependent on the precipitation rate itself. Also, the trace constituents liquid phase concentrations may be a factor of six or more lower when gas depletion is considered then when the depletion is ignored. However, the hydrogen ion concentration may be insensitive to the gas phase depletion.

Characterisation of aggregation of tributylphosphate molecules in organic solvent; Caracterisation de l'auto-organisation du phosphate de tributyle en solvant organique

Energy Technology Data Exchange (ETDEWEB)

Mandin, C.; Martinet, L.; Zemb, Th.; Berthon, L.; Madic, Ch

2000-07-01

This report presents a structural study of the aggregates formed with the organic phases of the extractant tri-n-butyl phosphate, used in the industrial PUREX process (Plutonium and Uranium Extraction; liquid-liquid solvent extraction) for the treatment of high radioactive waste. Combined Small Angle X-ray Scattering and Small Angle Neutron Scattering show that organic TBP solutions (in equilibrium with acid solutions) are organised in oligomeric aggregates. The influence of various parameters such as HNO{sub 3} or TBP concentrations, diluent or acid natures, does not seem to modify the aggregate shape and size, whereas the interactions are modified. Moreover the aggregates disappear under high temperatures, whereas the attractive interactions between them increase at low temperatures. The 'drop weight' method gives the critical micellar concentration values of TBP in case of H{sub 2}O or HNO{sub 3} extractions (H{sub 2}O: 0.48 M; HNO{sub 3} 2M: 0.65 M; at 21 deg C). Furthermore, the measures at different acid concentrations show that the c.m.c. varies with the acidity. The more acid the aqueous phase is, the smaller is the entropy in the system because of the numerous negative charges, i.e. the harder the micellization occurs, so the higher the c.m.c. value is. The sticky sphere model proposed by Baxter, can be used to model successfully small reverse micelles of the organic TBP phases. The aggregation number would be 4{+-}1 (water extraction) and 5{+-}1(HNO{sub 3}2M extraction). These values are also given by vapor pressure measurements. (authors)

Comparisons between ground-based FTIR and MIPAS N2O and HNO3 profiles before and after assimilation in BASCOE

Directory of Open Access Journals (Sweden)

C. Vigouroux

2007-01-01

Full Text Available Within the framework of the Network for Detection of Atmospheric Composition Change (NDACC, regular ground-based Fourier transform infrared (FTIR measurements of many species are performed at several locations. Inversion schemes provide vertical profile information and characterization of the retrieved products which are therefore relevant for contributing to the validation of MIPAS profiles in the stratosphere and upper troposphere. We have focused on the species HNO3 and N2O at 5 NDACC-sites distributed in both hemispheres, i.e., Jungfraujoch (46.5° N and Kiruna (68° N for the northern hemisphere, and Wollongong (34° S, Lauder (45° S and Arrival Heights (78° S for the southern hemisphere. These ground-based data have been compared with MIPAS offline profiles (v4.61 for the year 2003, collocated within 1000 km around the stations, in the lower to middle stratosphere. To get around the spatial collocation problem, comparisons have also been made between the same ground-based FTIR data and the corresponding profiles resulting from the stratospheric 4D-VAR data assimilation system BASCOE constrained by MIPAS data. This paper discusses the results of the comparisons and the usefullness of using BASCOE profiles as proxies for MIPAS data. It shows good agreement between MIPAS and FTIR N2O partial columns: the biases are below 5% for all the stations and the standard deviations are below 7% for the three mid-latitude stations, and below 10% for the high latitude ones. The comparisons with BASCOE partial columns give standard deviations below 4% for the mid-latitude stations to less than 8% for the high latitude ones. After making some corrections to take into account the known bias due to the use of different spectroscopic parameters, the comparisons of HNO3 partial columns show biases below 3% and standard deviations below 15% for all the stations except Arrival Heights (bias of 5%, standard deviation of 21%. The results for this species, which

Radiolysis of concentrated nitric acid solutions

International Nuclear Information System (INIS)

Nagaishi, R.; Jiang, P.Y.; Katsumura, Y.; Domae, M.; Ishigure, K.

1995-01-01

A study on electron pulse- and 60 Co γ-radiolysis of concentrated nitric acid and nitrate solutions has been carried out to elucidate the radiation induced reactions taking place in the solutions. Dissociation into NO 2 - and O( 3 P) was proposed as a direct action of the radiation on nitrate and gave the G-values were dependent on the chemical forms of nitrate: g s2 (-NO 3 - )=1.6 and g s2 (-HNO 3 )=2.2 (molecules/100eV). Based on the experimental yields of HNO 2 and reduced Ce IV , the primary yields of radiolysis products of water, g w , were evaluated to clarify the effects of nitrate on spur reactions of water in various nitrate solutions. (author)

HIGH PRESSURE VAPOR-LIQUID EQUILIBRIA OF PALM FATTY ACIDS DISTILLATES-CARBON DIOXIDE SYSTEM

Directory of Open Access Journals (Sweden)

Nélio T. MACHADO

1997-12-01

Full Text Available Vapor-Liquid equilibria of palm fatty acids distillates/carbon dioxide system has been investigated experimentally at temperatures of 333, 353, and 373 K and pressures of 20, 23, 26, and 29 MPa using the static method. Experimental data for the quasi-binary system palm fatty acids distillates/carbon dioxide has been correlated with Redlich-Kwong-Aspen equation of state. Modeling shows good agreement with experimental data. Selectivity obtained indicates that supercritical carbon dioxide is a reasonable solvent for separating saturated (palmitic acid and unsaturated (oleic+linoleic acids fatty acids from palm fatty acids distillates in a continuous multistage countercurrent column.Foi investigado experimentalmente o equilíbrio líquido-vapor para o sistema Destilado Ácido de Óleo de Palma (PFAD/Dióxido de Carbono, nas temperaturas de 333, 353 e 373 K e pressões de 20, 23, 26 e 29 MPa, usando-se o método estático. Os dados experimentais do sistema pseudo-binário PFAD/CO2 foram correlacionados com a equação de estado de Redlich-Kwong do pacote computacional ASPEN. O modelo reproduz bem os resultados experimentais. A seletividade obtida indica que o CO2 supercrítico é um solvente razoável para a separação em coluna multi-estágio e contínua, do ácido graxo saturado (ácido palmítico daqueles insaturados (ácido oleico e ácido linoleico contidos no PFAD.

Densities and apparent molar volumes for aqueous solutions of HNO3-UO2(NO3)2 at 298.15 K

International Nuclear Information System (INIS)

Yang-Xin Yu; Tie-Zhu Bao; Guang-Hua Gao; Yi-Gui Li

1999-01-01

In order to obtain the exact information of atomic number density in the ternary system of HNO 3 -UO 2 (NO 3 ) 2 -H 2 O, the densities were measured with an Anton-Paar DMA60/602 digital density meter thermostated at 298.15±0.01 K. The apparent molal volumes for the systems were calculated from the experimental data. The present measured apparent molar volumes have been fitted to the Pitzer ion-interaction model, which provides an adequate representation of the experimental data for mixed aqueous electrolyte solutions up to 6.2 mol/kg ionic strength. This fit yields θ V , and Ψ V , which are the first derivatives with respect to pressure of the mixing interaction parameters for the excess free energy. With the mixing parameters θ V , and ψ V , the densities and apparent molar volumes of the ternary system studied in this work can be calculated with good accuracy, as shown by the standard deviations. (author)

Improvement of Oil-Vapor Treatment Facility for Wolsong Unit 3,4

International Nuclear Information System (INIS)

Kim, Jeong Guk; Kwon, S. W.; Lee, H. S.

2009-11-01

With the purpose to minimize an oil-vapor discharge to the atmosphere and to be an environmentally friendly nuclear power plant by an improvement of mist eliminator for turbine lubricant system at Wolsong Nuclear Power Plant Unit 3,4, this project - project name : Improvement of Oil-vapor Treatment Facility for Wolsong Unit 3,4 - was conducted for six months (from Apr. 15, 2009 to Oct. 14, 2009). This Project contains Oil-vapor Source and Environmental Regulation, Analysis on the Present Oil-vapor Treatment Facility, Improvement of Oil-vapor Treatment Facility, Test Facility Design, Fabrication, Installation, Test Operation, Evaluation of the Facility

Comparison of hydrogen isotope exchange reactions between HTO vapor and the sodium salts of o-, m-, and p-aminobenzoic acid

International Nuclear Information System (INIS)

Okada, Minoru; Imaizumi, Hiroshi; Itoh, Tomoko

1991-01-01

Hydrogen isotope exchange reaction between HTO vapor and one of the sodium salts of o-, m-, and p-aminobenzoic acid (solid) was observed at 50 ∼ 80 degC. The acidity (acidity based on kinetic logic) for the materials at each temperature has been obtained with the A''-McKay plots based on the respective data obtained. The followings have been clarified by comparing these acidities (and the acidities obtained previously). 1) The acidity of aromatic amines can be expressed in terms of the acidity based on kinetic logic. 2) The reactivity of aromatic amine is strongly affected by both I-effect and R-effect. 3) It can be deduced that aromatic amines are more reactive than aliphatic amines. (author)

Thermochemical study of 2,4-, 2,6- and 3,4-dihydroxybenzoic acids in the liquid phase using a TG apparatus

International Nuclear Information System (INIS)

Vecchio, Stefano; Brunetti, Bruno

2011-01-01

Research highlights: → Vapor pressures of solid and liquid 2,4- 2,6- and 3,4-dihydroxybenzoic acids, that don't decompose appreciably in the temperature range considered, were determined by torsion-effusion technique and thermogravimetry, respectively. → Agreement between the experimental sublimation vapor pressures and literature data recently published is good for all the three isomers. → From the temperature dependence of vapor pressure the molar enthalpies of sublimation and vaporization were determined at the middle of the respective experimental temperature intervals. → For validation of TG pressure data, the TG vapor pressures of solid ferrocene and 1,2-dihydroxybenzoic acid were successfully compared with the corresponding literature values. → The following increasing-order of volatility can be established: 2,6-dihydroxybenzoic acid l g H m o ( ) were determined, respectively, at the middle of the respective temperature intervals. The melting temperatures and the molar enthalpies of fusion of these compounds were measured by d.s.c. The vapor pressures of these compounds in the solid state, measured by torsion-effusion technique, were compared with recently published data, while the corresponding molar sublimation enthalpies were determined. In order to validate the vapor pressure results determined by TG, the experimental vapor pressure data regarding solid ferrocene and 1,2-dihydroxybenzoic acid were successfully compared with literature values in the range 20-200 Pa. In addition, the experimental molar enthalpies of fusion were compared with those calculated by subtracting the molar vaporization enthalpies to the sublimation ones, both adjusted to their respective melting temperatures. Finally, the standard (p o = 0.1 MPa) molar enthalpies, entropies and Gibbs energies of sublimation, corrected at the reference temperature of 298.15 K, have been calculated using the estimated heat capacity differences between gas and liquid for vaporization

X-ray studies of the liquid/vapor interface: Water and polymer and fatty acid monolayers on water

International Nuclear Information System (INIS)

Schlossman, M.L.; Schwartz, D.K.; Kawamoto, E.H.; Kellogg, G.J.; Pershan, P.S.; Ocko, B.M.; Kim, M.W.; Chung, T.C.

1989-01-01

X-ray specular reflectivity is used to study the liquid-vapor interface of pure water and of fatty acid and polymer monolayers at that interface. For the pure water surface the reflectivity was measured for three different spectrometer resolutions and simultaneous fits with only one free parameter to all of the data are in excellent agreement with the prediction of capillary wave theory for the RMS surface roughness. Diffuse scattering away from the specular condition, at wavevectors corresponding to those of the capillary waves, yields intensities and line shapes in agreement with theory with no significant adjustable parameters. Reflectivity from separate monolayers of co-poly 1, 2-butadiene/butyl alcohol (50% random substitution) and lignoceric acid (CH 3 (CH 2 ) 22 COOH) at the water/vapor interface are interpreted to obtain profiles of the average electron density ρ(z) as a function of distance z along the surface normal. For the polymer monolayer we find the following: (1) a local maximum in the electron density approximately 10% larger than that of the bulk polymer and (2) the RMS roughness of the vapor/polymer interface agrees with capillary wave theory predictions for the lower surface pressures. For the highest surface pressure the RMS roughness exceeds the value predicted by the capillary wave model. Measurements of reflectivity from a lignoceric acid monolayer, as a function of surface pressure throughout an isotherm (near room temperature), reveal the following behavior: (1) the overall thickness of the monolayer increases with increasing pressure and (2) the head groups occupy a progressively larger region along the surface normal as the pressure increases, indicating that they rearrange normal to the interface. 15 refs., 5 figs., 2 tabs

The removal of nitric acid to atmospheric particles during a wintertime field study

Science.gov (United States)

Dasch, Jean Muhlbaier; Cadle, Steven H.

A field was conducted in Warren, MI, during the 1987/88 winter period to examined the reaction of HNO 3 with particulate salt from road deicing. Samples of gases and particles were collected on a daily basis over a 4-month period. If HNO 3 reacts with particulate salt, particles of sodium nitrate will be formed and gaseous hydrochloric acid will be released. Thus, during the periods of high salt concentrations, one would expect increases in HCl and particulate NO 3- and a decrease in HNO 3. The effect was observed, although the total amount of NaNO 3 formed was not large. The increase in particulate NO 3- did not appear in the large particle mode. Although more than 40% of the salt was present as very large particles (> 8 μm), most of the surface area was associated with small particles. Since the reaction occurred at the particle surface, the NO 3- appeared in the small particle mode. Large-particle nitrate has been observed in association with sea salt and crustal particles and has also been attributed to reactions with HNO 3. These cases will be reconsidered based on the road salt results.

XPS and STEM studies of Allende acid insoluble residues

Science.gov (United States)

Housley, R. M.; Clarke, D. R.

1980-01-01

Data on Allende acid residues obtained both before and after etching with hot HNO3 are presented. X-ray photoelectron spectra show predominantly carbonaceous material plus Fe-deficient chromite in both cases. The HNO3 oxidizes the carbonaceous material to some extent. The small chromites in these residues have a wide range of compositions somewhat paralleling those observed in larger Allende chromites and in Murchison chromites, especially in the high Al contents; however, they are deficient in divalent cations, which makes them metastable and indicates that they must have formed at relatively low temperatures. It is suggested that they formed by precipitation of Cr(3+) and Fe(3+) from olivine at low temperature or during rapid cooling.

Flame Atmospheric Pressure Chemical Ionization Coupled with Negative Electrospray Ionization Mass Spectrometry for Ion Molecule Reactions.

Science.gov (United States)

Cheng, Sy-Chyi; Bhat, Suhail Muzaffar; Shiea, Jentaie

2017-07-01

Flame atmospheric pressure chemical ionization (FAPCI) combined with negative electrospray ionization (ESI) mass spectrometry was developed to detect the ion/molecule reactions (IMRs) products between nitric acid (HNO 3 ) and negatively charged amino acid, angiotensin I (AI) and angiotensin II (AII), and insulin ions. Nitrate and HNO 3 -nitrate ions were detected in the oxyacetylene flame, suggesting that a large quantity of nitric acid (HNO 3 ) was produced in the flame. The HNO 3 and negatively charged analyte ions produced by a negative ESI source were delivered into each arm of a Y-shaped stainless steel tube where they merged and reacted. The products were subsequently characterized with an ion trap mass analyzer attached to the exit of the Y-tube. HNO 3 showed the strongest affinity to histidine and formed (M histidine -H+HNO 3 ) - complex ions, whereas some amino acids did not react with HNO 3 at all. Reactions between HNO 3 and histidine residues in AI and AII resulted in the formation of dominant [M AI -H+(HNO 3 )] - and [M AII -H+(HNO 3 )] - ions. Results from analyses of AAs and insulin indicated that HNO 3 could not only react with basic amino acid residues, but also with disulfide bonds to form [M-3H+(HNO 3 ) n ] 3- complex ions. This approach is useful for obtaining information about the number of basic amino acid residues and disulfide bonds in peptides and proteins. Graphical Abstract ᅟ.

Formation and electrical characteristics of silicon dioxide layers by use of nitric acid oxidation method

International Nuclear Information System (INIS)

Imal, S.; Takahashi, M.; Matsuba, K.; Asuha; Ishikawa, Y.; Kobayashi, Hikaru

2005-01-01

SiO 2 /Si structure can be formed at low temperatures by use of nitric acid (HNO 3 ) oxidation of Si (NAOS) method. When Si wafers are immersed in ∼ 40 wt% HNO 3 solutions at 108 deg C, ∼ 1 nm SiO 2 layers are formed. The subsequent immersion in 68 wt% HNO 3 (i.e., azeotropic mixture of HNO 3 with water) at 121 deg C increases the SiO 2 thickness. The 3,5 nm-thick SiO 2 layers produced by this two-step NAOS method possess a considerably low leakage current density (e.g. 1 x 10 2 A/cmi 2 at the forward gate bias, V G , of 1.5 V), in spite of the low temperature oxidation, and further decreased (e.g., 8 x 10 4 A/cm 2 at V G = 1.5 V) by post-metallization annealing at 250 deg C in hydrogen atmosphere. In order to increase the SiO 2 thickness, a bias voltage is applied during the NAOS method. When 10 V is applied to Si with respect to a Pt counter electrode both immersed in 1 M HNO 3 solutions at 25 deg C, SiO 2 layers with 8 nm thickness can be formed for 1 h(Authors)

The distribution of Th(NO3)4, UO2(NO3)2 and HNO3 between an aqueous phase and an organic tributyl phosphate phase

International Nuclear Information System (INIS)

Nakashima, T.; Zimmer, E.

1984-05-01

The distribution of Th(NO 3 ) 4 , UO 2 (NO 3 ) 2 and HNO 3 between an aqueous phase and an organic phase, consisting of 30 Vol.% tributyl phosphate in dodecane, has been experimentally investigated. About 120 distribution data have been determined in the concentration ranges that can be seen in the THOREX process for reprocessing spent thorium bearing fuel. Based on the experimental data, two computer programs have been developed which make possible interpolations and, to some extent, extrapolations. With model 1, concentrations in the organic phase can be calculated if that in the aqueous phase are known. With model 2, concentrations in the aqueous phase can be calculated vice versa. Besides the description of the calculation models, a large body of calculated data can be found in this report. In a addition, a calculation mode is presented that makes possible the calculation of distribution data for very low thorium concentrations. (orig.) [de

Cation exchange of 53 elements in nitric acid

International Nuclear Information System (INIS)

Marsh, S.F.; Alarid, J.E.; Hamond, C.F.; McLeod, M.J.; Roensch, F.R.; Rein, J.E.

1978-02-01

Cation-exchange distribution data are presented for 53 elements from 3 to 12M HNO 3 for three strong-acid resins, having cross-linkages of 8%, 4%, and macroporous. Data obtained by 16- to 18-h dynamic batch contacts are compared to cation-exchange distribution data from strong HCl and HClO 4

Structure of a microbial community in soil after prolonged addition of low levels of simulated acid rain

Science.gov (United States)

Pennanen; Fritze; Vanhala; Kiikkila; Neuvonen; Baath

1998-06-01

Humus samples were collected 12 growing seasons after the start of a simulated acid rain experiment situated in the subarctic environment. The acid rain was simulated with H2SO4, a combination of H2SO4 and HNO3, and HNO3 at two levels of moderate acidic loads close to the natural anthropogenic pollution levels of southern Scandinavia. The higher levels of acid applications resulted in acidification, as defined by humus chemistry. The concentrations of base cations decreased, while the concentrations of exchangeable H+, Al, and Fe increased. Humus pH decreased from 3.83 to 3.65. Basal respiration decreased with decreasing humus pH, and total microbial biomass, measured by substrate-induced respiration and total amount of phospholipid fatty acids (PLFA), decreased slightly. An altered PLFA pattern indicated a change in the microbial community structure at the higher levels of acid applications. In general, branched fatty acids, typical of gram-positive bacteria, increased in the acid plots. PLFA analysis performed on the bacterial community growing on agar plates also showed that the relative amount of PLFA specific for gram-positive bacteria increased due to the acidification. The changed bacterial community was adapted to the more acidic environment in the acid-treated plots, even though bacterial growth rates, estimated by thymidine and leucine incorporation, decreased with pH. Fungal activity (measured as acetate incorporation into ergosterol) was not affected. This result indicates that bacteria were more affected than fungi by the acidification. The capacity of the bacterial community to utilize 95 different carbon sources was variable and only showed weak correlations to pH. Differences in the toxicities of H2SO4 and HNO3 for the microbial community were not found.

Simultaneous desulfurization and denitrification of flue gas by ·OH radicals produced from O2+ and water vapor in a duct.

Science.gov (United States)

Bai, Mindi; Zhang, Zhitao; Bai, Mindong

2012-09-18

In the present study, simultaneous flue gas desulfurization and denitrification are achieved with ·OH radicals generated from O(2)(+) reacting with water vapor in a duct. The O(2)(+) ions are generated by a strong ionization dielectric barrier discharge and then injected into the duct. Compared with conventional gas discharge treatment, the present method does not need a plasma reaction reactor, additional catalysts, reductants, or oxidants. The main recovered products are the liquids H(2)SO(4) and HNO(3), which can be used in many processes. Removal rates of 97% for NO and 82% for SO(2) are obtained under the following optimal experimental conditions: molar ratio of reactive oxygen species (O(2)(+), O(3)) to SO(2) and NO, 5; inlet flue gas temperature, 65 °C; reaction time, 0.94 s; and H(2)O volume fraction, 8%. Production of O(2)(+) and the plasma reaction mechanisms are discussed, and the recovered acid is characterized. The experimental results show that the present method performs better for denitrification than for desulfurization. Compared with conventional air discharge flue gas treatments, the present method has lower initial investment and operating costs, and the equipment is more compact.

The effect of ultrasonic and HNO3 treatment of activated carbon from fruit stones on capacitive and pseudocapacitive energy storage in electrochemical supercapacitors.

Science.gov (United States)

Venhryn, B Ya; Stotsko, Z A; Grygorchak, I I; Bakhmatyuk, B P; Mudry, S I

2013-09-01

The effect of ultrasonic treatment and modification with nitric acid of activated carbon obtained from fruit stones, on the parameters of electric double-layer (EDL) as well as on farad-volt characteristics of its boundary with electrolyte 7.6 m KОН, 4 m KI and 2 m ZnI2 aqueous solutions has been studied by means of precision porometry, cyclic voltamperometry, electrochemical impedance spectroscopy and computer simulation methods. It is shown that HNO3 treatment results in an increase of the electrostatic capacitance up to 202 F/g in 7.6 m KОН-solution as well as pseudocapacitance up to 1250 F/g in 4 m KI. This increase is supposed to be related both with hydrophilicity and with an increase of the density of states on Fermi level. The ultrasonic treatment enables one to significantly increase (more than 200 times) the density of states on Fermi level which in turn causes both quantitative and qualitative changes in farad-volt dependences. A hybrid supercapacitor with specific capacitance of 1100 F/g and specific energy of 49 Wh/kg per active mass of two electrodes was developed. Copyright © 2013 Elsevier B.V. All rights reserved.

Concentrations of nitrous acid, nitric acid, nitrite and nitrate in the gas and aerosol phase at a site in the emission zone during ESCOMPTE 2001 experiment

Science.gov (United States)

Acker, K.; Möller, D.; Auel, R.; Wieprecht, W.; Kalaß, D.

2005-03-01

Ground-based measurements were performed at the "Expérience sur Site pour COntraindre les Modèles de Pollution atmosphérique et de Transport d`Emissions" (ESCOMPTE) field site E3 (Realtor) about 30 km north of the urban environment of Marseille and east of the industrial centre Berre pond to investigate the formation of nitrous and nitric acid and to detect the distribution of reactive N-species between the gas and particle phase during photochemical pollution events. A wet denuder sampling for gases followed by a steam jet collection for aerosols was both coupled to anion chromatographic analysis. The analytical system provided data continuously with 30-min time resolution between June 13 and July 13, 2001. Indications for heterogeneous formation of nitrous acid during nighttime and daytime on ground and aerosol surfaces were found, the average HNO 2/NO 2 ratio was 6%. Highest concentrations were observed during two episodes of strong pollution accumulation when sea breeze transported industrial, traffic and urban pollution land-inwards. After nocturnal heterogeneous formation (about 0.1 ppb v h -1 were estimated corresponding to increasing HNO 2/NO 2 ratios) and accumulation processes up to 1.2 ppb v HNO 2 were observed. Their photolysis produces up to 5-9×10 6 OH cm -3 s -1 and will contribute significantly to initiation of the daily photochemistry in the lowest part of the troposphere. For the key tropospheric species, HNO 3 daily peaks up to 4 ppb v were detected.

Extraction of indicator quantities of zirconium by di-n-cresylphosphoric acid

Energy Technology Data Exchange (ETDEWEB)

Fomin, V V; Potapova, S A

1976-01-01

The carrier-free extraction is studied of /sup 95/Zr from 1, 2, 5 and 9M HNO/sub 3/ with the solutions of d-n-cresyl-phosphoric acid (HA) in CHCl/sub 3/ concentrated from 1.25x10/sup -4/ to 5x10/sup -4/ M from the mixtures of HNO/sub 3/ and LiNO/sub 3/ NaNO/sub 3/, Ca(NO/sub 3/)/sub 2/ solutions and HClO/sub 4/ and NaClO/sub 4/ depending on the concentration of hydrogen ions at a constant concentration of HA in CHCl/sub 3/ equal to 2.5x10/sup -4/ M, and the concentration of NO/sub 3//sup -/ and ClO/sub 4//sup -/ ions equal to 5 g-ion/1. The results are presented in terms of bilogarithmic dependencies of the distribution coefficient (..cap alpha..) on the equilibrium concentration of the (HA)/sub 2/ - ions in the aqueous phase. It follows from the data obtained that the region 1-5 M HNO/sub 3/ is dominated by the hydrolyzed ions of Zr(OH)/sub 2//sup 2 +/, while the region 3-5 M HClO/sub 4/ - by Zr/sup 4 +/, and the compound to be extracted has the composition ZrA/sub 4/. In the extraction of /sup 95/Zr with a 2.5x10/sup -4/ M solution of HA from HNO/sub 3/ or HClO/sub 4/ only, ..cap alpha.. passes through a minimum at a concentration of 3.4 and 5.4 M, respectively. The extraction is studied of /sup 95/Zr with a 2.5x1g/sup -4/ M solution of HA from the mixtures of HNO/sub 3/ and HClO/sub 4/ with an aggregate concentration of 1 and 5 M, respectively. At a definite mixture composition corresponding to the 1.3 M HNO/sub 3/ and 3.7 M HClO/sub 4/, ..cap alpha.. passes through a maximum. The maximum value of ..cap alpha.. is 11 times that in the extraction from 5 M HClO/sub 4/ and 4.5 times that in the extraction from 5 M HNO/sub 3/.

Anion exchange purification of plutonium at lower acidities (Preprint No. CT-6)

International Nuclear Information System (INIS)

Kartha, P.K.S.; Ravi, S.; Achuthan, P.V.; Das, S.K.; Madhusudan, A.; Janardhanan, C.; Rao, K.S.; Ramanujam, A.; Dhumwad, R.K.

1988-02-01

During concentration and purification of plutonium by anion exchange, 7.2 M HNO 3 is used as loading acidity for absorbing Pu(IV). In this study, the feasibility of utilizing lower acidities like 5.2 and 6.2 M has been investigated. The results indicate that lower acidities can be used in this step if reduced resin capacities are acceptable. (author)

Microwave Acid Extraction to Analyze K and Mg Reserves in the Clay Fraction of Soils

Directory of Open Access Journals (Sweden)

Araína Hulmann Batista

Full Text Available ABSTRACT: Extraction of K and Mg with boiling 1 mol L-1 HNO3 in an open system for predicting K and Mg uptake by plants is a method of low reproducibility. The aim of this study was to compare the extraction capacity of different acid methods relative to hydrofluoric acid extraction for K and Mg. A further objective was to develop a chemical extraction method using a closed system (microwave for nonexchangeable and structural forms of these nutrients in order to replace the traditional method of extraction with boiling HNO3 on a hot plate (open system. The EPA 3051A method can be used to estimate the total content of K in the clay fraction of soils developed from carbonate and phyllite/mica schist rocks. In the clay fraction of soils developed from basalt, recoveries of K by the EPA 3051A (pseudo-total method were higher than for the EPA 3052 (total hydrofluoric extraction method. The relative abundance of K and Mg for soils in carbonate rocks, phyllite/mica schist, granite/gneiss, and basalt determined by aqua regia digestion is unreliable. The method using 1 mol L-1 HNO3 in an closed system (microwave showed potential for replacing the classical method of extraction of nonexchangeable forms of K (boiling 1 mol L-1 HNO3 in an open system - hot plate and reduced the loss of Si by volatilization.

Dissolution of uranium oxide TBP-HNO3 complex

International Nuclear Information System (INIS)

Mizuno, Mineo; Kosaka, Yuji; Mori, Yukihide; Shimada, Takashi

2002-12-01

As a head end process for the pulverization of the spent fuel, the mechanical method (the shredder method) and the pyro-chemical method (oxidisation heat-treatment) have been examined. UO 2 is a main ingredient of Uranium oxide powder by the mechanical method, and U 3 O 8 is that by the pyro-chemical method. Moreover, the particle size of the pulverized powder depend on the conditions of the pulverizing process. As it was considered that the difference of dissolution rates of samples was caused by the difference of sample chemical forms and dissolution temperature, parametric surveys on chemical form and particle size of powder and dissolution temperature were carried out, and the following results were obtained. 1) The remarkable difference of dissolution rate between U 3 O 8 powder (average particle size 3.7 μm) and UO 2 powder (average particle size 2.4 μm) which have comparatively similar particle size was not observed. 2) It was confirmed that the dissolution rate became lower according to the particle size increase (average particle size 2.4 μm-1 mm). And it was considered that dissolution rate had strong dependency on particle size, according to the results that the powder with 1 mm particle size did not dissolute completely after 5 hours test. 3) The temperature dependency of the dissolution rate was confirmed by dissolution test with UO 2 powder (average particle size 2.4 μm-1 mm). The higher dissolution rate was obtained in the higher dissolution temperature, and 11 kcal/mol was obtained as activation energy of dissolution. 4) In the dissolution test of UO 2 powder, the nitric acid concentration started to change earlier than that of U 3 O 8 powder and concentration change range became larger compared with that in the dissolution test of U 3 O 8 powder. It was considered that those differences were caused by difference in mole ratio of Uranium and nitric acid which are consumed in the dissolution reaction (3:7 for U 3 O 8 , 3:8 for UO 2 ). 5) In case

Polymorph-dependent titanium dioxide nanoparticle dissolution in acidic and alkali digestions

Science.gov (United States)

Multiple polymorphs (anatase, brookite and rutile) of titanium dioxide nanoparticles (TiO2-NPs) with variable structures were quantified in environmental matrices via microwave-based hydrofluoric (HF) and nitric (HNO3) mixed acid digestion and muffle furnace (MF)-based potassium ...

Simultaneous estimation of a binary mixture of a weak acid and a strong acid by volumetric titration and pH measurement

International Nuclear Information System (INIS)

Karmakar, Sanat; Mallika, C.; Kamachi Mudali, U.

2012-01-01

High level liquid waste (HLLW) generated in the aqueous reprocessing of spent nuclear fuels for the separation of uranium and plutonium by PUREX process, comprises the fission and corrosion products in 4 M nitric acid. Reduction in waste volume is accomplished by destroying the acidity of the waste solution from 4 to less than 2 M by treating it with formaldehyde and subsequent concentration by evaporation. In the denitration by HCHO, nitric acid in the waste solution is reduced to NOx and water via nitrous acid as the intermediate product: whereas formaldehyde is oxidized to formic acid which is converted to CO 2 and H 2 O subsequently. The reaction is highly exothermic and the release of all gaseous products may lead to uncontrollable process conditions. Hence, for the safe operation, it is desirable to estimate the concentration of residual formic acid as well as nitric acid in the product stream as a function of time. The acidity in the feed solution is 4 M and the concentration of HNO 3 in the product solution is in the range 1- 4 M. Since the formic acid generated during the reaction will be consumed immediately, the concentration of residual acid will be in the range 0.05-0.5 M. A simultaneous titration method based on pH measurement and volumetric analysis has been developed in the present work for the quantitative determination of the weak acid (HCOOH)with known pKa value and the strong acid (HNO 3 ) in the binary mixture

Thermal behavior of potato starch and water-vaporization behavior of its paste controlled with amino acid and peptide-rich food materials.

Science.gov (United States)

Sakauchi, Satoshi; Hattori, Makoto; Yoshida, Tadashi; Yagishita, Takahiro; Ito, Koichi; Akemitsu, Shin-Ichi; Takahashi, Koji

2010-03-01

The particular effect of 4 kinds of amino acid and peptide-rich food material (APRM) containing different charged amino acid contents on the gelatinization and retrogradation behavior of potato starch granules and on the water-vaporization behavior was analyzed by differential scanning calorimetry, rapid viscoanalysis, x-ray diffractometry, thermal gravimetry-differential thermal analysis, and pulsed NMR. APRM with a high-charged amino acid content produced unique gelatinization and retrogradation behavior in terms of an elevated gelatinization temperature, reduced viscosity, higher setback, and lower retrograded starch melting enthalpy. The recovered x-ray diffraction intensity decreased with increasing charged amino acid content. APRM with high-charged amino acid content could provide an improved paste having easy vaporization of external water in the swollen starch granules due to the reduced swelling.

Vaporization of GaI3Py adduct

International Nuclear Information System (INIS)

Timoshkina, A.Yu.; Grigor'ev, A.A.; Suvorov, A.V.

1995-01-01

Processes of GaI 3 Py complex vaporization have been studied by mass-spectrometric, tensimetric and calorimetric methods. It is shown that adduct transformation into vapour is accompanied by its thermal dissociation. Thermodynamic characteristics of evaporation and dissociation of GaI 3 Py complex have been obtained. 14 refs., 2 figs., 6 tabs

Prediction of the vapor pressure and vaporization enthalpy of 1-n-alkyl-3-methylimidazolium-bis-(trifluoromethanesulfonyl) amide ionic liquids.

Science.gov (United States)

Diedenhofen, Michael; Klamt, Andreas; Marsh, Kenneth; Schäfer, Ansgar

2007-09-07

The vapor pressures and vaporization enthalpies of a series of 1-n-alkyl-3-methylimidazolium-bis-(trifluoromethanesulfonyl) amide ionic liquids have been predicted with two different approaches using the COSMO-RS method and quantum chemical gas phase calculations. While the calculated enthalpies are in good agreement with the experimental data, COSMO-RS seems to underestimate the vapor pressures by roughly 0.5-4 log units dependent on the IL and approach used.

Measurements of atmospheric nitrous acid and nitric acid

Science.gov (United States)

Huang, Gu; Zhou, Xianliang; Deng, Guohong; Qiao, Huancheng; Civerolo, Kevin

A highly sensitive technique for the measurement of atmospheric HONO and HNO 3 is reported. The technique is based on aqueous scrubbing using two coil samplers, followed by conversion of HNO 3 to nitrite, derivatization of nitrite to a highly light-absorbing azo dye with sulfanilamide (SA) and N-(1-naphthyl) ethylenediamine (NED), and high performance liquid chromatography (HPLC) analysis. HNO 3 concentration was obtained by the difference of the two channels. Two scrubbing solutions were used for sampling the two species: a 1-mM phosphate buffer solution (pH 7) for the measurement of HONO and a 180 mM NH 4Cl/NH 3 buffer solution (pH 8.5) for the measurement of HONO+HNO 3. The scrubbing solution flow rate was 0.24 ml min -1 and the gas sampling flow rate was 2 l min -1. HNO 3 in the NH 4Cl/NH 3 buffer solution was quantitatively reduced to nitrite along an on-line 0.8-cm Cd reductor column. Nitrite in both channels was derivatized with 2 mM SA and 0.2 mM NED in 25 mM HCl. Quantitative derivatization was achieved within 5 min at 55°C. The azo dye derivative was then separated from the SA/NED reagent by reversed-phase HPLC and detected with a UV-vis detector at 540 nm. With an on-line SEP-PAK C-18 cartridge for the reagent purification, the method detection limit is estimated to be better than 1 pptv for HONO and about 20 pptv for HNO 3. The sample integration time was about 2 min and the sampling frequency is every 10 min. Data collected in downtown Albany and Whiteface Mountain, NY, are shown as examples of applications of this technique in both urban and remote clean environments.

Thermochemical study of 2,5-dimethyl-3-furancarboxylic acid, 4,5-dimethyl-2-furaldehyde, and 3-acetyl-2,5-dimethylfuran

International Nuclear Information System (INIS)

Ribeiro da Silva, Manuel A.V.; Amaral, Luisa M.P.F.

2011-01-01

The standard (p o = 0.1 MPa) molar enthalpies of formation, in the gaseous state, at T = 298.15 K, for 2,5-dimethyl-3-furancarboxylic acid, 3-acetyl-2,5-dimethylfuran, and 4,5-dimethyl-2-furaldehyde were derived from the values of the standard molar enthalpies of formation, in the condensed phase, and the standard molar enthalpies of phase transition from the condensed to the gaseous state. The values of the standard molar enthalpies of formation of the compounds in the condensed phases were calculated from the measurements of the standard massic energies of combustion obtained by static bomb combustion calorimetry. The enthalpies of vaporization/sublimation were measured by Calvet high temperature microcalorimetry. For 2,5-dimethyl-3-furancarboxylic acid the standard enthalpy of sublimation was also calculated, by the application of the Clausius-Clapeyron equation, to the temperature dependence of the vapor pressures measured by the Knudsen effusion technique. (table)

Atmospheric production of oxalic acid/oxalate and nitric acid/nitrate in the Tampa Bay airshed: Parallel pathways

Science.gov (United States)

Martinelango, P. Kalyani; Dasgupta, Purnendu K.; Al-Horr, Rida S.

Oxalic acid is the dominant dicarboxylic acid (DCA), and it constitutes up to 50% of total atmospheric DCAs, especially in non-urban and marine atmospheres. A significant amount of particulate H 2Ox/oxalate (Ox) occurred in the coarse particle fraction of a dichotomous sampler, the ratio of oxalate concentrations in the PM 10 to PM 2.5 fractions ranged from 1 to 2, with mean±sd being 1.4±0.2. These results suggest that oxalate does not solely originate in the gas phase and condense into particles. Gaseous H 2Ox concentrations are much lower than particulate Ox concentrations and are well correlated with HNO 3, HCHO, and O 3, supporting a photochemical origin. Of special relevance to the Bay Region Atmospheric Chemistry Experiment (BRACE) is the extent of nitrogen deposition in the Tampa Bay estuary. Hydroxyl radical is primarily responsible for the conversion of NO 2 to HNO 3, the latter being much more easily deposited. Hydroxyl radical is also responsible for the aqueous phase formation of oxalic acid from alkenes. Hence, we propose that an estimate of rad OH can be obtained from H 2Ox/Ox production rate and we accordingly show that the product of total oxalate concentration and NO 2 concentration approximately predicts the total nitrate concentration during the same period.

Vapor pressure and enthalpy of vaporization of aliphatic propanediamines

International Nuclear Information System (INIS)

Verevkin, Sergey P.; Chernyak, Yury

2012-01-01

Highlights: ► We measured vapor pressure of four aliphatic 1,3-diamines. ► Vaporization enthalpies at 298 K were derived. ► We examined consistency of new and available data in the literature. ► A group-contribution method for prediction was developed. - Abstract: Vapor pressures of four aliphatic propanediamines including N-methyl-1,3-propanediamine (MPDA), N,N-dimethyl-1,3-propanediamine (DMPDA), N,N-diethyl-1,3-propanediamine (DEPDA) and N,N,N′,N′-tetramethyl-1,3-propanediamine (4MPDA) were measured using the transpiration method. The vapor pressures developed in this work and reported in the literature were used to derive molar enthalpy of vaporization values at the reference temperature 298.15 K. An internal consistency check of the enthalpy of vaporization was performed for the aliphatic propanediamines studied in this work. A group-contribution method was developed for the validation and prediction vaporization enthalpies of amines and diamines.

Tuning the work function of monolayer graphene on 4H-SiC (0001) with nitric acid

International Nuclear Information System (INIS)

Günes, Fethullah; Arezki, Hakim; Alamarguy, David; Alvarez, José; Kleider, Jean-Paul; Boutchich, Mohamed; Pierucci, Debora; Ouerghi, Abdelkarim; Dappe, Yannick J

2015-01-01

Chemical doping of graphene is a key process for the modulation of its electronic properties and the design and fabrication of graphene-based nanoelectronic devices. Here, we study the adsorption of diluted concentrations of nitric acid (HNO_3) onto monolayer graphene/4H-SiC (0001) to induce a variation of the graphene work function (WF). Raman spectroscopy indicates an increase in the defect density subsequent to the doping. Moreover, ultraviolet photoemission spectroscopy (UPS) was utilized to quantify the WF shift. UPS data show that the WF of the graphene layer decreased from 4.3 eV (pristine) down to 3.8 eV (30% HNO_3) and then increased to 4.4 eV at 100% HNO_3 concentration. These observations were confirmed using density functional theory (DFT) calculations. This straightforward process allows a large WF modulation, rendering the molecularly modified graphene/4H-SiC(0001) a highly suitable electron or hole injection electrode. (paper)

On hydrazine oxidation in nitric acid media

International Nuclear Information System (INIS)

Zil'berman, B.Ya.; Lelyuk, G.A.; Mashkin, A.N.; Yasnovitskaya, A.L.

1988-01-01

Yield of products of radiolytic ( 60 Co gamma radiation) and chemical hydrazine (HZ) oxidation in nitric acid media is studied. Under radiolyte HZ oxidation by nitric acid hydrazoic acid, ammonia and nitrogen appear to be the reaction products. HN 3 yield maximum under HZN oxidation makes up ∼ 0.35 mol per a mol of oxiduzed HZN. Under chemical oxidation HZN is oxidized by HNO 3 according to reaction catalysed by technetium HN 3 yield makes up ∼ 0.35 mol per a mol of oxidized HZN. Radiation-chemical oxidation of HN 3 proceeds up to its complete decomposition, decomposition rate is comparable with HZ oxidation rate. Under the chemical oxidation HN 3 is more stable, it is slowly decomposed after complete HZ decomposition

Size-controlled synthesis and formation mechanism of manganese oxide OMS-2 nanowires under reflux conditions with KMnO4 and inorganic acids

Science.gov (United States)

Zhang, Qin; Cheng, Xiaodi; Qiu, Guohong; Liu, Fan; Feng, Xionghan

2016-05-01

This study presents a simplified approach for size-controlled synthesis of manganese oxide octahedral molecular sieve (OMS-2) nanowires using potassium permanganate (KMnO4) and different inorganic acids (HCl, HNO3, and H2SO4) under reflux conditions. The morphology and nanostructure of the synthesized products are characterized by X-ray diffraction, Ar adsorption, and electron microscopy analysis, in order to elucidate the controlling effects of acid concentration and type as well as the formation mechanism of OMS-2 nanowires. The concentration of inorganic acid is a crucial factor controlling the phase of the synthesized products. OMS-2 nanowires are obtained with HCl at the concentration ≥0.96 mol/L or with HNO3 and H2SO4 at the concentrations ≥0.72 mol/L. Differently, the type of inorganic acid effectively determines the particle size of OMS-2 nanowires. When the acid is changed from HCl to HNO3 and H2SO4 in the reflux system, the average length of OMS-2 declines significantly by 60-70% (1104-442 and 339 nm), with minor decreased in the average width (43-39 and 34 nm). The formation of OMS-2 nanowires under reflux conditions with KMnO4 and inorganic acids involves a two-step process, i.e., the initial formation of layered manganese oxides, and subsequent transformation to OMS-2 via a dissolution-recrystallization process under acidic conditions. The proposed reflux route provides an alternative approach for synthesizing OMS-2 nanowires as well as other porous nano-crystalline OMS materials.

Rate of Pu(IV) polymer formation in nitric acid solutions. A parametric study

Energy Technology Data Exchange (ETDEWEB)

Toth, L.M.; Osborne, M.M.

1984-07-01

The kinetics of Pu(IV) polymer formation has been examined with the intent of developing a simple mathematical equation that would predict the appearance of polymer. The fundamental polymerization rate has been found to be dependent on [Pu(IV)]{sup 1} {sup 2} and [HNO{sub 3}]{sup -6}. The activation energy for polymer formation is real temperature dependent, varying from 66.9 kJ/mol (16 kcal/mol) at 25{sup 0}C to 150.5 kJ/mol (36 kcal/mol) at 105{sup 0}C. These relationships have guided the developement of an empirical model that gives time to form 2% polymer in hours, t = [Pu/sub T/]/sup a/[HNO{sub 3}]/sup b/ Ae/sup c/T/, where a = -1.6, b = 4.6, c = 12.300 K, and A = 7.66 x 10{sup -16} h M{sup -3}; [Pu/sub T/] is the total plutonium concentration, mol/L; and [HNO{sub 3}] is the makeup nitric acid concentration, mol/L. 11 references, 26 figures, 1 table.

Study of the dissolution of uranium nitrides in nitric acid by measuring the isotope ratios, 15N/14N, of the formed products

International Nuclear Information System (INIS)

Hadibi-Olschewski, Nathalie

1991-01-01

The aim of this study was to investigate the dissolution behavior of nitride fuels in nitric acid. The use of nitride fuels in nuclear reactor has many advantages compared with the oxide fuels. One problem in employing nitrides as fuels is the formation of radio-toxic 14 C upon irradiation of natural nitrogen ( 14 N:99.64 pc, 15 N:0.36 pc) in a nuclear reactor ( 14 N (n,p) 14 C reaction). The use of 15 N-enriched fuels avoids these drawbacks. This study was undertaken so as to better understand the mechanisms of the dissolution process and also to follow the distribution of the expensive nitrogen isotope 15 N from the point of view of its behaviour during the recycling process. This study is based on previous work, where the evolution of the nitrogen compounds formed during the dissolution was measured as a function of time for different dissolution parameters. Using 15 N-enriched uranium nitrides or 15 N-enriched nitric acid, two methods were developed to study the influence of the dissolution parameters, nitric acid temperature and concentration, on the 15 N/ 14 N ratios of the nitrogen, nitrogen oxides and ammonium ions utilising a coupled gas-chromatograph/mass spectrometer. The main results are: - similar isotopic composition for NH 4 + and UN; - mixed 14 N/ 15 N composition for N 2 and N 2 O; - similar isotopic composition for NO, NO 2 and HNO 3 ; - no influence of the dissolution parameters on the isotopic composition of the products; an exception maybe made for the N 2 case, which contains more 15 N with increasing acidity and temperature. This work confirms that the first dissolution step is the oxidation of UN with HNO 3 to form NH 4 + and HNO 2 and that HNO 2 has a catalytic role in the dissolution to form other products. And we can conclude that to recycle 15 N, the ammonium ions must be recycled, at least for the case where nitrides are dissolved directly in HNO 3 . (author) [fr

Decontamination of Uranium-Contaminated Soil Sand Using Supercritical CO2 with a TBP–HNO3 Complex

Directory of Open Access Journals (Sweden)

Kwangheon Park

2015-09-01

Full Text Available An environmentally friendly decontamination process for uranium-contaminated soil sand is proposed. The process uses supercritical CO2 as the cleaning solvent and a TBP–HNO3 complex as the reagent. Four types of samples (sea sand and coarse, medium, and fine soil sand were artificially contaminated with uranium. The effects of the amount of the reagent, sand type, and elapsed time after the preparation of the samples on decontamination were examined. The extraction ratios of uranium in all of the four types of sand samples were very high when the time that elapsed after preparation was less than a few days. The extraction ratio of uranium decreased in the soil sand with a higher surface area as the elapsed time increased, indicating the possible formation of chemisorbed uranium on the surface of the samples. The solvent of supercritical CO2 seemed to be very effective in the decontamination of soil sand. However, the extraction of chemisorbed uranium in soil sand may need additional processes, such as the application of mechanical vibration and the addition of bond-breaking reagents.

Measurements of atmospheric nitrous acid and nitric acid

Energy Technology Data Exchange (ETDEWEB)

Huang, G.; Deng, G. [State University of New York (United States). School of Public Health; Zhou, X. [State University of New York (United States). School of Public Health; New York State Dept. of Health (United States). Wadsworth Center; Qiao, H.; Civerolo, K. [New York State Dept. of Health (United States). Wadsworth Center

2002-05-01

A highly sensitive technique for the measurement of atmospheric HONO and HNO{sub 3} is reported. The technique is based on aqueous scrubbing using two coil samplers, followed by conversion of HNO{sub 3} to nitrite, derivatization of nitrite to a highly light-absorbing azo dye with sulfanilamide (SA) and N-(1-naphthyl) ethylenediamine (NED), and high performance liquid chromatography (HPLC) analysis. HNO{sub 3} concentration was obtained by the difference of the two channels. Two scrubbing solutions were used for sampling the two species: a 1-mM phosphate buffer solution (pH 7) for the measurement of HONO and a 180 mM NH{sub 4}Cl/NH{sub 3} buffer solution (pH 8.5) for the measurement of HONO+HNO{sub 3}. The scrubbing solution flow rate was 0.24 ml min{sup -1} and the gas sampling flow rate was 2l min{sup -1}. HNO{sub 3} in the NH{sub 4}Cl/NH{sub 3} buffer solution was quantitatively reduced to nitrite along an on-line 0.8-cm Cd reductor column. Nitrite in both channels was derivatized with 2 mM SA and 0.2 mM NED in 25 mM HCl. Quantitative derivatization was achieved within 5 min at 55{sup o}C. The azo dye derivative was then separated from the SA/NED reagent by reversed-phase HPLC and detected with a UV-vis detector at 540 nm. With an on-line SEP-PAK C-18 cartridge for the reagent purification, the method detection limit is estimated to be better than 1 pptv for HONO and about 20 pptv for HNO{sub 3}. The sample integration time was about 2 min and the sampling frequency is every 10 min. Data collected in downtown Albany and Whiteface Mountain, NY, are shown as examples of applications of this technique in both urban and remote clean environments. (Author)

Ultrasound-assisted acid hydrolysis of cellulose to chemical building blocks: Application to furfural synthesis.

Science.gov (United States)

Santos, Daniel; Silva, Ubiratan F; Duarte, Fabio A; Bizzi, Cezar A; Flores, Erico M M; Mello, Paola A

2018-01-01

In this work, the use of ultrasound energy for the production of furanic platforms from cellulose was investigated and the synthesis of furfural was demonstrated. Several systems were evaluated, as ultrasound bath, cup horn and probe, in order to investigate microcrystalline cellulose conversion using simply a diluted acid solution and ultrasound. Several acid mixtures were evaluated for hydrolysis, as diluted solutions of HNO 3 , H 2 SO 4 , HCl and H 2 C 2 O 4 . The influence of the following parameters in the ultrasound-assisted acid hydrolysis (UAAH) were studied: sonication temperature (30 to 70°C) and ultrasound amplitude (30 to 70% for a cup horn system) for 4 to 8molL -1 HNO 3 solutions. For each evaluated condition, the products were identified by ultra-performance liquid chromatography with high-resolution time-of-flight mass spectrometry (UPLC-ToF-MS), which provide accurate information regarding the products obtained from biomass conversion. The furfural structure was confirmed by nuclear magnetic resonance ( 1 H and 13 C NMR) spectroscopy. In addition, cellulosic residues from hydrolysis reaction were characterized using scanning electron microscopy (SEM), which contributed for a better understanding of physical-chemical effects caused by ultrasound. After process optimization, a 4molL -1 HNO 3 solution, sonicated for 60min at 30°C in a cup horn system at 50% of amplitude, lead to 78% of conversion to furfural. This mild temperature condition combined to the use of a diluted acid solution represents an important contribution for the selective production of chemical building blocks using ultrasound energy. Copyright © 2017 Elsevier B.V. All rights reserved.

Characteristics and mechanism of explosive reactions of Purex solvents with Nitric Acid at elevated temperatures

Energy Technology Data Exchange (ETDEWEB)

Miyata, Teijiro [Radiation Application Development Association, Tokai, Ibaraki (Japan); Takada, Junichi; Koike, Tadao; Tsukamoto, Michio; Watanabe, Koji [Department of Fuel Cycle Safety Research, Nuclear Safety Research Center, Tokai Research Establishment, Japan Atomic Energy Research Institute, Tokai, Ibaraki (Japan); Ida, Masaaki [JGC PLANTECH CO., LTD (Japan); Nakagiri, Naotaka [JGC Corp., Tokyo (Japan); Nishio, Gunji [Research Organization for Information Science and Technology, Tokai, Ibaraki (Japan)

2000-03-01

This investigation was undertaken to make clear the energetic properties and mechanism of explosive decomposition of Purex solvent systems (TBP/n-Dodecane/HNO{sub 3}) by Nitric Acid at elevated temperatures using a calorimetric technique (DSC, ARC) and a chromatographic technique (GC, GC/MS). The measurement of exothermic events of solvent-HNO{sub 3} reactions using DSC with a stainless steel sealed cell showed distinct two peaks with maxima at around 170 and 320degC, respectively. The peak at around 170degC was mainly attributed to the reactions of dealkylation products (n-butyl nitrate) of TBP and the solvent with nitric acid, and the peak at around 320degC was attributed to the exothermic decomposition of nitrated dodecanes formed in the foregoing exothermic reaction of dodecane with nitric acid. By using the data obtained in ARC experiments, activation energies of 123.2 and 152.5 kJ/mol were determined for the exothermic reaction of TBP with nitric acid and for the exothermic pyrolysis of n-butyl nitrate, respectively. Some possible pathways were considered for the explosive decomposition of TBP by nitric acid at elevated temperatures. (author)

Ultrasound-assisted vapor generation of mercury.

Science.gov (United States)

Ribeiro, Anderson S; Vieira, Mariana A; Willie, Scott; Sturgeon, Ralph E

2007-06-01

Cold vapor generation arising from reduction of both Hg(2+) and CH(3)Hg(+) occurs using ultrasonic (US) fields of sufficient density to achieve both localized heating as well as radical-based attack in solutions of formic and acetic acids and tetramethylammonium hydroxide (TMAH). A batch sonoreactor utilizing an ultrasonic probe as an energy source and a flow through system based on a US bath were optimized for this purpose. Reduction of CH(3)Hg(+) to Hg(0) occurs only at relatively high US field density (>10 W cm(-3) of sample solution) and is thus not observed when a conventional US bath is used for cold vapor generation. Speciation of mercury is thus possible by altering the power density during the measurement process. Thermal reduction of Hg(2+) is efficient in formic acid and TMAH at 70 degrees C and occurs in the absence of the US field. Room temperature studies with the batch sonoreactor reveal a slow reduction process, producing temporally broad signals having an efficiency of approximately 68% of that arising from use of a conventional SnCl(2) reduction system. Molecular species of mercury are generated at high concentrations of formic and acetic acid. Factors affecting the generation of Hg(0) were optimized and the batch sonoreactor used for the determination of total mercury in SLRS-4 river water reference material.

Phase Engineering of Perovskite Materials for High-Efficiency Solar Cells: Rapid Conversion of CH3NH3PbI3 to Phase-Pure CH3NH3PbCl3 via Hydrochloric Acid Vapor Annealing Post-Treatment.

Science.gov (United States)

Zhou, Weiran; Zhou, Pengcheng; Lei, Xunyong; Fang, Zhimin; Zhang, Mengmeng; Liu, Qing; Chen, Tao; Zeng, Hualing; Ding, Liming; Zhu, Jun; Dai, Songyuan; Yang, Shangfeng

2018-01-17

Organometal halide CH 3 NH 3 PbI 3 (MAPbI 3 ) has been commonly used as the light absorber layer of perovskite solar cells (PSCs), and, especially, another halide element chlorine (Cl) has been often incorporated to assist the crystallization of perovskite film. However, in most cases, a predominant MAPbI 3 phase with trace of Cl - is obtained ultimately and the role of Cl involvement remains unclear. Herein, we develop a low-cost and facile method, named hydrochloric acid vapor annealing (HAVA) post-treatment, and realize a rapid conversion of MAPbI 3 to phase-pure MAPbCl 3 , demonstrating a new concept of phase engineering of perovskite materials toward efficiency enhancement of PSCs for the first time. The average grain size of perovskite film after HAVA post-treatment increases remarkably through an Ostwald ripening process, leading to a denser and smoother perovskite film with reduced trap states and enhanced crystallinity. More importantly, the generation of MAPbCl 3 secondary phase via phase engineering is beneficial for improving the carrier mobility with a more balanced carrier transport rate and enlarging the band gap of perovskite film along with optimized energy level alignment. As a result, under the optimized HAVA post-treatment time (2 min), we achieved a significant enhancement of the power conversion efficiency (PCE) of the MAPbI 3 -based planar heterojunction-PSC device from 14.02 to 17.40% (the highest PCE reaches 18.45%) with greatly suppressed hysteresis of the current-voltage response.

Comment on “Observations of ammonia, nitric acid, and fine particles in a rural gas production region” by Yi Li, Florian M. Schwandnera, H. James Sewell, Angela Zivkovich, Mark Tigges, Suresh Raja, Stephen Holcomb, John V. Molenar, Lincoln Sherman, Cassie Archuleta, Taehyoung Lee and Jeffrey L. Collett Jr. Atmospheric Environment (in press)

Science.gov (United States)

Phillips, Gavin J.

2014-05-01

An artefact of the detection of nitric acid (HNO3) by denuder methods is discussed. This artefact arises from the likely reaction of dinitrogen pentoxide (N2O5) on the denuder train resulting in the report of some fraction of N2O5 as HNO3.

Thermal decomposition of gaseous ammonium nitrate at low pressure: kinetic modeling of product formation and heterogeneous decomposition of nitric acid.

Science.gov (United States)

Park, J; Lin, M C

2009-12-03

The thermal decomposition of ammonium nitrate, NH(4)NO(3) (AN), in the gas phase has been studied at 423-56 K by pyrolysis/mass spectrometry under low-pressure conditions using a Saalfeld reactor coated with boric acid. The sublimation of NH(4)NO(3) at 423 K was proposed to produce equal amounts of NH(3) and HNO(3), followed by the decomposition reaction of HNO(3), HNO(3) + M --> OH + NO(2) + M (where M = third-body and reactor surface). The absolute yields of N(2), N(2)O, H(2)O, and NH(3), which can be unambiguously measured and quantitatively calibrated under a constant pressure at 5-6.2 torr He are kinetically modeled using the detailed [H,N,O]-mechanism established earlier for the simulation of NH(3)-NO(2) (Park, J.; Lin, M. C. Technologies and Combustion for a Clean Environment. Proc. 4th Int. Conf. 1997, 34-1, 1-5) and ADN decomposition reactions (Park, J.; Chakraborty, D.; Lin, M. C. Proc. Combust. Inst. 1998, 27, 2351-2357). Since the homogeneous decomposition reaction of HNO(3) itself was found to be too slow to account for the consumption of reactants and the formation of products, we also introduced the heterogeneous decomposition of HNO(3) in our kinetic modeling. The heterogeneous decomposition rate of HNO(3), HNO(3) + (B(2)O(3)/SiO(2)) --> OH + NO(2) + (B(2)O(3)/SiO(2)), was determined by varying its rate to match the modeled result to the measured concentrations of NH(3) and H(2)O; the rate could be represented by k(2b) = 7.91 x 10(7) exp(-12 600/T) s(-1), which appears to be consistent with those reported by Johnston and co-workers (Johnston, H. S.; Foering, L.; Tao, Y.-S.; Messerly, G. H. J. Am. Chem. Soc. 1951, 73, 2319-2321) for HNO(3) decomposition on glass reactors at higher temperatures. Notably, the concentration profiles of all species measured could be satisfactorily predicted by the existing [H,N,O]-mechanism with the heterogeneous initiation process.

Thermal Decomposition of Gaseous Ammonium Nitrate at Low Pressure: Kinetic Modeling of Product Formation and Heterogeneous Decomposition of Nitric Acid

Science.gov (United States)

Park, J.; Lin, M. C.

2009-10-01

The thermal decomposition of ammonium nitrate, NH4NO3 (AN), in the gas phase has been studied at 423-56 K by pyrolysis/mass spectrometry under low-pressure conditions using a Saalfeld reactor coated with boric acid. The sublimation of NH4NO3 at 423 K was proposed to produce equal amounts of NH3 and HNO3, followed by the decomposition reaction of HNO3, HNO3 + M → OH + NO2 + M (where M = third-body and reactor surface). The absolute yields of N2, N2O, H2O, and NH3, which can be unambiguously measured and quantitatively calibrated under a constant pressure at 5-6.2 torr He are kinetically modeled using the detailed [H,N,O]-mechanism established earlier for the simulation of NH3-NO2 (Park, J.; Lin, M. C. Technologies and Combustion for a Clean Environment. Proc. 4th Int. Conf. 1997, 34-1, 1-5) and ADN decomposition reactions (Park, J.; Chakraborty, D.; Lin, M. C. Proc. Combust. Inst. 1998, 27, 2351-2357). Since the homogeneous decomposition reaction of HNO3 itself was found to be too slow to account for the consumption of reactants and the formation of products, we also introduced the heterogeneous decomposition of HNO3 in our kinetic modeling. The heterogeneous decomposition rate of HNO3, HNO3 + (B2O3/SiO2) → OH + NO2 + (B2O3/SiO2), was determined by varying its rate to match the modeled result to the measured concentrations of NH3 and H2O; the rate could be represented by k2b = 7.91 × 107 exp(-12 600/T) s-1, which appears to be consistent with those reported by Johnston and co-workers (Johnston, H. S.; Foering, L.; Tao, Y.-S.; Messerly, G. H. J. Am. Chem. Soc. 1951, 73, 2319-2321) for HNO3 decomposition on glass reactors at higher temperatures. Notably, the concentration profiles of all species measured could be satisfactorily predicted by the existing [H,N,O]-mechanism with the heterogeneous initiation process.

Effect of petroleum vapors inhalation on intestinal absorption of glucose and some amino acids in the rat

International Nuclear Information System (INIS)

Szablicka, E.; Oledzka, R.

1989-01-01

The proper intestinal absorption of nutrients, particularly sugars and amino acids, is necessary to keep the organism healthy. It is well known that various toxic compounds present in the environment can have an unfavorable influence. On the other hand it is also known that crude oil which pollutes the aqueous environment affects birds' gastrointestinal tract. Little is known about the influence of petroleum vapors on the gastrointestinal tract of animals and humans. The present study was undertaken to determine the effect of petroleum vapors inhalation on intestinal absorption of some nutrients (glucose, leucine, methionine) in rats

GOZCARDS Source Data for Nitric Acid Monthly Zonal Means on a Geodetic Latitude and Pressure Grid V1.01

Data.gov (United States)

National Aeronautics and Space Administration — The GOZCARDS Source Data for Nitric Acid Monthly Zonal Averages on a Geodetic Latitude and Pressure Grid product (GozSmlpHNO3) contains zonal means and related...

GOZCARDS Merged Data for Nitric Acid Monthly Zonal Means on a Geodetic Latitude and Pressure Grid V1.01

Data.gov (United States)

National Aeronautics and Space Administration — The GOZCARDS Merged Data for Nitric Acid Monthly Zonal Averages on a Geodetic Latitude and Pressure Grid product (GozMmlpHNO3) contains zonal means and related...

Photoassisted vapor generation in the presence of organic acids for ultrasensitive determination of Se by electrothermal-atomic absorption spectrometry following headspace single-drop microextraction

International Nuclear Information System (INIS)

Figueroa, Raul; Garcia, Monica; Lavilla, Isela; Bendicho, Carlos

2005-01-01

A method is described for the determination of selenium at the pg/mL level by electrothermal-atomic absorption spectrometry using in situ photogeneration of Se vapors, headspace sequestration onto an aqueous microdrop containing Pd(II) and subsequent injection in a graphite tube. Several organic acids (formic, oxalic, acetic, citric and ethylenediaminetetraacetic) have been tried for photoreduction of Se(IV) into volatile Se compounds under UV irradiation. Experimental variables such as UV irradiation time, organic acid concentration, Pd(II) concentration in the drop, sample and drop volumes, extraction time and pH were fully optimized. Low-molecular weight acids such as formic and acetic provided optimal photogeneration of volatile Se species at a 0.6 mol/L concentration. Citric and ethylenediaminetetraacetic acid allowed to use a concentration as low as 1 mmol/L, but extraction times were longer than for formic and acetic acids. Photogeneration of (CH 3 ) 2 Se from Se(IV) in the presence of acetic acid provided a detection limit of 20 pg/mL, a preconcentration factor of nearly 285 and a precision, expressed as relative standard deviation, of 4%. Analytical performance seemed to depend not only on the photogeneration efficiency obtained with each acid but also on the stability of the vapors in the headspace. The method showed a high freedom from interferences caused by saline matrices, but interferences were observed for transition metals at a relatively low concentration

A two staged condensation of vapors of an isobutane tower in installations for sulfuric acid alkylation

Energy Technology Data Exchange (ETDEWEB)

Smirnov, N.P.; Feyzkhanov, R.I.; Idrisov, A.D.; Navalikhin, P.G.; Sakharov, V.D.

1983-01-01

In order to increase the concentration of isobutane to greater than 72 to 76 percent in an installation for sulfuric acid alkylation, a system of two staged condensation of vapors from an isobutane tower is placed into operation. The first stage condenses the heavier part of the upper distillate of the tower, which is achieved through somewhat of an increase in the condensate temperature. The product which is condensed in the first stage is completely returned to the tower as a live irrigation. The vapors of the isobutane fraction which did not condense in the first stage are sent to two newly installed condensers, from which the product after condensation passes through intermediate tanks to further depropanization. The two staged condensation of vapors of the isobutane tower reduces the content of the inert diluents, the propane and n-butane in the upper distillate of the isobutane tower and creates more favorable conditions for the operation of the isobutane and propane tower.

Nitric Acid Poisoning: Case Report

International Nuclear Information System (INIS)

Quintero Giraldo, Maria Paulina; Quiceno Calderon, William de Jesus; Melo Arango Catalina

2011-01-01

Nitric acid (HNO 3 ) is a corrosive fluid that, when in contact with reducing agents, generates nitrogen oxides that are responsible for inhalation poisoning. We present two cases of poisoning from nitric acid gas inhalation resulting from occupational exposure. Imaging findings were similar in both cases, consistent with adult respiratory distress syndrome (ARDS): bilaterally diffuse alveolar opacities on the chest X-ray and a cobblestone pattern on computed tomography (CT).one of the patients died while the other evolved satisfactorily after treatment with n-acetyl cysteine and mechanical ventilation. The diagnosis of nitric acid poisoning was made on the basis of the history of exposure and the way in which the radiological findings evolved.

Cesium absorption from acidic solutions using ammonium molybdophosphate on a polyacrylonitrile support (AMP-PAN)

International Nuclear Information System (INIS)

Miller, C.J.; Olson, A.L.; Johnson, C.K.

1995-01-01

Recent efforts at the Idaho Chemical Processing Plant (ICPP) have included evaluation of cesium removal technologies as applied to ICPP acidic radioactive waste streams. Ammonium molybdophosphate (AMP) immobilized on a polyacrylonitrile support (AMP-PAN) has been studied as an ion exchange agent for cesium removal from acidic waste solutions. Capacities, distribution coefficients, elutability, and kinetics of cesium-extraction have been evaluated. Exchange breakthrough curves using small columns have been determined from 1M HNO 3 and simulated waste solutions. The theoretical capacity of AMP is 213 g Cs/kg AMP. The average experimental capacity in batch contacts with various acidic solutions was 150 g Cs/kg AMP. The measured cesium distribution coefficients from actual waste solutions were 3287 mL/g for dissolved zirconia calcines, and 2679 mL/g for sodium-bearing waste. The cesium in the dissolved alumina calcines was analyzed for; however, the concentration was below analytical detectable limits resulting in inconclusive results. The reaction kinetics are very rapid (2-10 minutes). Cesium absorption appears to be independent of acid concentration over the range tested (0.1 M to 5 M HNO 3 )

Acidic weathering of carbonate building stones: experimental assessment

Directory of Open Access Journals (Sweden)

Ryszard Kryza

2009-06-01

Full Text Available Three types of carbonate rocks, travertine, limestone and marble have been studied to determine their selected technical parameters (water absorption, resistance to salt crystallization damage and reaction to experimentally modelled acid rain weathering imitating the polluted urban atmospheric conditions. The acidic agents present in natural acid rain precipitation, H2SO4, HCl, HNO3, CH3COOH and mixture of all the acids, “Acid mix”, were tested. The initial stages of acid weathering involve, apart from chemical dissolution, particularly intense physical detachment of rock particles (granular disintegration significantly contributing to the total mass loss. Travertine was found to be most prone to salt crystallization damage and to acid weathering, and these features should be taken into account especially in external architectural usage of this stone in cold climate conditions and polluted urban atmosphere.

Radical Cations and Acid Protection during Radiolysis

Energy Technology Data Exchange (ETDEWEB)

Mincher, Bruce J. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Zarzana, Christopher A. [Idaho National Lab. (INL), Idaho Falls, ID (United States); Mezyk, Stephen P. [Idaho National Lab. (INL), Idaho Falls, ID (United States)

2016-09-09

Ligand molecules for used nuclear fuel separation schemes are exposed to high radiation fields and high concentrations of acid. Thus, an understanding of the complex interactions between extraction ligands, diluent, and acid is critical to understanding the performance of a separation process. The diglycolamides are ligands with important structural similarities to CMPO; however, previous work has shown that their radiolytic degradation has important mechanistic differences from CMPO. The DGAs do not enjoy radioprotection by HNO3 and the kinetics of DGA radiolytic degradation are different. CMPO degrades with pseudo-zero-order kinetics in linear fashion with absorbed dose while the DGAs degrade in pseudo-first-order, exponential fashion. This suggests that the DGAs degrade by simple reaction with some product of direct diluent radiolysis, while CMPO degradation is probably multi-step, with a slow step that is not dependent on the CMPO concentration, and mitigated by HNO₃. It is thus believed that radio-protection and the zero-order radiolytic degradation kinetics are related, and that these phenomena are a function of either the formation of strong acid complexes with CMPO and/or to the presence of the CMPO phenyl ring. Experiments to test both these hypotheses have been designed and partially conducted. This report summarizes findings related to these phenomena for FY16, in satisfaction of milestone M3FT-16IN030104053. It also reports continued kinetic measurements for the reactions of the dodecane radical cation with solvent extraction ligands.

Radical Cations and Acid Protection during Radiolysis

International Nuclear Information System (INIS)

Mincher, Bruce J.; Zarzana, Christopher A.; Mezyk, Stephen P.

2016-01-01

Ligand molecules for used nuclear fuel separation schemes are exposed to high radiation fields and high concentrations of acid. Thus, an understanding of the complex interactions between extraction ligands, diluent, and acid is critical to understanding the performance of a separation process. The diglycolamides are ligands with important structural similarities to CMPO; however, previous work has shown that their radiolytic degradation has important mechanistic differences from CMPO. The DGAs do not enjoy radioprotection by HNO3 and the kinetics of DGA radiolytic degradation are different. CMPO degrades with pseudo-zero-order kinetics in linear fashion with absorbed dose while the DGAs degrade in pseudo-first-order, exponential fashion. This suggests that the DGAs degrade by simple reaction with some product of direct diluent radiolysis, while CMPO degradation is probably multi-step, with a slow step that is not dependent on the CMPO concentration, and mitigated by HNO 3 . It is thus believed that radio-protection and the zero-order radiolytic degradation kinetics are related, and that these phenomena are a function of either the formation of strong acid complexes with CMPO and/or to the presence of the CMPO phenyl ring. Experiments to test both these hypotheses have been designed and partially conducted. This report summarizes findings related to these phenomena for FY16, in satisfaction of milestone M3FT-16IN030104053. It also reports continued kinetic measurements for the reactions of the dodecane radical cation with solvent extraction ligands.

Use of technical mixtures of carboxylic acids to the extraction of silver

International Nuclear Information System (INIS)

Smulek, W.

1983-01-01

The application of technical mixtures of carboxylic acids, obtained from a Polish oil mill, to the extraction of silver, gold, and europium is described. The distribution ratio is given as a function of HNO 3 and H 2 SO 4 concentrations, extractant and metal concentrations, and nature of diluent. (author)

Synthesis of freestanding water-soluble indium oxide nanocrystals capped by alanine nitric acid via ligand exchange for thin film transistors and effects of ligands on the electrical properties

International Nuclear Information System (INIS)

Choi, Jin-Kyu; Koh, Ye-Seul; Jeong, Hyun-Dam

2015-01-01

We demonstrate synthesis of freestanding water-soluble indium oxide nanocrystals (In 2 O 3 NCs) by ligand exchange to β-alanine nitric acid (Ala·HNO 3 ) and its application for active channel layer in thin film transistors (TFTs), with investigation of the effect of curing temperatures on the TFT properties in terms of thermal behaviour of the ligand molecules at 150, 300, and 350 °C. After ligand exchange from long alkyl ligand (myristic acid, MA) to short Ala·HNO 3 , the mobility of NC TFTs cured at 150 °C increased by over 1 order of magnitude, from 1.3 × 10 −4 cm 2 V -1 s −1 to 4.5 × 10 −3 cm 2 V -1 s −1 , due to enhanced tunnelling rate (Γ) between adjective NCs. Higher curing temperatures such as 300 and 350 °C, inducing thermal decomposition of the organic ligands, led to further enhancement of the mobility, particularly up to 2.2 cm 2 V -1 s −1 for the In 2 O 3 NC-Ala·HNO 3 TFT cured at 350 °C. It is also found that the ligand exchange of In 2 O 3 NC in acidic condition (e.g. HNO 3 ) would be simple and effective to reduce the surface defects by surface etching, which may lead to better device performances. - Graphical abstract: Display Omitted - Highlights: • Freestanding water-soluble In 2 O 3 nanocrystals (NCs) were synthesized by ligand exchange. • Thin film transistors (TFTs) of colloidal NCs were fabricated by spin-coating method. • Water-soluble In 2 O 3 NC TFTs showed higher mobilities due to shorter ligand length. • Surface defects of NCs were notably reduced by surface etching during ligand exchange

Medicinal Cannabis: In Vitro Validation of Vaporizers for the Smoke-Free Inhalation of Cannabis.

Science.gov (United States)

Lanz, Christian; Mattsson, Johan; Soydaner, Umut; Brenneisen, Rudolf

2016-01-01

Inhalation by vaporization is a promising application mode for cannabis in medicine. An in vitro validation of 5 commercial vaporizers was performed with THC-type and CBD-type cannabis. Gas chromatography/mass spectrometry was used to determine recoveries of total THC (THCtot) and total CBD (CBDtot) in the vapor. High-performance liquid chromatography with photodiode array detection was used for the quantitation of acidic cannabinoids in the residue and to calculate decarboxylation efficiencies. Recoveries of THCtot and CBDtot in the vapor of 4 electrically-driven vaporizers were 58.4 and 51.4%, 66.8 and 56.1%, 82.7 and 70.0% and 54.6 and 56.7% for Volcano Medic®, Plenty Vaporizer®, Arizer Solo® and DaVinci Vaporizer®, respectively. Decarboxylation efficiency was excellent for THC (≥ 97.3%) and CBD (≥ 94.6%). The gas-powered Vape-or-Smoke™ showed recoveries of THCtot and CBDtot in the vapor of 55.9 and 45.9%, respectively, and a decarboxylation efficiency of ≥ 87.7 for both cannabinoids. However, combustion of cannabis was observed with this device. Temperature-controlled, electrically-driven vaporizers efficiently decarboxylate inactive acidic cannabinoids and reliably release their corresponding neutral, active cannabinoids. Thus, they offer a promising application mode for the safe and efficient administration of medicinal cannabis.

Vapor pressure and enthalpy of vaporization of linear aliphatic alkanediamines

International Nuclear Information System (INIS)

Pozdeev, Vasiliy A.; Verevkin, Sergey P.

2011-01-01

Highlights: → We measured vapor pressure of diamines H 2 N-(CH 2 ) n -NH 2 with n = 3 to 12. → Vaporization enthalpies at 298 K were derived. → We examined consistency of new and available in the literature data. → Enthalpies of vaporization show linear dependence on numbers n. → Enthalpies of vaporization correlate linearly with Kovat's indices. - Abstract: Vapor pressures and the molar enthalpies of vaporization of the linear aliphatic alkanediamines H 2 N-(CH 2 ) n -NH 2 with n = (3 to 12) have been determined using the transpiration method. A linear correlation of enthalpies of vaporization (at T = 298.15 K) of the alkanediamines with the number n and with the Kovat's indices has been found, proving the internal consistency of the measured data.

Spatial and temporal distribution of ambient nitric acid and ammonia in the Athabasca Oil Sands Region, Alberta

Science.gov (United States)

A. Bytnerowicz; W. Fraczek; S. Schilling; D. Alexander

2010-01-01

Monthly average ambient concentrations of gaseous nitric acid (HNO3) and ammonia (NH3) were monitored at the Athabasca Oils Sands Region (AOSR), Alberta, Canada, between May 2005 and September 2008. Generally, concentrations of both pollutants were elevated and highly variable in space and time. The highest atmospheric...

Vapor pressure isotope effect in 13CClF3/12CClF3 by cryogenic distillation kinetics

International Nuclear Information System (INIS)

Wieck, H.J.; Ishida, T.

1975-08-01

The vapor pressure of 13 CClF 3 relative to the vapor pressure of 12 CClF 3 was measured as a function of temperature between 169 0 and 206 0 K by using a modified Bigeleisen distillation column. The transient build-up of the isotopic concentration gradient along the length of the packed column during the start-up period was monitored by taking samples from the condenser section as a function of time. The gaseous samples were completely oxidized to carbon dioxide in the presence of a platinum catalyst and a large excess of oxygen at temperatures between 1050 and 1100 0 C. The combustion products were purified by means of gas chromatography, and the purified carbon dioxide samples were analyzed in a Nier-type isotope-ratio mass spectrometer. The data of each distillation run were reduced in the light of Cohen's theory of the kinetics of square cascade of close-separation stages. The vapor pressure isotope effect for the carbon substitution in CClF 3 at temperatures between 169 0 and 206 0 K was found to be an inverse effect and to be rather insensitive to changes in temperature. The relative vapor pressure may be expressed 1n(P'/P) = [(1.5 +- 14.1)/T 2 ] - [(0.159 +- 0.076)/T], or 1n(P'/P) = [(0.173 +- 0.098)/T] - [(0.11 +- 0.53) x 10 -3 ], where P' and P are the vapor pressures of 12 CClF 3 and 13 CClF 3 , respectively. To the first-order, the presence of chlorine isotopes would not affect the fractionation of carbon isotopes by the distillation of CClF 3

Ultrasound-assisted vapor generation of mercury

Energy Technology Data Exchange (ETDEWEB)

Ribeiro, Anderson S.; Vieira, Mariana A. [Universidade Federal de Santa Catarina, Departamento de Quimica, Florianopolis, SC (Brazil); Willie, Scott; Sturgeon, Ralph E. [National Research Council Canada, Institute for National Measurement Standards, Ottawa, ON (Canada)

2007-06-15

Cold vapor generation arising from reduction of both Hg{sup 2+} and CH{sub 3}Hg{sup +} occurs using ultrasonic (US) fields of sufficient density to achieve both localized heating as well as radical-based attack in solutions of formic and acetic acids and tetramethylammonium hydroxide (TMAH). A batch sonoreactor utilizing an ultrasonic probe as an energy source and a flow through system based on a US bath were optimized for this purpose. Reduction of CH{sub 3}Hg{sup +} to Hg{sup 0} occurs only at relatively high US field density (>10 W cm{sup -3} of sample solution) and is thus not observed when a conventional US bath is used for cold vapor generation. Speciation of mercury is thus possible by altering the power density during the measurement process. Thermal reduction of Hg{sup 2+} is efficient in formic acid and TMAH at 70 C and occurs in the absence of the US field. Room temperature studies with the batch sonoreactor reveal a slow reduction process, producing temporally broad signals having an efficiency of approximately 68% of that arising from use of a conventional SnCl{sub 2} reduction system. Molecular species of mercury are generated at high concentrations of formic and acetic acid. Factors affecting the generation of Hg{sup 0} were optimized and the batch sonoreactor used for the determination of total mercury in SLRS-4 river water reference material. (orig.)

Mechanical properties of PET composites using multi-walled carbon nanotubes functionalized by inorganic and itaconic acids

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A. May-Pat

2012-02-01

Full Text Available Multi-walled carbon nanotubes (MWCNTs were oxidized by two different acid treatments and further functionalized with itaconic acid (IA. The functionalized MWCNTs were used to fabricate Poly(ethylene terephthalate (PET composites by melt mixing. The presence of functional groups on the surface of the treated MWCNTs was confirmed by infrared spectroscopy and thermogravimetric analysis. The MWCNTs oxidized with a concentrated mixture of HNO3 and H2SO4 exhibited more oxygen containing functional groups (OH, COOH but also suffer larger structural degradation than those oxidized by a mild treatment based on diluted HNO3 followed by H2O2. PET composites were fabricated using the oxidized-only and oxidized followed by functionalization with IA MWCNTs. PET composites fabricated with MWCNT oxidized by mild conditions showed improved tensile strength and failure strain, while harsh MWCNT oxidation render them overly brittle.

Use of cationites for separation of transplutonium elements from other elements from aqueous and aqua-alcohol solutions of hydrochloric and nitric acids

International Nuclear Information System (INIS)

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

1984-01-01

The behaviour of Am, Cm, Pu and certain fragment elements (Cs, Sr, Y, Zr, Nb, Ru, Eu) on cationite dauex-50 in aqueous and aqueous-alcohol solutions of HCl and HNO 3 has been studied. Dependences of distribution coefficients and separation factors of the elements on the acid concentration and alcohol content in the solutions are presented. The sorption of TPE by cationite from HCl and HNO 3 solutions in the presence of alcohol is shown to increase over the range of concentrations studied (from 0.5 mol/L to 4-5 mol/L), which is explained by the salting-out effect of alcohol. The distribution coefficients of TPE in the solutions, containing >= 50% alcohol, constitute >= 10 2 . The distribution coefficients of the fragment elements in the presence of alcohol also increase, but to a considerably lesser extent, which results in a better separation. The study of the washing-out curves has shown that, to separate TPE from fragment elements on cationites, both HCl and HNO 3 solutions can be used, at that, in the case of aqueous solutions a better separation is attained at acid concentration, equal to 1 mol/L, and in the case of eluating by aqueous-alcohol solutions a good separation is achieved at hig-her concentrations of the acids as well

The radiolysis of CMPO: effects of acid, metal complexation and alpha vs. gamma radiation

Energy Technology Data Exchange (ETDEWEB)

Bruce J. Mincher; Stephen P. Mezyk; Gary S. Groenewold

2016-05-01

Abstract The group actinide/lanthanide complexing agent octylphenylcarbamoylmethyl phosphine oxide (CMPO) has been examined for its radiation stability by measuring the kinetics of its reactions with free radicals in both the aqueous and organic phases for the free and metal-complexed ligand, identifying its degradation products for both alpha and gamma irradiation, measuring the effects on solvent extraction performance, and measuring the G-values for its degradation under various conditions. This includes the G-values for CMPO in the absence of, and in contact with the acidic aqueous phase, where it is shown that the acidic aqueous phase provides radio-protection for this ligand. It was found that both solvent and metal complexation affect the kinetics of the reaction of the •NO3 radical, a product of HNO3 radiolysis, with CMPO. For example, CMPO complexed with lanthanides has a rate constant for this reaction an order of magnitude higher than for the free ligand, and the reaction for the free ligand in the organic phase is about three times faster than in the aqueous phase. In steady state radiolysis kinetics it was determined that HNO3, although not NO3- anion, provides radio-protection to CMPO, with the G-value for its degradation decreasing with increasing acidity, until it was almost completely suppressed by irradiation in contact with 5 M HNO3. The same degradation products were produced by irradiation with alpha and gamma-sources, except that the relative abundances of these products varied. For example, the product of C-C bond scission was produced only in low amounts for gamma-radiolysis, but it was an important product for samples irradiated with a He ion beam. These results are compared to the new data appearing in the literature on DGA radiolysis, since CMPO and the DGAs both contain the amide functional group.

Role of dust alkalinity in acid mobilization of iron

OpenAIRE

A. Ito; Y. Feng

2010-01-01

Atmospheric processing of mineral aerosols by acid gases (e.g., SO₂, HNO₃, N₂O₅, and HCl) may play a key role in the transformation of insoluble iron (Fe in the oxidized or ferric (III) form) to soluble forms (e.g., Fe(II), inorganic soluble species of Fe(III), and organic complexes of iron). On the other hand, mineral dust particles have a potential of neutralizing the acidic species due to the alkali...

Investigations of AlGaN/GaN HFETs utilizing post-metallization etching by nitric acid treatment

International Nuclear Information System (INIS)

Chou, Bo-Yi; Hsu, Wei-Chou; Liu, Han-Yin; Tsai, Chih-Ming; Ho, Chiu-Sheng; Lee, Ching-Sung

2013-01-01

This work investigates AlGaN/GaN heterostructure field-effect transistors (HFETs) processed by using a simple post-metallization etching (PME) treatment. Decreased gate length (L G ) can be achieved by using nitric acid (HNO 3 ) PME treatment owing to the high etching selectivity of HNO 3 of Ni against the Au and GaN layer. Influences on L G , etched gate profiles and device characteristics with respect to different PME processing parameters by HNO 3 treatment are systematically investigated. Optimum device performance is obtained as L G was reduced to 0.5 µm by using a 1 µm long gate mask by immersing the device into a 45% diluted HNO 3 solution for 35 s. Improved device performances, including maximum drain–source current density (I DS,max : 657.6 mA mm −1 → 898.5 mA mm −1 ), drain–source saturation current density at zero gate bias (I DSS0 : 448.3 mA mm −1 → 653.4 mA mm −1 ), maximum extrinsic transconductance (g m,max : 158.3 mS mm −1 → 219.2 mS mm −1 ), unity-gain cut-off frequency (f T : 12.35 GHz → 22.05 GHz), maximum oscillation frequency (f max : 17.55 GHz → 29.4 GHz) and power-added efficiency (P.A.E.: 26.3% → 34.5%) compared to the untreated reference device, have been successfully achieved. (invited paper)

Vapor Pressures of Several Commercially Used Alkanolamines

NARCIS (Netherlands)

Klepacova, Katarina; Huttenhuis, Patrick J. G.; Derks, Peter W. J.; Versteeg, Geert F.; Klepáčová, Katarína

For the design of acid gas treating processes, vapor-liquid equilibrium (VLE) data must be available of the solvents to be applied. In this study the vapor pressures of seven frequently industrially used alkanolamines (diethanolamine, N-methylethanolamine, N,N-dimethylethanolamine,

Bionanomaterials and Bioinspired Nanostructures for Selective Vapor Sensing

Science.gov (United States)

2013-04-03

agricultural crops. To meet the requirements for these and other demanding applications, new sensing approaches with improved sensor selectivity are required...of these vapors with key side- chain amino acids. DNT-binding peptide receptors were further conjugated to an oligo(ethylene glycol) hydrogel for vapor...coefficient for DNT over TNT vapor. Vapor-phase binding performance was attributed to the ability of the oligo(ethylene glycol) hydrogel to maintain the

The influence of SO4 and NO3 to the acidity (pH) of rainwater using minimum variance quadratic unbiased estimation (MIVQUE) and maximum likelihood methods

Science.gov (United States)

Dilla, Shintia Ulfa; Andriyana, Yudhie; Sudartianto

2017-03-01

Acid rain causes many bad effects in life. It is formed by two strong acids, sulfuric acid (H2SO4) and nitric acid (HNO3), where sulfuric acid is derived from SO2 and nitric acid from NOx {x=1,2}. The purpose of the research is to find out the influence of So4 and NO3 levels contained in the rain to the acidity (pH) of rainwater. The data are incomplete panel data with two-way error component model. The panel data is a collection of some of the observations that observed from time to time. It is said incomplete if each individual has a different amount of observation. The model used in this research is in the form of random effects model (REM). Minimum variance quadratic unbiased estimation (MIVQUE) is used to estimate the variance error components, while maximum likelihood estimation is used to estimate the parameters. As a result, we obtain the following model: Ŷ* = 0.41276446 - 0.00107302X1 + 0.00215470X2.

A pilot study of gaseous pollutants' measurement (NO2, SO2, NH3, HNO3 and O3) in Abidjan, Côte d'Ivoire: contribution to an overview of gaseous pollution in African cities

Science.gov (United States)

Bahino, Julien; Yoboué, Véronique; Galy-Lacaux, Corinne; Adon, Marcellin; Akpo, Aristide; Keita, Sékou; Liousse, Cathy; Gardrat, Eric; Chiron, Christelle; Ossohou, Money; Gnamien, Sylvain; Djossou, Julien

2018-04-01

This work is part of the DACCIWA FP7 project (Dynamics-Aerosol-Chemistry-Cloud Interactions in West Africa) in the framework of the Work Package 2 Air Pollution and Health. This study aims to characterize urban air pollution levels through the measurement of NO2, SO2, NH3, HNO3 and O3 in Abidjan, the economic capital of Côte d'Ivoire. Measurements of inorganic gaseous pollutants, i.e. NO2, SO2, NH3, HNO3 and O3 were performed in Abidjan during an intensive campaign within the dry season (15 December 2015 to 16 February 2016), using INDAAF (International Network to study Deposition and Atmospheric chemistry in AFrica) passive samplers exposed in duplicate for 2-week periods. Twenty-one sites were selected in the district of Abidjan to be representative of various anthropogenic and natural sources of air pollution in the city. Results from this intensive campaign show that gas concentrations are strongly linked to surrounding pollution sources and show a high spatial variability. Also, NH3, NO2 and O3 gases were present at relatively higher concentrations at all the sites. NH3 average concentrations varied between 9.1 ± 1.7 ppb at a suburban site and 102.1 ± 9.1 ppb at a domestic fires site. NO2 mean concentration varied from 2.7 ± 0.1 ppb at a suburban site to 25.0 ± 1.7 ppb at an industrial site. Moreover, we measured the highest O3 concentration at the two coastal sites of Gonzagueville and Félix-Houphouët-Boigny International Airport located in the southeast of the city, with average concentrations of 19.1 ± 1.7 and 18.8 ± 3.0 ppb, respectively. The SO2 average concentration never exceeded 7.2 ± 1.2 ppb over all the sites, with 71.5 % of the sampling sites showing concentrations ranging between 0.4 and 1.9 ppb. The HNO3 average concentration ranged between 0.2 and 1.4 ppb. All these results were combined with meteorological parameters to provide the first mapping of gaseous pollutants on the scale of the district of Abidjan using geostatistical analysis

Validation of nitric acid retrieved by the IMK-IAA processor from MIPAS/ENVISAT measurements

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D. Y. Wang

2007-01-01

Full Text Available The Michelson Interferometer for Passive Atmospheric Sounding (MIPAS onboard the ENVISAT satellite provides profiles of temperature and various trace-gases from limb-viewing mid-infrared emission measurements. The stratospheric nitric acid (HNO3 from September 2002 to March 2004 was retrieved from the MIPAS observations using the science-oriented data processor developed at the Institut für Meteorologie und Klimaforschung (IMK, which is complemented by the component of non-local thermodynamic equilibrium (non-LTE treatment from the Instituto de Astrofísica de Andalucía (IAA. The IMK-IAA research product, different from the ESA operational product, is validated in this paper by comparison with a number of reference data sets. Individual HNO3 profiles of the IMK-IAA MIPAS show good agreement with those of the balloon-borne version of MIPAS (MIPAS-B and the infrared spectrometer MkIV, with small differences of less than 0.5 ppbv throughout the entire altitude range up to about 38 km, and below 0.2 ppbv above 30 km. However, the degree of consistency is largely affected by their temporal and spatial coincidence, and differences of 1 to 2 ppbv may be observed between 22 and 26 km at high latitudes near the vortex boundary, due to large horizontal inhomogeneity of HNO3. Statistical comparisons of MIPAS IMK-IAA HNO3 VMRs with respect to those of satellite measurements of Odin/SMR, ILAS-II, ACE-FTS, as well as the MIPAS ESA product show good consistency. The mean differences are generally ±0.5 ppbv and standard deviations of the differences are of 0.5 to 1.5 ppbv. The maximum differences are 2.0 ppbv around 20 to 25 km. This gives confidence in the general reliability of MIPAS HNO3 VMR data and the other three satellite data sets.

New analysis of the ν5 and 2 ν9 bands of HNO 3 by infrared and millimeter wave techniques: line positions and intensities

Science.gov (United States)

Perrin, A.; Orphal, J.; Flaud, J.-M.; Klee, S.; Mellau, G.; Mäder, H.; Walbrodt, D.; Winnewisser, M.

2004-12-01

Nitric acid (HNO 3) plays an important role in the Earth's atmosphere as a reservoir molecule of NO x species. It has a strong infrared signature at 11 μm which is one of the most commonly used for the infrared retrieval of this species in the atmosphere since this spectral region coincides with an atmospheric window. It is therefore essential to have high quality spectral parameters in this spectral region. The main goal of this work is then to generate as reliable as possible line positions and intensities for the ν5 and 2 ν9 cold bands centered at 879.1075 and 896.4467 cm -1, respectively. In particular the existing line parameters need improvement in the wings of the 11 μm window in order to retrieve more accurately the CFC-11 (CCl 3F) and CFC-12 (CCl 2F 2) atmospheric species at ˜850 and ˜920 cm -1, respectively. This work is also motivated by theoretical considerations. Very strong resonances couple indeed the 5 1 and 9 2 rotational levels. In addition the ν9 mode (OH torsion) is a "large amplitude" motion, and torsional splittings affect both the v9=2 and the v5=1 rotational transitions. In the present study, these effects are accounted for simultaneously both for the line position and line intensity calculations. To calculate the line positions the Hamiltonian matrix accounts for the very strong Fermi and the weaker Coriolis interactions linking the 5 1⇔9 2 rotational levels, and the torsional effects are accounted for within the frame of the IAM (Internal Axis Method) approach. In addition, the v-diagonal blocks involve non-orthorhombic operators together with Watson's type rotational operators. This means that the z-quantization axis deviates from the a inertial axis for both the 5 1 and 9 2 vibrational states. The line intensity calculations were performed accounting also for the axis switching effects. As far as the experimental line positions are concerned we have used the millimeter wave data available in the literature [J. Mol. Spectrosc

Studies in the solubility of Pu(III) oxalate

Energy Technology Data Exchange (ETDEWEB)

Hasilkar, S P; Khedekar, N B; Chander, K; Jadhav, V; Jain, H C [Bhabha Atomic Research Centre, Bombay (India). Fuel Reprocessing Div.

1994-11-01

Studies have been carried out on the solubility of Pu(III) oxalate by precipitation of Pu(III) oxalate from varying concentrations of HNO[sub 3]/HCl (0.5-2.0M) solutions and also by equilibrating freshly prepared Pu(III) oxalate with solutions containing varying concentrations of HNO[sub 3]/HCl, oxalic acid and ascorbic acid. Pu(III) solutions in HNO[sub 3] and HCl media were prepared by reduction of Pu(IV) with ascorbic acid. 0.01-0.10M ascorbic acid concentration in the aqueous solution was maintained as holding reductant. The solubility of Pu(III) oxalate was found to be a minimum in 0.5M-1M HNO[sub 3]/HCl solutions containing 0.05M ascorbic acid and 0.2M excess oxalic acid in the supernatant. (author) 6 refs.; 6 tabs.

Determination of Hg(II) in waters by on-line preconcentration using Cyanex 923 as a sorbent - Cold vapor atomic absorption spectrometry

International Nuclear Information System (INIS)

Duan Taicheng; Song Xuejie; Xu Jingwei; Guo Pengran; Chen Hangting; Li Hongfei

2006-01-01

Using a solid phase extraction mini-column home-made from a neutral extractant Cyanex 923, inorganic Hg could be on-line preconcentrated and simultaneously separated from methyl mercury. The preconcentrated Hg (II) was then eluted with 10% HNO 3 and subsequently reduced by NaBH 4 to form Hg vapor before determination by cold vapor atomic absorption spectrometry (CVAAS). Optimal conditions for and interferences on the Hg preconcentration and measurement were at 1% HCl, for a 25 mL sample uptake volume and a 10 mL min -1 sample loading rate. The detection limit was 0.2 ng L -1 and much lower than that of conventional method (around 15.8 ng L -1 ). The relative standard deviation (RSD) is 1.8% for measurements of 40 ng L -1 of Hg and the linear working curve is from 20 to 2000 ng L -1 (with a correlation coefficient of 0.9996). The method was applied in determination of inorganic Hg in city lake and deep well water (from Changchun, Jilin, China), and recovery test results for both samples were satisfactory

Medicinal Cannabis: In Vitro Validation of Vaporizers for the Smoke-Free Inhalation of Cannabis.

Directory of Open Access Journals (Sweden)

Christian Lanz

Full Text Available Inhalation by vaporization is a promising application mode for cannabis in medicine. An in vitro validation of 5 commercial vaporizers was performed with THC-type and CBD-type cannabis. Gas chromatography/mass spectrometry was used to determine recoveries of total THC (THCtot and total CBD (CBDtot in the vapor. High-performance liquid chromatography with photodiode array detection was used for the quantitation of acidic cannabinoids in the residue and to calculate decarboxylation efficiencies. Recoveries of THCtot and CBDtot in the vapor of 4 electrically-driven vaporizers were 58.4 and 51.4%, 66.8 and 56.1%, 82.7 and 70.0% and 54.6 and 56.7% for Volcano Medic®, Plenty Vaporizer®, Arizer Solo® and DaVinci Vaporizer®, respectively. Decarboxylation efficiency was excellent for THC (≥ 97.3% and CBD (≥ 94.6%. The gas-powered Vape-or-Smoke™ showed recoveries of THCtot and CBDtot in the vapor of 55.9 and 45.9%, respectively, and a decarboxylation efficiency of ≥ 87.7 for both cannabinoids. However, combustion of cannabis was observed with this device. Temperature-controlled, electrically-driven vaporizers efficiently decarboxylate inactive acidic cannabinoids and reliably release their corresponding neutral, active cannabinoids. Thus, they offer a promising application mode for the safe and efficient administration of medicinal cannabis.

Ammonia vapor sensing properties of polyaniline-titanium(IV)phosphate cation exchange nanocomposite.

Science.gov (United States)

Khan, Asif Ali; Baig, Umair; Khalid, Mohd

2011-02-28

In this study, the electrically conducting polyaniline-titanium(IV)phosphate (PANI-TiP) cation exchange nanocomposite was synthesized by sol-gel method. The cation exchange nanocomposite based sensor for detection of ammonia vapors was developed at room temperature. It was revealed that the sensor showed good reversible response towards ammonia vapors ranging from 3 to 6%. It was found that the sensor with p-toluene sulphonic acid (p-TSA) doped exhibited higher sensing response than hydrochloric acid doped. This sensor has detection limit ≤1% ammonia. The response of resistivity changes of the cation exchange nanocomposite on exposure to different concentrations of ammonia vapors shows its utility as a sensing material. These studies suggest that the cation exchange nanocomposite could be a good material for ammonia sensor at room temperature. Copyright © 2010 Elsevier B.V. All rights reserved.

Determination of mercury in gasoline by cold vapor atomic absorption spectrometry with direct reduction in microemulsion media

Energy Technology Data Exchange (ETDEWEB)

Brandao, Geisamanda Pedrini [Department of Chemistry, Pontifical Catholic University of Rio de Janeiro, Rua Marques de S. Vicente, 225, Gavea, 22453-900, Rio de Janeiro, RJ (Brazil); Calixto de Campos, Reinaldo [Department of Chemistry, Pontifical Catholic University of Rio de Janeiro, Rua Marques de S. Vicente, 225, Gavea, 22453-900, Rio de Janeiro, RJ (Brazil)]. E-mail: rccampos@rdc.puc-rio.br; Luna, Aderval Severino [Department of Analytical Chemistry, Rio de Janeiro State University, Rua S. Francisco Xavier, s/n, Maracana, 20550-900, Rio de Janeiro, RJ (Brazil)

2005-06-30

The determination of Hg in gasoline by cold vapor atomic absorption spectrometry, after direct aqueous NaBH{sub 4} reduction in a three-component (microemulsion) medium, was investigated. Microemulsions were prepared by mixing gasoline with propan-1-ol and 50% v / v HNO{sub 3} at a 20 : 15 : 1 volume ratio. A long-term homogeneous system was immediately formed this way. After reduction, the Hg vapor generated in a reaction flask was transported to an intermediate K{sub 2}Cr{sub 2}O{sub 7}/H{sub 2}SO{sub 4} trap solution in order to avoid poisoning of the Au-Pt trap by the gasoline vapors. A second reduction step was then conducted and the generated Hg vapor transported to the Au-Pt trap, followed by thermal release of Hg{sup 0} and atomic absorption measurement. Purified N{sub 2} was used as purge and transport gas. After multivariate optimization by central composite design calibration graphs showed coefficients of correlation of 0.9999 and a characteristic mass of 2 ng was obtained. Typical coefficients of variation of 5% and 6% were found for ten consecutive measurements at concentration levels of 1 and 8 {mu}g L{sup -1} of Hg{sup 2+}, respectively. The limit of detection was 0.10 {mu}g L{sup -1} (0.14 {mu}g kg{sup -1}) in the original sample. A total measurement cycle took 11 min, permitting duplicate analysis of 3 samples per hour. The results obtained with the proposed procedure in the analysis of commercial gasoline samples were in agreement with those obtained by a comparative procedure. Gasoline samples of the Rio de Janeiro city have shown Hg concentrations below 0.27 {mu}g L{sup -1}.

Liquid-vapor equilibrium in VOCl3-Si2OCl6 and VOCl3-CCl3COCl systems

International Nuclear Information System (INIS)

Tret'yakova, K.V.

1976-01-01

Two methods were used in a study of liquid-vapor equilibrium of VOCl 3 -Si 2 OCl 6 (1) and VOCl 3 -CCl 3 COCl (2) systems. The first, ebulliometric method was used for determining the relationship saturated vapor pressure in the range from 450-500 to 1450-1500 mm Hg and the temperature which is in the range from 100-110 to 150-160 deg C. The data on saturated vapor pressure of pure substances and their mixtures were interpreted by the least squares method according to an equations of the type lgP=A-B/T. For 760 mm Hg isobar the dependence of the b.p. of system 1 on the concentration of its components considerably deviates fron the ideal state. In this case positive azeotrope is formed (b.p. 126.5 deg C) containing 83.5% mole VOCl 3 . The Van Laar euqation was used in calculating the relative volatility. At 760 mm Hg pressure in I, Si 2 OCl 6 is more volatile, the difference between the normal b.p. of VOCl 6 (127.7 deg C) and that of the azeotropic mixture (126.5 deg C) being only 1.2 deg C. The Rayleigh distillation method was used for direct determination of the volatility of this system. The average value for αsub(Si 2 OCl 6 /VOCl 3 ) was found to be 1.44. It accords well with the value of 1.47 obtained from an extrapolation of results for pure VOCl 3 on the basis of the ebulloimetric measurements. In the case of system 2 a considerable positive deviation from the ideal state was observed within the entire range of concentrations. Calculations of the activity coefficients for the components of this system, the composition of the vapor phase and the relative volatility were made with the aid of the Dugem-Margulis equation. The value for the relative volatility αsub(CCl 3 COCl/VOCl 3 ), as extrapolated for pure VOCl 3 , was 1.8. No direct measurements of α were made in this case owing to difficulties in analysis of the two components

Optimization of a single-drop microextraction method for multielemental determination by electrothermal vaporization inductively coupled plasma mass spectrometry following in situ vapor generation

International Nuclear Information System (INIS)

Gil, Sandra; Loos-Vollebregt, Margaretha T.C. de; Bendicho, Carlos

2009-01-01

A headspace single-drop microextraction (HS-SDME) method has been developed in combination with electrothermal vaporization inductively coupled plasma mass spectrometry (ETV-ICP-MS) for the simultaneous determination of As, Sb, Bi, Pb, Sn and Hg in aqueous solutions. Vapor generation is carried out in a 40 mL volume closed-vial containing a solution with the target analytes in hydrochloric acid and potassium ferricyanide medium. Hydrides (As, Sb, Bi, Pb, Sn) and Hg vapor are trapped onto an aqueous single drop (3 μL volume) containing Pd(II), followed by the subsequent injection in the ETV. Experimental variables such as medium composition, sodium tetrahydroborate (III) volume and concentration, stirring rate, extraction time, sample volume, ascorbic acid concentration and palladium amount in the drop were fully optimized. The limits of detection (LOD) (3σ criterion) of the proposed method for As, Sb, Bi, Pb, Sn and Hg were 0.2, 0.04, 0.01, 0.07, 0.09 and 0.8 μg/L, respectively. Enrichment factors of 9, 85, 138, 130, 37 and 72 for As, Sb, Bi, Pb, Sn and Hg, respectively, were achieved in 210 s. The relative standard deviations (N = 5) ranged from 4 to 8%. The proposed HS-SDME-ETV-ICP-MS method has been applied for the determination of As, Sb, Bi, Pb, Sn and Hg in NWRI TM-28.3 certified reference material.

Vaporization of protic ionic liquids derived from organic superbases and short carboxylic acids.

Science.gov (United States)

Ribeiro, Filipe M S; Lima, Carlos F R A C; Vaz, Inês C M; Rodrigues, Ana S M C; Sapei, Erlin; Melo, André; Silva, Artur M S; Santos, Luís M N B F

2017-06-28

This work presents a comprehensive evaluation of the phase behaviour and cohesive enthalpy of protic ionic liquids (PILs) composed of 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) or 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) organic superbases with short-chain length (acetic, propionic and butyric) carboxylic acids. Glass transition temperatures, T g , and enthalpies of vaporization, ΔH vap , were measured for six [BH][A] (1 : 1) PILs (B = DBN, DBU; A = MeCOO, EtCOO, nPrCOO), revealing more significant changes upon increasing the number of -CH 2 - groups in the base than in the acid. The magnitude of ΔH vap evidences that liquid PILs have a high proportion of ions, although the results also indicate that in DBN PILs the concentration of neutral species is not negligible. In the gas phase, these PILs exist as a distribution of ion pairs and isolated neutral species, with speciation being dependent on the temperature and pressure conditions - at high temperatures and low pressures the separated neutral species dominate. The higher T g and ΔH vap of the DBU PILs are explained by the stronger basicity of DBU (as supported by NMR and computational calculations), which increases the extent of proton exchange and the ionic character of the corresponding PILs, resulting in stronger intermolecular interactions in condensed phases.

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

Science.gov (United States)

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.

HF effect on dissociation kinetics of plutonium and neptunium complexes with 1,2-diaminocyclohexanetetraacetic acid in nitric acid solutions

International Nuclear Information System (INIS)

Nikitina, S.A.; Stepanov, A.V.

1982-01-01

Dissociation kinetics of Pusup((4)) and Np sup((4)) complexes with DCTA were investigated in HNO 3 solutions in the presence of HF and arsenazo 3. It was found that HF or NaF produced a differentiating effect on the reactivity of the complexes at [HNO 3 ]=1-6 mol/l as well as inhibiting effect at [HNO 3 ]=0.01 mol/l. Conditions of the differential kinetic analysis of plutonium and neptunium in the mixture and differential spectrophotometric analysis of uranium (6) during the camouflage of neptunium (4) and plutonium (4) were determined

Understanding the doping effects on the structural and electrical properties of ultrathin carbon nanotube networks

International Nuclear Information System (INIS)

Zhou, Ying; Shimada, Satoru; Azumi, Reiko; Saito, Takeshi

2015-01-01

Similar to other semiconductor technology, doping of carbon nanotube (CNT) thin film is of great significance for performance improvement or modification. However, it still remains a challenge to seek a stable and effective dopant. In this paper, we unitize several spectroscopic techniques and electrical characterizations under various conditions to investigate the effects of typical dopants and related methods. Nitric acid (HNO 3 ) solution, I 2 vapor, and CuI nanoparticles are used to modify a series of ultrathin CNT networks. Although efficient charge transfer is achieved initially after doping, HNO 3 is not applicable because it suffers from severe reliability problems in structural and electrical properties, and it also causes a number of undesired structural defects. I 2 vapor doping at 150 °C can form some stable C-I bonding structures, resulting in relatively more stable but less efficient electrical performances. CuI nanoparticles seem to be an ideal dopant. Photonic curing enables the manipulation of CuI, which not only results in the construction of novel CNT-CuI hybrid structures but also encourages the deepest level of charge transfer doping. The excellent reliability as well as processing feasibility identify the bright perspective of CNT-CuI hybrid film for practical applications

Understanding the doping effects on the structural and electrical properties of ultrathin carbon nanotube networks

Energy Technology Data Exchange (ETDEWEB)

Zhou, Ying, E-mail: y-shuu@aist.go.jp; Shimada, Satoru; Azumi, Reiko [Electronics and Photonics Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, 305-8565 Tsukuba (Japan); Saito, Takeshi [Nanomaterials Research Institute, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, 305-8565 Tsukuba (Japan)

2015-12-07

Similar to other semiconductor technology, doping of carbon nanotube (CNT) thin film is of great significance for performance improvement or modification. However, it still remains a challenge to seek a stable and effective dopant. In this paper, we unitize several spectroscopic techniques and electrical characterizations under various conditions to investigate the effects of typical dopants and related methods. Nitric acid (HNO{sub 3}) solution, I{sub 2} vapor, and CuI nanoparticles are used to modify a series of ultrathin CNT networks. Although efficient charge transfer is achieved initially after doping, HNO{sub 3} is not applicable because it suffers from severe reliability problems in structural and electrical properties, and it also causes a number of undesired structural defects. I{sub 2} vapor doping at 150 °C can form some stable C-I bonding structures, resulting in relatively more stable but less efficient electrical performances. CuI nanoparticles seem to be an ideal dopant. Photonic curing enables the manipulation of CuI, which not only results in the construction of novel CNT-CuI hybrid structures but also encourages the deepest level of charge transfer doping. The excellent reliability as well as processing feasibility identify the bright perspective of CNT-CuI hybrid film for practical applications.

A novel tandem differential mobility analyzer with organic vapor treatment of aerosol particles

Directory of Open Access Journals (Sweden)

J. Joutsensaari

2001-01-01

Full Text Available A novel method to characterize the organic composition of aerosol particles has been developed. The method is based on organic vapor interaction with aerosol particles and it has been named an Organic Tandem Differential Mobility Analyzer (OTDMA. The OTDMA method has been tested for inorganic (sodium chloride and ammonium sulfate and organic (citric acid and adipic acid particles. Growth curves of the particles have been measured in ethanol vapor and as a comparison in water vapor as a function of saturation ratio. Measurements in water vapor show that sodium chloride and ammonium sulfate as well as citric acid particles grow at water saturation ratios (S of 0.8 and above, whereas adipic acid particles do not grow at S S = 0.75 and S = 0.79, respectively. Citric acid particles grow monotonously with increasing saturation ratios already at low saturation ratios and no clear deliquescence point is found. For sodium chloride and ammonium sulfate particles, no growth can be seen in ethanol vapor at saturation ratios below 0.93. In contrast, for adipic acid particles, the deliquescence takes place at around S = 0.95 in the ethanol vapor. The recrystallization of adipic acid takes place at S The results show that the working principles of the OTDMA are operational for single-component aerosols. Furthermore, the results indicate that the OTDMA method may prove useful in determining whether aerosol particles contain organic substances, especially if the OTDMA is operated in parallel with a hygroscopicity TDMA, as the growth of many substances is different in ethanol and water vapors.

Dissolution of oxalate precipitate and destruction of oxalate ion by hydrogen peroxide in nitric acid solution

International Nuclear Information System (INIS)

Kim, Eung-Ho; Chung, Dong-Yong; Park, Jin-Ho; Yoo, Jae-Hyung

2000-01-01

This study aims at developing an oxalate precipitation process, which is applicable to a partitioning of long-lived radionuclides from the high-level radioactive liquid waste. In order to achieve this, a study for decomposition-reaction of oxalic acid by hydrogen peroxide was first carried out. The decomposition rates of H 2 O 2 and oxalic acid increased with an increase of nitric acid concentration, and especially those decomposition rates steeply increased at more than 2 M HNO 3 . Based on this result, the decomposition kinetics of H 2 O 2 and oxalic acid were suggested in this work. Then, the dissolution of oxalate precipitate and the destruction of oxalate ion in the solution were examined. Oxalate precipitates were prepared by adding oxalic acid into a simulated radioactive waste containing 8 metallic elements. The precipitates obtained thereby were dissolved in various nitric acid concentrations and reacted with H 2 O 2 at 90degC. When the oxalates were completely dissolved, most of the oxalates were decomposed by adding H 2 O 2 , but in a slurry state the decomposition yield of the oxalate decreased with an increase of the slurry density in the solution. Such phenomenon was considered to be due to a catalytic decomposition of H 2 O 2 on a solid surface of oxalate and the decomposition mechanism was explained by a charge transfer from a surface of oxalate solid to H 2 O 2 , producing OH radicals which can destruct H 2 O 2 explosively. Accordingly, the experimental condition for the decomposition of the oxalate precipitates was found to be most favorable at 3 M HNO 3 under the initial concentrations of 0.2 M oxalate and 1 M H 2 O 2 . At 3M HNO 3 , oxalate precipitates could be safely and completely dissolved, and almost decomposed. Additionally, it was observed that the presence of ferric ion in the solution largely affects the decomposition rate of H 2 O 2 . This could be explained by a chain reaction of hydrogen peroxide with ferric ion in the solution

Surface functionalization of 3D-printed plastics via initiated chemical vapor deposition

Directory of Open Access Journals (Sweden)

Christine Cheng

2017-08-01

Full Text Available 3D printing is a useful fabrication technique because it offers design flexibility and rapid prototyping. The ability to functionalize the surfaces of 3D-printed objects allows the bulk properties, such as material strength or printability, to be chosen separately from surface properties, which is critical to expanding the breadth of 3D printing applications. In this work, we studied the ability of the initiated chemical vapor deposition (iCVD process to coat 3D-printed shapes composed of poly(lactic acid and acrylonitrile butadiene styrene. The thermally insulating properties of 3D-printed plastics pose a challenge to the iCVD process due to large thermal gradients along the structures during processing. In this study, processing parameters such as the substrate temperature and the filament temperature were systematically varied to understand how these parameters affect the uniformity of the coatings along the 3D-printed objects. The 3D-printed objects were coated with both hydrophobic and hydrophilic polymers. Contact angle goniometry and X-ray photoelectron spectroscopy were used to characterize the functionalized surfaces. Our results can enable the use of iCVD to functionalize 3D-printed materials for a range of applications such as tissue scaffolds and microfluidics.

Moessbauer study of corrosion induced by acid rain

International Nuclear Information System (INIS)

Arshed, M.; Hussain, N.; Siddiqui, M.; Anwar-ul-Islam, M.; Rehman, S.; Butt, N.M.

1997-01-01

Strictly speaking acid rain refers to wet precipitation of pollutants S0/sub 2/SO/sub 3/ and NO/sub x/HNO/sub 3/ which have dissolved in cloud and rain droplets to from sulphuric and nitric acids. Acid rain has seriously damaged pine and spruce forests in Canada, USA and Europe. In these areas it has caused damage to buildings, reduced fish population due to acidification of lakes and rivers, and affected health of human beings as a result of poor water quality. The corrosion products formed in a simulated acid rain environment have been identified with transmission Moessbauer spectroscopy using a /sup 57/Co source. They were found to be gamma-FeOOH, alpha-FeOOH, gamma-Fe/sub 2/O/sub 3/ and a phase with unfamiliar parameters which seems to be amorphous in nature and can be considered as an intermediate phase. (author)

Li vaporization property of two-phase material of Li{sub 2}TiO{sub 3} and Li{sub 2}SiO{sub 3} for tritium breeder

Energy Technology Data Exchange (ETDEWEB)

Ogawa, Seiya [Course of Mechanical Engineering, Graduate School of Engineering, Tokai University, 4-1-1 Kitakaname, Hiratsuka, Kanagawa 259-1292 (Japan); Masuko, Yuki; Kato, Hirokazu; Yuyama, Hayato; Sakai, Yutaro [Department of Prime Mover Engineering, School of Engineering, Tokai University, 4-1-1 Kitakaname, Hiratsuka, Kanagawa 259-1292 (Japan); Niwa, Eiki; Hashimoto, Takuya [Department of Physics, College of Humanities and Sciences, Nihon University, 3-8-1 Sakurajousui, Setagaya-ku, Tokyo 156-8550 (Japan); Mukai, Keisuke [Department of Nuclear Engineering and Management, School of Engineering, The University of Tokyo, 7-3-1 Bunkyo-ku, Tokyo 113-8656 (Japan); Hosino, Tsuyoshi [Breeding Functional Materials Development Group, Department of Blanket Systems Research, Rokkasho Fusion Institute, Sector of Fusion Research and Development, Japan Atomic Energy Agency, 2-166 Obuch, Omotedate, Rokkasho-mura, Kamikita-gun, Aomori 039-3212 (Japan); Sasaki, Kazuya, E-mail: k_sasaki@tokai-u.jp [Course of Mechanical Engineering, Graduate School of Engineering, Tokai University, 4-1-1 Kitakaname, Hiratsuka, Kanagawa 259-1292 (Japan); Department of Prime Mover Engineering, School of Engineering, Tokai University, 4-1-1 Kitakaname, Hiratsuka, Kanagawa 259-1292 (Japan); Course of Mechanical Engineering and Aeronautics and Astronautics, Graduate School of Science and Technology, Tokai University, 4-1-1 Kitakaname, Hiratsuka, Kanagawa 259-1292 (Japan)

2015-10-15

Highlights: • We synthesized two phase materials based on Li{sub 2}SiO{sub 3} and Li{sub 2}TiO{sub 3}. • We investigated the Li vaporization property of the two-phase materials. • Li vaporization occurs significantly from only Li{sub 2}SiO{sub 3} grains in the vicinity of the surface of the pellets. • The Li vaporization is remarkable only for an early short time for the vaporization from Li{sub 2}SiO{sub 3} grains at the vicinity of the surface. • The second stable phase added functions effectively for inhibition of the Li vaporization. - Abstract: Li vaporization property of two-phase materials of Li{sub 2}TiO{sub 3} and Li{sub 2}SiO{sub 3} in a working condition for the solid tritium breeder used in the demonstration power plant of fusion reactor was investigated, and the suppression mechanism of the vaporization was considered. The Li vaporization rate from the specimen pellet was measured by gravimetric method, and the change of Li concentration distribution in the pellet was analyzed by time-of-flight secondary ion mass spectrometer. Li was vaporized only from the Li{sub 2}SiO{sub 3} at the vicinity of the surface of the pellet. The remarkable vaporization of Li arose only in an early short time. The inhibition of the vaporization from the Li{sub 2}SiO{sub 3} was successful by adding the small amount of the stable secondary phase of Li{sub 2}TiO{sub 3}.

The thermodynamic characteristics of vaporization in the NaI-PrI3 system

Science.gov (United States)

Motalov, V. B.; Kudin, L. S.; Markus, T.

2009-05-01

The vaporization of the NaI-PrI3 quasi-binary system was studied by high-temperature mass spectrometry over the whole concentration range. At 623-994 K, saturated vapor contained not only (NaI) n and (PrI3) n molecules ( n = 1, 2) and Na+(NaI) n ( n = 0-4) and I-(PrI3) n ( n = 1-2) ions but also mixed molecular and ionic associates recorded for the first time (NaPrI4, Na2PrI5, NaPrI{3/+}, Na2PrI{4/+}, Na3PrI{5/+}, Na4PrI{6/+}, NaPrI{5/-}, and NaPr2I{8/-}). The partial vapor pressures of molecules were calculated, and the equilibrium constants of the dissociation of neutral and charged associates were measured. The enthalpies of molecular and ion-molecular reactions were determined, and the enthalpies of formation of gaseous molecules and ions were obtained.

Uniformly Distributed Graphene Domain Grows on Standing Copper via Low-Pressure Chemical Vapor Deposition

Directory of Open Access Journals (Sweden)

Shih-Hao Chan

2013-01-01

Full Text Available Uniformly distributed graphene domains were synthesized on standing copper foil by a low-pressure chemical vapor deposition system. This method improved the distribution of the graphene domains at different positions on the same piece of copper foil along the forward direction of the gas flow. Scanning electron microscopy (SEM showed the average size of the graphene domains to be about ~20 m. This results show that the sheet resistance of monolayer graphene on a polyethylene terephthalate (PET substrate is about ~359 /□ whereas that of the four-layer graphene films is about ~178 /□, with a transmittance value of 88.86% at the 550 nm wavelength. Furthermore, the sheet resistance can be reduced with the addition of HNO3 resulting in a value of 84 /□. These values meet the absolute standard for touch sensor applications, so we believe that this method can be a candidate for some transparent conductive electrode applications.

COMPARATIVE ANALYSIS OF OXALIC ACID PRODUCED FROM RICE HUSK AND PADDY

OpenAIRE

P.I. Oghome; K.O.Amanze; C.I.O.Kamalu; A.C Nkwocha; S.O.Opebiyi

2012-01-01

In this research work, comparative analysis of Oxalic acid produced from Rice husk and Paddy was carried out in order to ascertain which waste sample produced a better yield. Nitric acid oxidation of carbohydrates was the method adopted in the production. The variable ratios of HNO3:H2SO4 used were 80:20, 70:30, 60:40, and 50:50. The variable ratio of 60:40 gave the maximum yield and at a maximum temperature of 75oC. Rice husk sample gave a percentage yield of 53.2, 64.4, 81.0, and 53.3 at te...

Synthesis of freestanding water-soluble indium oxide nanocrystals capped by alanine nitric acid via ligand exchange for thin film transistors and effects of ligands on the electrical properties

Energy Technology Data Exchange (ETDEWEB)

Choi, Jin-Kyu; Koh, Ye-Seul; Jeong, Hyun-Dam, E-mail: hdjeong@chonnam.ac.kr

2015-07-15

We demonstrate synthesis of freestanding water-soluble indium oxide nanocrystals (In{sub 2}O{sub 3} NCs) by ligand exchange to β-alanine nitric acid (Ala·HNO{sub 3}) and its application for active channel layer in thin film transistors (TFTs), with investigation of the effect of curing temperatures on the TFT properties in terms of thermal behaviour of the ligand molecules at 150, 300, and 350 °C. After ligand exchange from long alkyl ligand (myristic acid, MA) to short Ala·HNO{sub 3}, the mobility of NC TFTs cured at 150 °C increased by over 1 order of magnitude, from 1.3 × 10{sup −4} cm{sup 2}V{sup -1}s{sup −1} to 4.5 × 10{sup −3} cm{sup 2}V{sup -1}s{sup −1}, due to enhanced tunnelling rate (Γ) between adjective NCs. Higher curing temperatures such as 300 and 350 °C, inducing thermal decomposition of the organic ligands, led to further enhancement of the mobility, particularly up to 2.2 cm{sup 2}V{sup -1}s{sup −1} for the In{sub 2}O{sub 3} NC-Ala·HNO{sub 3} TFT cured at 350 °C. It is also found that the ligand exchange of In{sub 2}O{sub 3} NC in acidic condition (e.g. HNO{sub 3}) would be simple and effective to reduce the surface defects by surface etching, which may lead to better device performances. - Graphical abstract: Display Omitted - Highlights: • Freestanding water-soluble In{sub 2}O{sub 3} nanocrystals (NCs) were synthesized by ligand exchange. • Thin film transistors (TFTs) of colloidal NCs were fabricated by spin-coating method. • Water-soluble In{sub 2}O{sub 3} NC TFTs showed higher mobilities due to shorter ligand length. • Surface defects of NCs were notably reduced by surface etching during ligand exchange.

Chronic administration of the HNO donor Angeli's salt does not lead to tolerance, cross-tolerance, or endothelial dysfunction: comparison with GTN and DEA/NO.

Science.gov (United States)

Irvine, Jennifer C; Kemp-Harper, Barbara K; Widdop, Robert E

2011-05-01

Nitroxyl (HNO) displays distinct pharmacology to its redox congener nitric oxide (NO(•)) with therapeutic potential in the treatment of heart failure. It remains unknown if HNO donors are resistant to tolerance development following chronic in vivo administration. Wistar-Kyoto rats received a 3-day subcutaneous infusion of one of the NO(•) donors, glyceryl trinitrate (GTN) or diethylamine/NONOate (DEA/NO), or the HNO donor Angeli's salt (AS). GTN infusion (10 μg/kg/min) resulted in significantly blunted depressor responses to intravenous bolus doses of GTN, demonstrating tolerance development. By contrast, infusion with AS (20 μg/kg/min) or DEA/NO (2 μg/kg/min) did not alter their subsequent depressor responses. Similarly, ex vivo vasorelaxation responses in isolated aortae revealed that GTN infusion elicited a significant 6-fold decrease in the sensitivity to GTN and reduction in the maximum response to acetylcholine (ACh). Chronic infusion of AS or DEA/NO had no effect on subsequent vasorelaxation responses to themselves or to ACh. No functional cross-tolerance between nitrovasodilators was evident, either in vivo or ex vivo, although an impaired ability of a nitrovasodilator to increase tissue cGMP content was not necessarily indicative of a reduced functional response. In conclusion, HNO donors may represent novel therapies for cardiovascular disease with therapeutic potential over clinically used organic nitrates.

HF effect on dissociation kinetics of plutonium and neptunium complexes with 1,2-diaminocyclohexanetetraacetic acid in nitric acid solutions

Energy Technology Data Exchange (ETDEWEB)

Nikitina, S.A.; Stepanov, A.V.

1982-01-01

Dissociation kinetics of Pusup((4)) and Np sup((4)) complexes with DCTA were investigated in HNO/sub 3/ solutions in the presence of HF and arsenazo 3. It was found that HF or NaF produced a differentiating effect on the reactivity of the complexes at (HNO/sub 3/)=1-6 mol/l as well as inhibiting effect at (HNO/sub 3/)=0.01 mol/l. Conditions of the differential kinetic analysis of plutonium and neptunium in the mixture and differential spectrophotometric analysis of uranium (6) during the camouflage of neptunium (4) and plutonium (4) were determined.

Experimental vapor pressures (from 1 Pa to 100 kPa) of six saturated Fatty Acid Methyl Esters (FAMEs): Methyl hexanoate, methyl octanoate, methyl decanoate, methyl dodecanoate, methyl tetradecanoate and methyl hexadecanoate

International Nuclear Information System (INIS)

Sahraoui, Lakhdar; Khimeche, Kamel; Dahmani, Abdallah; Mokbel, Ilham; Jose, Jacques

2016-01-01

Highlight: • Vapor-liquid equilibria, Enthalpy of Vaporization, saturated Fatty Acid Methyl Ester. - Abstract: Vapor pressures of six saturated Fatty Acid Methyl Esters (FAMEs), methyl hexanoate (or methyl caproate), methyl octanoate (or methyl caprylate), Methyl decanoate (or methyl caprate), methyl dodecanoate (or methyl laurate), methyl tetradecanoate (or methyl myristate), and methyl hexadecanoate (or methyl palmitate) were measured from 1 Pa to 100 kPa and at temperature range between 262 and 453 K using a static apparatus. The experimental data (P-T) were compared with the available literature data.

Characterization of lignocellulosic biomass thermal degradation and physiochemical structure: Effects of demineralization by diverse acid solutions

International Nuclear Information System (INIS)

Asadieraghi, Masoud; Wan Daud, Wan Mohd Ashri

2014-01-01

Highlights: • HF showed interesting results on EFB (empty fruit bunches) and PMF (palm mesocarp fibre) deashing. • HCl indicated maximum ash removal from PKS (palm kernel shell). • Significant pyrolysis reactions took place at ∼250 °C to ∼400 °C. • Inorganics played a considerable catalytic role during the biomasses pyrolysis. • Acid pretreatment introduced some impacts on the biomasses structure. - Abstract: To eliminate the negative impacts of inorganic constituents during biomass thermochemical processes, leaching method by different diluted acid solutions was chosen. The different palm oil biomass samples (palm kernel shell (PKS), empty fruit bunches (EFB) and palm mesocarp fiber (PMF)) were pretreated by various diluted acid solutions (H 2 SO 4 , HClO 4 , HF, HNO 3 , HCl). Acids with the highest degrees of demineralization were selected to investigate the dematerialization impacts on the biomass thermal characteristics and physiochemical structure. Thermogravimetric analysis coupled with mass spectroscopy (TGA-MS) and Fourier transform infrared spectroscopy (TGA-FTIR) were employed to examine the biomass thermal degradation. TGA and DTG (Derivative thermogravimetry) indicated that the maximum degradation temperatures increased after acid pretreatment due to the minerals catalytic effects. The main permanent evolved gases comprising H 2 , CO 2 , CO were detected online during analysis. The major permanent gases produced at the temperature range of 250–750 °C were attributed to the condensable vapors cracking and probably some secondary reactions. The physiochemical structure change of the acid-treated biomass samples was examined by using Brunauer Emmett Teller (BET) method, Scanning Electron Microscope (SEM) and FTIR. The pyrolysis kinetics of the different palm oil biomasses were investigated using first order reaction model

How do organic vapors contribute to new-particle formation?

CERN Document Server

Donahue, Neil M; Chuang, Wayne; Riipinen, Ilona; Riccobono, Francesco; Schobesberger, Siegfried; Dommen, Josef; Baltensperger, Urs; Kulmala, Markku; Worsnop, Douglas R; Vehkamaki, Hanna

2013-01-01

Highly oxidised organic vapors can effectively stabilize sulphuric acid in heteronuclear clusters and drive new-particle formation. We present quantum chemical calculations of cluster stability, showing that multifunctional species can stabilize sulphuric acid and also present additional polar functional groups for subsequent cluster growth. We also model the multi-generation oxidation of vapors associated with secondary organic aerosol formation using a two-dimensional volatility basis set. The steady-state saturation ratios and absolute concentrations of extremely low volatility products are sufficient to drive new-particle formation with sulphuric acid at atmospherically relevant rates.

A high selective cataluminescence sensor for the determination of tetrahydrofuran vapor

Science.gov (United States)

Cao, Xiaoan; Dai, Huimei; Chen, Suilin; Zeng, Jiayi; Zhang, Keke; Sun, Yan

2013-02-01

A novel tetrahydrofuran (THF) vapor sensor was designed based on the cataluminescence (CTL) of THF on nanosized γ-Al2O3/MgO (mol ratio = 1.5:1). SEM and XRD were applied for its characterization. We found that the CTL was strongly produced when THF vapor flowed through a nanosized Al-Mg mixed-metal oxide surface, while the CTL was weakly generated when THF vapor flowed through a single nanosized γ-Al2O3 or MgO surface. Quantitative analysis was performed at an optimal temperature of 279 °C, a wavelength of 460 nm and a flow rate of 360 mL min-1. The linear range of the CTL intensity versus concentrations of THF vapor was 1.0-3000 mL m-3 with a detection limit of 0.67 mL m-3. No (or only very low) interference was observed by formaldehyde, methanol, ethanol, benzene, toluene, ethyl acetate, ammonia, cyclohexane, chloroform, glycol armour ether, glycol ether, isopropyl ether and n-butyl ether or acetic acid. Since the response of the sensor was rapid and the system was easy to handle, we believe that the sensor has great potential for real-world use.

Thermophysical properties of energetic ionic liquids/nitric acid mixtures: insights from molecular dynamics simulations.

Science.gov (United States)

Hooper, Justin B; Smith, Grant D; Bedrov, Dmitry

2013-09-14

Molecular dynamics (MD) simulations of mixtures of the room temperature ionic liquids (ILs) 1-butyl-4-methyl imidazolium [BMIM]/dicyanoamide [DCA] and [BMIM][NO3(-)] with HNO3 have been performed utilizing the polarizable, quantum chemistry based APPLE&P(®) potential. Experimentally it has been observed that [BMIM][DCA] exhibits hypergolic behavior when mixed with HNO3 while [BMIM][NO3(-)] does not. The structural, thermodynamic, and transport properties of the IL/HNO3 mixtures have been determined from equilibrium MD simulations over the entire composition range (pure IL to pure HNO3) based on bulk simulations. Additional (non-equilibrium) simulations of the composition profile for IL/HNO3 interfaces as a function of time have been utilized to estimate the composition dependent mutual diffusion coefficients for the mixtures. The latter have been employed in continuum-level simulations in order to examine the nature (composition and width) of the IL/HNO3 interfaces on the millisecond time scale.

Closed vessels microwave digestion method for uranium analysis of soils using alpha-spectroscopy

International Nuclear Information System (INIS)

Salar Amoli, H.; Barker, J.; Flowers, A.

2007-01-01

This paper describes our development of an accurate determination of uranium by alpha spectrometry using various kinds of sample digestion methods. The sample preparation techniques employed an acid digestion with HNO 3 , and microwave oven digestion either by HNO 3 or by combination of HNO 3 and HF. The samples were obtained from surface and in depth(40 cm) soils from residential area. An extraction chromatography column has been used to separate the uranium from interference matrix and elements. Results show that the microwave method significantly speeds up the analysis time, reduces the volume of acids used and eliminates a large fraction of acid vapour emission. Compared with the uranium recoveries it was shown that microwave HNO 3 +HF achieved greater recovery (83%) than microwave HNO 3 (78%), while less obtained by HNO 3 digestion using hot plate (75%). Various kind of digestion methods have been applied (24 times) for two kind of soil sample . The reproducibility was acceptable and the average precision (coefficient of variation) was between 4 to 5. No significant differences between the precision of the methods have been observed. Acid volume required for the microwave procedures are a fraction of 5 times lower and the analysis time 6 times lower than traditional digestion by hot plate technique. (author)

Determination of trace amount of titanium in 2.5% Nb-Zr alloy by anion exchange separation and sulfo salicylic acid photometry

International Nuclear Information System (INIS)

Sakai, Fumiaki; Wachi, Isamu; Tsuji, Nobuo; Satoh, Hitoshi

1973-01-01

A trace amount of Ti in 2.5% Nb-Zr alloy can be determined by a combined method of the characteristic anion exchange separation of Ti from Nb and the absorption photometry of Ti with sulfo salicylic acid. The alloy (1g) was dissolved in 5 ml of HF (1 + 1), and 5 ml of HNO 3 was added to them. The resultant 5M HF - 6M HNO 3 mixed acid solution was passed into an anion exchange resin column with 10 mm internal diameter and 100 mm high, at the rate of 1 to 2 ml/min. Niobium was adsorbed on to the column, through which Ti passed. The collected passing and washing solutions were converted into H 2 SO 4 medium by twice successive fuming treatments. The solution was transferred into a volumetric flask of 50 ml, and 10 ml of 10% sulfo salicylic acid in H 2 SO 4 was added. Diluting to a mark with H 2 SO 4 , the solution was allowed to stand for 15 min. Titanium was then determined by measuring absorption intensity at the wavelength of 410 mm. The influence of coexisting elements on the coloration of Ti and some adsorption conditions of Nb was experimentally investigated by using 95 Nb as a tracer. The experiment revealed that the removal of Nb is essential, and that higher HF concentration and lower HNO 3 concentration contribute to higher Nb adsorption. A variable rate type cockless column is useful for this routine analysis. The standard deviation and the coefficient of variation of analysis are 1.3 and 4.06% respectively for the concentration level of 32 ppm Ti (NZ-3). (Iwakiri, K.)

Process for recovery of uranium from wet process phosphoric acid

International Nuclear Information System (INIS)

Wiewiorowski, T.K.; Thornsberry, W.L. Jr.

1978-01-01

Process is claimed for the recovery of uranium from wet process phosphoric acid solution in which an organic extractant, containing uranium values and dissolved iron impurities and comprising a dialkylphosphoric acid and a trialkylphosphine oxide dissolved in a water immiscible organic solvent, is contacted with a substantially iron-free dilute aqueous phosphoric acid to remove said iron impurities. The removed impurities are bled from the system by feeding the resulting iron-loaded phosphoric acid to a secondary countercurrent uranium extraction operation from which they leave as part of the uranium-depleted acid raffinate. Also, process for recovering uranium in which the extractant, after it has been stripped of uranium values by aqueous ammonium carbonate, is contacted with a dilute aqueous acid selected from the group consisting of H 2 SO 4 , HCl, HNO 3 and iron-free H 3 PO 4 to improve the extraction efficiency of the organic extractant

Mercury determination in non- and biodegradable materials by cold vapor capacitively coupled plasma microtorch atomic emission spectrometry

International Nuclear Information System (INIS)

Frentiu, Tiberiu; Mihaltan, Alin I.; Ponta, Michaela; Darvasi, Eugen; Frentiu, Maria; Cordos, Emil

2011-01-01

Highlights: → Use of a miniaturized analytical system with microtorch plasma for Hg determination. → Determination of Hg in non- and biodegradable materials using cold vapor generation. → Figures of merit and advantages of the miniaturized system for Hg determination. - Abstract: A new analytical system consisting of a low power capacitively coupled plasma microtorch (20 W, 13.56 MHz, 150 ml min -1 Ar) and a microspectrometer was investigated for the Hg determination in non- and biodegradable materials by cold-vapor generation, using SnCl 2 reductant, and atomic emission spectrometry. The investigated miniaturized system was used for Hg determination in recyclable plastics from electronic equipments and biodegradable materials (shopping bags of 98% biodegradable polyethylene and corn starch) with the advantages of easy operation and low analysis costs. Samples were mineralized in HNO 3 -H 2 SO 4 mixture in a high-pressure microwave system. The detection limits of 0.05 ng ml -1 or 0.08 μg g -1 in solid sample were compared with those reported for other analytical systems. The method precision was 1.5-9.4% for Hg levels of 1.37-13.9 mg kg -1 , while recovery in two polyethylene certified reference materials in the range 98.7 ± 4.5% (95% confidence level).

Synthesis and characterization of bisdiglycolamides for comparable extraction of Th"4"+, UO_2"2"+ and Eu"3"+ from nitric acid solution

International Nuclear Information System (INIS)

Peng Ren; Ze-Yi Yan; Yang Li; Zuo-Miao Wu; Lei Wang; Yi-Quan Gao; Wang-Suo Wu; Lian-Biao Zhao

2017-01-01

The novel ligand N,N,N'''',N''''-tetrabutyl-N''',N'''-(N',N'-diethyl)-ethidene bisdiglycolamide (TBEE-BisDGA) and other eight analogous extractants have been synthesized and characterized by NMR and HRMS. The solvent extraction of Th"4"+, UO_2"2"+ and Eu"3"+ from nitric acid solution using the above BisDGA extractants was investigated in 1-dodecanol at 30 ± 1 deg C. The extractants exhibited higher affinity toward Th"4"+ than UO_2"2"+ and Eu"3"+ in the present system. The maximum value of separation factor SF_T_h_(_I_V_)_/_U_(_V_I_) and SF_T_h_(_I_V_)_/_E_u_(_I_I_I_) is 78.5 and 53.3 respectively for TBEE-BisDGA, 88.1 and 69.5 respectively in the case of TBi-PE-BisDGA at 3 M HNO_3 solution. (author)

Potentiometric titrations in anhydrous acetic acid

International Nuclear Information System (INIS)

Le Port, L.

1966-03-01

The method used for studying anhydrous acetic acid is potentiometry with a glass electrode. We have in this way studied the titration of common inorganic acids (HClO 4 - HBr - H 2 SO 4 - HCl - HNO 3 - H 3 PO 4 ) and of some metallic salts. Furthermore we have shown that complex acids are formed between HCl and some metallic chlorides. An analysis of the titration curves for the inorganic acids against pyridinium chloride has made it possible to calculate a certain number of values for the dissociation pK of these acids and of the corresponding pyridinium salts. The titration of metallic perchlorates constitutes a method of studying the stability of acetates; we have thus been able to draw up a classification for some of these acetates. The metallic chlorides studied fall into two groups according to their behaviour in weak or strong acids. The differences have been explained on the basis of the role played by solvolysis. In the third part we have studied the acidic properties of mixtures of HCl with certain metallic chlorides. This work has demonstrated the existence, in certain cases, of acid complexes of the type (HCl) m MCl n . (author) [fr

Decomposition of ammonium nitrate in homogeneous and catalytic denitration

International Nuclear Information System (INIS)

Anan'ev, A. V.; Tananaev, I. G.; Shilov, V. P.

2005-01-01

Ammonium nitrate is one of potentially explosive by-products of spent fuel reprocessing. Decomposition of ammonium nitrate in the HNO 3 -HCOOH system was studied in the presence or absence of Pt/SiO 2 catalyst. It was found that decomposition of ammonium nitrate is due to homogeneous noncatalytic oxidation of ammonium ion with nitrous acid generated in the HNO 3 -HCOOH system during denitration. The platinum catalyst initiates the reaction of HNO 3 with HCOOH to form HNO 2 . The regular trends were revealed and the optimal conditions of decomposition of ammonium nitrate in nitric acid solutions were found [ru

Reactive Chemical Vapor Deposition Method as New Approach for Obtaining Electroluminescent Thin Film Materials

Directory of Open Access Journals (Sweden)

Valentina V. Utochnikova

2012-01-01

Full Text Available The new reactive chemical vapor deposition (RCVD method has been proposed for thin film deposition of luminescent nonvolatile lanthanide aromatic carboxylates. This method is based on metathesis reaction between the vapors of volatile lanthanide dipivaloylmethanate (Ln(dpm3 and carboxylic acid (HCarb orH2Carb′ and was successfully used in case of HCarb. Advantages of the method were demonstrated on example of terbium benzoate (Tb(bz3 and o-phenoxybenzoate thin films, and Tb(bz3 thin films were successfully examined in the OLED with the following structure glass/ITO/PEDOT:PSS/TPD/Tb(bz3/Ca/Al. Electroluminescence spectra of Tb(bz3 showed only typical luminescent bands, originated from transitions of the terbium ion. Method peculiarities for deposition of compounds of dibasic acids H2Carb′ are established on example of terbium and europium terephtalates and europium 2,6-naphtalenedicarboxylate.

In hydrofluoric acid corrosion-resistant materials

International Nuclear Information System (INIS)

Hauffe, K.

1985-01-01

Copper, red brass (Cu-15 Zn), special treated carbon steel and chromium-nickel-molybdenum steel represent materials of high resistivity against concentrated hydrofluoric acid ( 2 O 3 ) are employed for windows in the presence of hydrogen fluoride and/or hydrofluoric acid because of their superior optical properties and their excellent corrosion resistance. Polyethylen, polypropylene and polyvinyl chloride (PVC) belong to the cheapest corrosion resistant material for container and for coatings in the presence of hydrofluoric acid. Special polyester resins reinforced by glass or graphite fibers have been successfully employed as material for production units with hydrofluoric acid containing liquids up to 330 K. By carbon reinforced epoxy resin represents a corrosion resistant coating. Because of their excellent friction and corrosion resistance against concentrated hot hydrofluoric acid and HNO 3 -HF-solutions, PTFE and polyvinylidene fluoride are used as material for valves and axles in such environment. The expensive alloys, as for instance hastelloy and monel, are substituted more and more by fiber-reinfored polyolefins, PVC and fluorine containing polymers. (orig.) [de

Advanced interface modelling of n-Si/HNO3 doped graphene solar cells to identify pathways to high efficiency

Science.gov (United States)

Zhao, Jing; Ma, Fa-Jun; Ding, Ke; Zhang, Hao; Jie, Jiansheng; Ho-Baillie, Anita; Bremner, Stephen P.

2018-03-01

In graphene/silicon solar cells, it is crucial to understand the transport mechanism of the graphene/silicon interface to further improve power conversion efficiency. Until now, the transport mechanism has been predominantly simplified as an ideal Schottky junction. However, such an ideal Schottky contact is never realised experimentally. According to literature, doped graphene shows the properties of a semiconductor, therefore, it is physically more accurate to model graphene/silicon junction as a Heterojunction. In this work, HNO3-doped graphene/silicon solar cells were fabricated with the power conversion efficiency of 9.45%. Extensive characterization and first-principles calculations were carried out to establish an advanced technology computer-aided design (TCAD) model, where p-doped graphene forms a straddling heterojunction with the n-type silicon. In comparison with the simple Schottky junction models, our TCAD model paves the way for thorough investigation on the sensitivity of solar cell performance to graphene properties like electron affinity. According to the TCAD heterojunction model, the cell performance can be improved up to 22.5% after optimizations of the antireflection coatings and the rear structure, highlighting the great potentials for fabricating high efficiency graphene/silicon solar cells and other optoelectronic devices.

Comparison of Microwave Assisted Acid Digestion Methods for ICP-MS Determination of Total Arsenic in Fish Tissue

International Nuclear Information System (INIS)

Ghanthimathi, S.; Aminah Abdullah; Salmijah, S.; Ujang, T.; Nurul, I.A.

2012-01-01

Fish is one of the most important sources of arsenic exposure in human diet and the Food Safety and Quality Division, Ministry of Health since 2007 has required routine monitoring of total arsenic in sea foods such as fish. This study describes an improved extraction method of total arsenic in fish using microwave assisted acid digestion procedure before being analysed by inductively coupled plasma mass spectrometry (ICP-MS). The parameters studied were pre-treatment of sample, digestion temperature, time programme and the chemicals (HNO 3 / H 2 O 2 ) used. Arsenic contents in fish samples under these conditions were compared using the standards additions technique. Microwave assisted acid digestion method with a combination of ultrapure concentrated nitric acid (HNO 3 ) to concentrated hydrogen peroxide (H 2 O 2 ) at a ratio of 7 mL: 1 mL, run time of 25 min and digestion temperature of 200 degree Celsius with no pre-treatment was found to have recovery of 100.7 % as compared to other digestion procedure where the recovery were 115.5, 111.6 and 101.8 %. Validation using certified reference material (CRM) of fish tissue (DORM-3) showed a recovery of 101.4 ± 2.5 % for total arsenic from the CRM. (author)

4f and 5f trivalent ions complexation by diamides and uses in solvent extraction

International Nuclear Information System (INIS)

Huber, H.

1984-06-01

Extractive properties of N,N'-tetraalkylmalonamides were investigated in view to separate the actinides contained in highly radioactive wastes. N,N'-dimethyldioctylmalonamide (DMDOMA) was selected. It extracts trivalent actinide and lanthanide from concentrated nitric acid. Mineral acids extraction was studied, especially HNO 3 extraction. The distribution of HNO 3 can be interpreted by assuming that in the organic phase three main species are present: HNO 3 (DMDOMA) 2 , HNO 3 DMDOMA, (HNO 3 ) 2 DMDOMA. 5f and 4f trivalent ions are extracted according to the mechanism: M 3+ + 3NO 3 - + 4DMDOMA in equilibrium with [M(DMDOMA) 2 (NO 3 ) 3 ].(DMDOMA) 2 . The extraction of important ions like U(VI), Np(V), Pu(IV), Pu(VI), Zr(IV) and Fe(III) was investigated. The results showed that DMDOMA behave line the carbamoylmethylenephosphonates and could be an interesting alternative to these organophosphorus extractants [fr

Studies of Physicochemical Processes in Atmospheric Particles and Acid Deposition.

Science.gov (United States)

Pandis, Spyros N.

A comprehensive chemical mechanism for aqueous -phase atmospheric chemistry was developed and its detailed sensitivity analysis was performed. The main aqueous-phase reaction pathways for the system are the oxidation of S(IV) to S(VI) by H_2O_2 , OH, O_2 (catalysed by Fe ^{3+} and Mn^ {2+}), O_3 and HSO_sp{5}{-}. The gas-phase concentrations of SO_2, H_2O_2, HO _2, OH, O_3 HCHO, NH_3, HNO_3 and HCl and the liquid water content of the cloud are of primary importance. The Lagrangian model predictions for temperature profile, fog development, liquid water content, gas-phase concentrations of SO_2 , HNO_3, and NH_3 , pH, aqueous-phase concentrations of SO _sp{4}{2-}, NH _sp{4}{+} and NO _sp{3}{-}, and finally deposition rates of the above ions match well the observed values. A third model was developed to study the distribution of acidity and solute concentration among the various droplet sizes in a fog or a cloud. Significant solute concentration differences can occur in aqueous droplets inside a fog or a cloud. Fogs in polluted environments have the potential to increase aerosol sulfate concentrations, but at the same time to cause reductions in the aerosol concentration of nitrate, chloride, ammonium and sodium as well as in the total aerosol mass concentration. The sulfate producd during fog episodes favors the aerosol particles that have access to most of the fog liquid water. Aerosol scavenging efficiencies of around 80% were calculated for urban fogs. Sampling and subsequent mixing of fog droplets of different sizes may result in measured concentrations that are not fully representative of the fogwater chemical composition. Isoprene and beta-pinene, at concentration levels ranging from a few ppb to a few ppm were reacted photochemically with NO_ {x} in the Caltech outdoor smog chamber facility. Aerosol formation from the isoprene photooxidation was found to be negligible even under extreme ambient conditions due to the relatively high vapor pressure of its

Polybenzimidazole-based mixed membranes with exceptional high water vapor permeability and selectivity

KAUST Repository

Akhtar, Faheem Hassan

2017-09-13

Polybenzimidazole (PBI), a thermal and chemically stable polymer, is commonly used to fabricate membranes for applications like hydrogen recovery at temperatures of more than 300 °C, fuel cells working in a highly acidic environment, and nanofiltration in aggressive solvents. This report shows for the first time use of PBI dense membranes for water vapor/gas separation applications. They showed an excellent selectivity and high water vapor permeability. Incorporation of inorganic hydrophilic titanium-based nano-fillers into the PBI matrix further increased the water vapor permeability and water vapor/N2 selectivity. The most selective mixed matrix membrane with 0.5 wt% loading of TiO2 nanotubes yielded a water vapor permeability of 6.8×104 Barrer and a H2O/N2 selectivity of 3.9×106. The most permeable membrane with 1 wt% loading of carboxylated TiO2 nanoparticles had a 7.1×104 Barrer water vapor permeability and a H2O/N2 selectivity of 3.1×106. The performance of these membranes in terms of water vapor transport and selectivity is among the highest reported ones. The remarkable ability of PBI to efficiently permeate water versus other gases opens the possibility to fabricate membranes for dehumidification of streams in harsh environments. This includes the removal of water from high temperature reaction mixtures to shift the equilibrium towards products.

Polybenzimidazole-based mixed membranes with exceptional high water vapor permeability and selectivity

KAUST Repository

Akhtar, Faheem Hassan; Kumar, Mahendra; Villalobos, Luis Francisco; Shevate, Rahul; Vovusha, Hakkim; Schwingenschlö gl, Udo; Peinemann, Klaus-Viktor

2017-01-01

Polybenzimidazole (PBI), a thermal and chemically stable polymer, is commonly used to fabricate membranes for applications like hydrogen recovery at temperatures of more than 300 °C, fuel cells working in a highly acidic environment, and nanofiltration in aggressive solvents. This report shows for the first time use of PBI dense membranes for water vapor/gas separation applications. They showed an excellent selectivity and high water vapor permeability. Incorporation of inorganic hydrophilic titanium-based nano-fillers into the PBI matrix further increased the water vapor permeability and water vapor/N2 selectivity. The most selective mixed matrix membrane with 0.5 wt% loading of TiO2 nanotubes yielded a water vapor permeability of 6.8×104 Barrer and a H2O/N2 selectivity of 3.9×106. The most permeable membrane with 1 wt% loading of carboxylated TiO2 nanoparticles had a 7.1×104 Barrer water vapor permeability and a H2O/N2 selectivity of 3.1×106. The performance of these membranes in terms of water vapor transport and selectivity is among the highest reported ones. The remarkable ability of PBI to efficiently permeate water versus other gases opens the possibility to fabricate membranes for dehumidification of streams in harsh environments. This includes the removal of water from high temperature reaction mixtures to shift the equilibrium towards products.

Redox reactions of U(IV) and Pu(IV) with H2O2 generated in nitric acid media by power ultrasound

International Nuclear Information System (INIS)

Moisy, P.; Venault, L.; Madic, C.; Nikitenko, S.

1998-01-01

Power ultrasound causes water molecule dissociation on H o and OH o radicals due to high local temperatures and pressures generated in the cavitation threshold. In nitric acid media scavenging of OH o radicals with NO 3 - followed by NO 3 o radicals hydrolysis leads to H 2 O 2 formation. It was shown that H 2 O 2 generated under the effect of ultrasound with the frequency 20 kHz and intensity 1-3 Wcm -2 (Ar atmosphere) oxidizes U(IV) to U(VI) or reduces Pu(IV) to Pu(III) in 1-4 M HNO 3 in the presence of antinitrous reagents ( N 2 H 5 NO 3 or NH 2 SO 3 H). The effect of HNO 3 concentration and ultrasonic intensity on the kinetics of U(IV) oxidation and Pu(IV) reduction was studied. (author)

A pilot study of gaseous pollutants' measurement (NO2, SO2, NH3, HNO3 and O3 in Abidjan, Côte d'Ivoire: contribution to an overview of gaseous pollution in African cities

Directory of Open Access Journals (Sweden)

J. Bahino

2018-04-01

Full Text Available This work is part of the DACCIWA FP7 project (Dynamics-Aerosol-Chemistry-Cloud Interactions in West Africa in the framework of the Work Package 2 Air Pollution and Health. This study aims to characterize urban air pollution levels through the measurement of NO2, SO2, NH3, HNO3 and O3 in Abidjan, the economic capital of Côte d'Ivoire. Measurements of inorganic gaseous pollutants, i.e. NO2, SO2, NH3, HNO3 and O3 were performed in Abidjan during an intensive campaign within the dry season (15 December 2015 to 16 February 2016, using INDAAF (International Network to study Deposition and Atmospheric chemistry in AFrica passive samplers exposed in duplicate for 2-week periods. Twenty-one sites were selected in the district of Abidjan to be representative of various anthropogenic and natural sources of air pollution in the city. Results from this intensive campaign show that gas concentrations are strongly linked to surrounding pollution sources and show a high spatial variability. Also, NH3, NO2 and O3 gases were present at relatively higher concentrations at all the sites. NH3 average concentrations varied between 9.1 ± 1.7 ppb at a suburban site and 102.1 ± 9.1 ppb at a domestic fires site. NO2 mean concentration varied from 2.7 ± 0.1 ppb at a suburban site to 25.0 ± 1.7 ppb at an industrial site. Moreover, we measured the highest O3 concentration at the two coastal sites of Gonzagueville and Félix-Houphouët-Boigny International Airport located in the southeast of the city, with average concentrations of 19.1 ± 1.7 and 18.8 ± 3.0 ppb, respectively. The SO2 average concentration never exceeded 7.2 ± 1.2 ppb over all the sites, with 71.5 % of the sampling sites showing concentrations ranging between 0.4 and 1.9 ppb. The HNO3 average concentration ranged between 0.2 and 1.4 ppb. All these results were combined with meteorological parameters to provide the first mapping of gaseous pollutants

Influence of Biomass Burning on Temporal and Diurnal Variations of Acidic Gases, Particulate Nitrate, and Sulfate in a Tropical Urban Atmosphere

Directory of Open Access Journals (Sweden)

Sailesh N. Behera

2014-01-01

Full Text Available The present study investigated the temporal and diurnal distributions of atmospheric acidic gases (sulphur dioxide (SO2, nitrous acid (HONO, and nitric acid (HNO3 and those of particulate nitrate (NO3- and sulfate (SO42- through a comprehensive field campaign during the largest smoke haze episode in Singapore, a representative country in Southeast Asia (SEA. To identify the atmospheric behavior of these pollutants during the smoke haze period, the data generated from the measurement campaign were divided into three distinct periods: prehaze, during haze, and posthaze periods. The 24 hr average data indicated that ambient SO2, HONO, and HNO3 during the smoke haze episodes increased by a factor ranging from 1.2 to 2.6 compared to those during the prehaze and posthaze periods. Similarly, in the case of particulates SO42- and NO3-, the factor ranged from 2.3 to 4.2. Backward air trajectories were constructed and used to find the sources of biomass burning to the recurring smoke haze in this region. The air trajectory analysis showed that the smoke haze episodes experienced in Singapore were influenced by transboundary air pollution, caused by severe biomass burning events in the islands of Indonesia.

Desorption of 137Cs from Cetraria islandica (L. Ach. using solutions of acids and their salts mixtures

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ANA A. ČUČULOVIĆ

2009-06-01

Full Text Available The desorption of 137Cs from Cetraria islandica (L. Ach. lichen was investigated using the solutions: A H2SO4–HNO3–K2SO4, B H2SO4–HNO3–Na2SO4 and C H2SO4–HNO3– (NH42SO4–(NH4NO3 at pH 2.00, 2.58, 2.87, 3.28 and 3.75, similar to acid rain. After five consecutive desorptions using solutions A, B and C, from 44.0 % (solution B, pH 3.75 to 68.8 % (solution C, pH 3.28 of 137Cs had been desorbed from the lichen. In all cases, the most successful 137Cs desorption was the first one. In the presence of K+ (solution A the total amount of desorbed 137Cs did not depend on the pH of the solution and this was confirmed by the analogous reactions of Cs+ and K+, due to their similar ionic radii. The dependencies of the non-desorbed content of 137Cs on the number of desorptions gave curves indicating that at least two types of sorption occur. One of them can be dominant if suitable desorbants are used. The results indicate lichens as secondary sources of environment pollution with 137Cs.

Tank vapor characterization project - headspace vapor characterization of Hanford Waste Tank 241-C-107: Second comparison study results from samples collected on 3/26/96

International Nuclear Information System (INIS)

Evans, J.C.; Pool, K.H.; Thomas, B.L.

1997-01-01

This report describes the analytical results of vapor samples taken from the headspace of waste storage tank 241-C-107 (Tank C-107) at the Hanford Site in Washington State. The results described in this report is the second in a series comparing vapor sampling of the tank headspace using the Vapor Sampling System (VSS) and In Situ Vapor Sampling (ISVS) system without high efficiency particulate air (HEPA) prefiltration. The results include air concentrations of water (H 2 O) and ammonia (NH 3 ), permanent gases, total non-methane organic compounds (TO-12), and individual organic analytes collected in SUMMA trademark canisters and on triple sorbent traps (TSTs). Samples were collected by Westinghouse Hanford Company (WHC) and analyzed by Pacific Northwest National Laboratory (PNNL). Analyses were performed by the Vapor Analytical Laboratory (VAL) at PNNL. Analyte concentrations were based on analytical results and, where appropriate, sample volume measurements provided by WHC

Tank vapor characterization project. Headspace vapor characterization of Hanford waste tank 241-BY-108: Second comparison study results from samples collected on 3/28/96

International Nuclear Information System (INIS)

Thomas, B.L.; Pool, K.H.; Evans, J.C.

1997-01-01

This report describes the analytical results of vapor samples taken from the headspace of waste storage tank 241-BY-108 (Tank BY-108) at the Hanford Site in Washington State. The results described in this report is the second in a series comparing vapor sampling of the tank headspace using the Vapor Sampling System (VSS) and In Situ Vapor Sampling (ISVS) system without high efficiency particulate air (HEPA) prefiltration. The results include air concentrations of water (H 2 O) and ammonia (NH 3 ), permanent gases, total non-methane organic compounds (TO-12), and individual organic analytes collected in SUMMA trademark canisters and on triple sorbent traps (TSTs). Samples were collected by Westinghouse Hanford Company (WHC) and analyzed by Pacific Northwest National Laboratory (PNNL). Analyses were performed by the Vapor Analytical Laboratory (VAL) at PNNL. Analyte concentrations were based on analytical results and, where appropriate, sample volume measurements provided by WHC

Determination of trace amount of titanium in 2. 5% Nb-Zr alloy by anion exchange separation and sulfo salicylic acid photometry

Energy Technology Data Exchange (ETDEWEB)

Sakai, F; Wachi, I; Tsuji, N; Satoh, Hitoshi [Power Reactor and Nuclear Fuel Development Corp., Tokyo (Japan)

1973-04-01

A trace amount of Ti in 2.5% Nb-Zr alloy can be determined by a combined method of the characteristic anion exchange separation of Ti from Nb and the absorption photometry of Ti with sulfo salicylic acid. The alloy (1g) was dissolved in 5 ml of HF (1 + 1), and 5 ml of HNO/sub 3/ was added to them. The resultant 5M HF - 6M HNO/sub 3/ mixed acid solution was passed into an anion exchange resin column with 10 mm internal diameter and 100 mm high, at the rate of 1 to 2 ml/min. Niobium was adsorbed on to the column, through which Ti passed. The collected passing and washing solutions were converted into H/sub 2/SO/sub 4/ medium by twice successive fuming treatments. The solution was transferred into a volumetric flask of 50 ml, and 10 ml of 10% sulfo salicylic acid in H/sub 2/SO/sub 4/ was added. Diluting to a mark with H/sub 2/SO/sub 4/, the solution was allowed to stand for 15 min. Titanium was then determined by measuring absorption intensity at the wavelength of 410 mm. The influence of coexisting elements on the coloration of Ti and some adsorption conditions of Nb was experimentally investigated by using /sup 95/Nb as a tracer. The experiment revealed that the removal of Nb is essential, and that higher HF concentration and lower HNO/sub 3/ concentration contribute to higher Nb adsorption. A variable rate type cockless column is useful for this routine analysis. The standard deviation and the coefficient of variation of analysis are 1.3 and 4.06% respectively for the concentration level of 32 ppm Ti (NZ-3).

Acidic gases, ammonia and water-soluble ions in PM 2.5 at a coastal site in the Pearl River Delta, China

Science.gov (United States)

Hu, Min; Wu, Zhijun; Slanina, J.; Lin, Peng; Liu, Shang; Zeng, Limin

Real-time measurements of acidic trace gases (HCl, HNO 3, HONO, and SO 2), ammonia, and water-soluble ions in PM 2.5 were conducted at Xinken, a coastal site downwind of Guangzhou, from 4 October to 4 November 2004, as part of the Pearl River Delta (PRD) intensive field campaign. The average concentrations of HCl, HONO, HNO 3, SO 2, and NH 3 are 2.8, 2.9, 6.3, 55.4, and 7.3 μg m -3, respectively, and 2.4, 7.2, 24.1, and 9.2 μg m -3 for Cl -, NO 3-, SO 42-, and NH 4+ in PM 2.5. The diurnal variations of both HCl and HNO 3 showed higher concentrations during daytime and lower concentrations at night, and aerosol Cl - and NO 3- showed an opposite diurnal patterns to HCl and HNO 3. The diurnal variation of NH 3 showed the similar pattern to that of aerosol NH 4+ with lower concentration during daytime and higher concentration at night. The average concentration of SO 2 during daytime was higher than that at night. The transportation of urban plumes to the sampling site could explain the higher concentration of SO 2 during daytime. HONO showed a clear diurnal variation with lower concentration during daytime and higher concentration at night. The HONO concentrations were positively correlated with the particle surface area concentrations, suggesting the formation of HONO through the heterogeneous conversion on particle surfaces could be significant. The ionic charge balance analysis included the cations derived from filter measurements indicates that the contribution of the cations in fine particle (PM 1.8) to the charge balance is not pronounced. The theoretical equilibrium constant ( Ke) of NH 4NO 3 is higher than the observed concentration product ( Km=[NH 3]×[HNO 3]) during daytime, and lower than Km at night. This indicates that the atmospheric conditions during the sampling period did not favor the formation of NH 4NO 3 during daytime.

Quaternary isobaric (vapor + liquid + liquid) equilibrium and (vapor + liquid) equilibrium for the system (water + ethanol + cyclohexane + heptane) at 101.3 kPa

International Nuclear Information System (INIS)

Pequenin, Ana; Asensi, Juan Carlos; Gomis, Vicente

2011-01-01

Highlights: → Water-ethanol-cyclohexane-heptane and water-cyclohexane-heptane isobaric VLLE. → Isobaric experimental data were determined at 101.3 kPa. → A dynamic recirculating still with an ultrasonic homogenizer was used. → The quaternary system does not present quaternary azeotropes. - Abstract: Experimental isobaric (vapor + liquid + liquid) and (vapor + liquid) equilibrium data for the ternary system {water (1) + cyclohexane (2) + heptane (3)} and the quaternary system {water (1) + ethanol (2) + cyclohexane (3) + heptane (4)} were measured at 101.3 kPa. An all-glass, dynamic recirculating still equipped with an ultrasonic homogenizer was used to determine the VLLE. The results obtained show that the system does not present quaternary azeotropes. The point-by-point method by Wisniak for testing the thermodynamic consistency of isobaric measurements was used to test the equilibrium data.

Application of power ultrasound in radiochemistry

International Nuclear Information System (INIS)

Moisy, Ph.; Venault, L.; Blanc, P.; Madic, C.; Nikitenko, S.

1998-01-01

The chemical effects of ultrasound are related to cavitation process: nucleation, bubble growth and cavitation collapse. Sono-chemical reactions occur due to the rapid heating of the contents of cavitation bubbles. The shock-waves generated by cavitation collapse cause intense emulsification of the immiscible liquids. The CEA/Marcoule research group investigated the effect of power ultrasound on the homogeneous and heterogeneous (liquid-liquid) actinide reactions, in aqueous nitric acid media. It was found that U(IV), Np(V) and Pu(III) can be rapidly oxidized in HNO 3 solutions by HNO 2 , generated by the effect of power ultrasound on HNO 3 solutions. HNO 2 , formed during HNO 3 sono-lysis, decomposes hydrazinium nitrate within the cavitation bubbles. This makes it possible to the control actinide oxidation states without adding any side chemical reagents (NaNO 2 , for example). The quantitative data on the effect in the ultrasonic field in nitric acid medium are discussed, and sono-chemical mechanisms are proposed for nitrous acid formation and hydrazinium nitrate decomposition. In the presence of anti-nitrous reagents, such as hydrazinium nitrate and sulfamic acid, U(IV) was found to be oxidized and Pu(IV) reduced by H 2 O 2 formed as the result of aqueous nitric acid sono-lysis. The kinetics of H 2 O 2 formation is faster than in water, for the same sono-chemical conditions. Np(V) is rapidly oxidized, by aqueous phase HNO 2 , under the effect of ultrasound on the two-phase system TBP-dodecane/HNO 3 . Intense emulsification of the liquid/liquid system accelerates the mass transfer, of Np(VI) formed, into the organic phase. The quantitative effect of power ultrasound in aqueous nitric acid, with or without anti-nitrous reagents, can be used to predict the behavior of actinides in the ultrasonic field in nitric acid medium. (author)

Argon Shrouded Plasma Spraying of Tantalum over Titanium for Corrosion Protection in Fluorinated Nitric Acid Media

Science.gov (United States)

Vetrivendan, E.; Jayaraj, J.; Ningshen, S.; Mallika, C.; Kamachi Mudali, U.

2018-02-01

Argon shrouded plasma spraying (ASPS) was used to deposit a Ta coating on commercially pure Ti (CP-Ti) under inert argon, for dissolver vessel application in the aqueous spent fuels reprocessing plant with high plutonium content. Oxidation during plasma spraying was minimized by shrouding argon system. Porosity and oxide content were controlled by optimizing the spraying parameters, to obtain a uniform and dense Ta coating. The Ta particle temperature and velocity were optimized by judiciously controlling the spray parameters, using a spray diagnostic charge-coupled device camera. The corrosion resistance of the Ta coatings developed by ASPS was investigated by electrochemical studies in 11.5 M HNO3 and 11.5 M HNO3 + 0.05 M NaF. Similarly, the durability of the ASPS Ta coating/substrate was evaluated as per ASTM A262 Practice-C test in boiling nitric acid and fluorinated nitric acid for 240 h. The ASPS Ta coating exhibited higher corrosion resistance than the CP-Ti substrate, as evident from electrochemical studies, and low corrosion rate with excellent coating stability in boiling nitric, and fluorinated nitric acid. The results of the present study revealed that tantalum coating by ASPS is a promising strategy for improving the corrosion resistance in the highly corrosive reprocessing environment.

Hydrogenation of furfural at the dynamic Cu surface of CuOCeO2/Al2O3 in vapor phase packed bed reactor

Science.gov (United States)

The hydrogenation of furfural to furfuryl alcohol over a CuOCeO2/'-Al2O3 catalyst in a flow reactor is reported. The catalyst was prepared by the wet impregnation of Cu onto a CeO2/'-Al2O3 precursor. The calcined catalyst was then treated with HNO3 to remove surface CuO resulting in a mixed CuCe oxi...

Analytical applications of N-phenyl-n-butyro hydroxamic and N-p-tolyl-n-butyro hydroxamic acids towards chromium (VI), copper (II), iron (III) and uranium (VI)

International Nuclear Information System (INIS)

Elkhadir, A. Y. F.

2001-05-01

Two aliphatic hydroxamic acids were prepared; N-phenyl-n-butyro hydroxamic acid and N-p-tolyl-n-butyro hydroxamic acid, by the reaction of β-phenylhydroxylamine and p-tolyl hydroxylamine with n-butyryl chloride. The acids were identified by: their melting points, characteristic reactions with acidic solutions of vanadium (V) and iron (III), infrared spectroscopy, nitrogen content and molecular weight determination. The extractability of these acids towards Cr (VI), Cu (II), Fe (III) and U (VI) were investigated at different pH values and molar acid concentrations. N-phenyl-n- butyro hydroxamic acid has a maximum extraction (98.80%) for Cr (VI) at 4 M H 2 SO 4 , (83.25%) for Cu (II) at pH 6, (99.17%) for Fe (III) at pH 5 and (99.76%) at 4 M HNO 3 for U (VI) respectively. N-p-tolyl-n-butyro hydroxamic acid has a maximum extraction (98.40%) for Cr (VI)at 4 M H 2 SO 4 , (81.30%) for Cu (II) at pH 6, (92.80%) for Fe (III) at pH 5 and (99.64%) for U (VI) at 4 M HNO 3 , respectively. The ratios of the metal to ligands were determined by job method (continuous variation method) and were found to be 1:2 for Cr (VI) and U (VI). (Author)

Analytical applications of N-phenyl-n-butyro hydroxamic and N-p-tolyl-n-butyro hydroxamic acids towards chromium (VI), copper (II), iron (III) and uranium (VI)

Energy Technology Data Exchange (ETDEWEB)

Elkhadir, A Y. F. [Department of Chemistry, Faculty of Science, University of Khartoum, Khartoum (Sudan)

2001-05-01

Two aliphatic hydroxamic acids were prepared; N-phenyl-n-butyro hydroxamic acid and N-p-tolyl-n-butyro hydroxamic acid, by the reaction of {beta}-phenylhydroxylamine and p-tolyl hydroxylamine with n-butyryl chloride. The acids were identified by: their melting points, characteristic reactions with acidic solutions of vanadium (V) and iron (III), infrared spectroscopy, nitrogen content and molecular weight determination. The extractability of these acids towards Cr (VI), Cu (II), Fe (III) and U (VI) were investigated at different pH values and molar acid concentrations. N-phenyl-n- butyro hydroxamic acid has a maximum extraction (98.80%) for Cr (VI) at 4 M H{sub 2}SO{sub 4}, (83.25%) for Cu (II) at pH 6, (99.17%) for Fe (III) at pH 5 and (99.76%) at 4 M HNO{sub 3} for U (VI) respectively. N-p-tolyl-n-butyro hydroxamic acid has a maximum extraction (98.40%) for Cr (VI)at 4 M H{sub 2} SO{sub 4}, (81.30%) for Cu (II) at pH 6, (92.80%) for Fe (III) at pH 5 and (99.64%) for U (VI) at 4 M HNO{sub 3}, respectively. The ratios of the metal to ligands were determined by job method (continuous variation method) and were found to be 1:2 for Cr (VI) and U (VI). (Author)

Chromatography of 49 metal ions on stannic antimonate papers in dimethylsulfoxide: nitric acid systems and aqueous nitric acid systems

International Nuclear Information System (INIS)

Qureshi, M.; Varshney, K.G.; Rajput, R.P.S.

1975-01-01

Chromatographic separations of 49 metal ions on stannic antimonate papers have been performed using mixed solvent systems containing DMSO. Aqueous HNO 3 systems have also been used. The utility of the papers has been demonstrated by achieving various difficult separations. Some of the important separations (R/sub f/ values given in parentheses) are: Cs + (0.20)-K + (0.30) and Sm 3+ (0.00)-Pr 3+ (0.72) in pure DMSO; Nb 5+ (0.14)-VO 2+ (0.95) in DMSO-6M HNO 3 (1:1); Ti 4+ (0.00)-VO 2 (0.97) in DMSO-0.5M HNO 3 (1:1); and Ba 2+ (0.06)-K + (0.52)-Sr 2+ (0.95), Ba 2+ (0.04)-Cs + (0.41)-Mg 2+ (0.93), and Ca 2+ (0.10)-Sr 2+ (0.94) in DMSO-0.1M HNO 3 (1:1). The time of development in each case is two hours. A discussion is presented on the dependence of Ri, log R/sub f/, and R/sub M/ on pH of the solvent to understand the mechanism of the movement of metal ions on papers impregnated with inorganic materials. (U.S.)

Nitration Study of Cyclic Ladder Polyphenylsilsesquioxane

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LIANG Jia-xiang

2017-05-01

Full Text Available Several nitration reagents including fuming nitric acid, HNO3-H2SO4, KNO3-H2SO4, HNO3-KNO3, CH3COOH-KNO3, (CH3CO2O-HNO3 were used to nitrate cyclic ladder polyphenylsilsesquioxane (CL-PPSQ in different conditions in order to enhance the compatibility of the CL-PPSQ in polymers, the NO2-PPSQ was obtained. FTIR, element analysis, GPC, TGA and 1H NMR were used to characterize the structures of the nitrated products. The results show that the nitrating abilities of the fuming nitric acid, HNO3-H2SO4 and KNO3-H2SO4 are very strong. Many nitro groups can be linked with phenyl groups in CL-PPSQ, but with low molecular mass, fracture occurs in siloxane segment. However, the Mn of the product NO2-PPSQ sharply drops by 50% compared with that of CL-PPSQ, so the nitration reagents can break the cyclic structure of CL-PPSQ. The nitrating reagents of HNO3-KNO3 and CH3COOH-KNO3 have no nitration effects on CL-PPSQ. At last, NO2-CL-PPSQ was prepared using (CH3CO2O-HNO3 because of the moderate nitration process and ability. The cyclic structure of PPSQ is remained, although the number of —NO2 group is not too much. At the same time, the nitration mechanism using different nitration reagents was analyzed. A certain amount of NO2+, which is a kind of activator owning strong nitration ability, can be found in the fuming nitric acid and H2SO4-HNO3(KNO3 systems. As to the (CH3CO2O-HNO3 system, the main activator is CH3COONO2.

Thermodynamic properties of isomeric iso-butoxybenzoic acids: Experimental and theoretical study

International Nuclear Information System (INIS)

Jakubczyk, Michał; Sporzyński, Andrzej; Emel’yanenko, Vladimir N.; Varfolomeev, Mikhail A.; Verevkin, Sergey P.

2015-01-01

Highlights: • Vapor pressures of butoxy benzoic acid derivatives were measured. • Vaporization, sublimation and fusion enthalpies were derived. • Molar enthalpies of formation were measured by calorimetry. • Thermochemical data tested for consistency using additivity rules and computations. • Simple additivity method suggested for prediction thermochemical properties. - Abstract: Standard (p° = 0.1 MPa) molar enthalpies of formation at the temperature T = 298.15 K of the 2-, 3-, and 4-iso-butoxybenzoic acids were measured using the combustion calorimetry. Standard molar enthalpies of vaporization and sublimation were derived from the vapor pressure temperature dependencies measured by the transpiration method. Molar enthalpies of the solid state phase transitions were measured by the DSC. Thermodynamic data on alkoxy substituted benzoic acids available in the literature were collected and combined with own experimental results. This data set on alkoxybenzoic acids was evaluated by using quantum-chemical and group-additivity methods

Thermodynamic properties of isomeric iso-butoxybenzoic acids: Experimental and theoretical study

Energy Technology Data Exchange (ETDEWEB)

Jakubczyk, Michał; Sporzyński, Andrzej [Faculty of Chemistry, Warsaw University of Technology, 00-664 Warszawa (Poland); Emel’yanenko, Vladimir N.; Varfolomeev, Mikhail A. [Department of Physical Chemistry, Kazan Federal University, 420008 Kazan (Russian Federation); Verevkin, Sergey P., E-mail: sergey.verevkin@uni-rostock.de [Department of Physical Chemistry, Kazan Federal University, 420008 Kazan (Russian Federation); Department of Physical Chemistry and Department, Science and Technology of Life, Light and Matter, University of Rostock, D-18059 Rostock (Germany)

2015-09-10

Highlights: • Vapor pressures of butoxy benzoic acid derivatives were measured. • Vaporization, sublimation and fusion enthalpies were derived. • Molar enthalpies of formation were measured by calorimetry. • Thermochemical data tested for consistency using additivity rules and computations. • Simple additivity method suggested for prediction thermochemical properties. - Abstract: Standard (p° = 0.1 MPa) molar enthalpies of formation at the temperature T = 298.15 K of the 2-, 3-, and 4-iso-butoxybenzoic acids were measured using the combustion calorimetry. Standard molar enthalpies of vaporization and sublimation were derived from the vapor pressure temperature dependencies measured by the transpiration method. Molar enthalpies of the solid state phase transitions were measured by the DSC. Thermodynamic data on alkoxy substituted benzoic acids available in the literature were collected and combined with own experimental results. This data set on alkoxybenzoic acids was evaluated by using quantum-chemical and group-additivity methods.

EPA Method 245.2: Mercury (Automated Cold Vapor Technique)

Science.gov (United States)

Method 245.2 describes procedures for preparation and analysis of drinking water samples for analysis of mercury using acid digestion and cold vapor atomic absorption. Samples are prepared using an acid digestion technique.

Fully Automated Concentration Control of the Acidic Texturisation Process

OpenAIRE

Dannenberg, T.; Zimmer, M.; Rentsch, J.

2012-01-01

To enable a concentration control in the acidic texturing process we have closed the feedback loop from analytical data to the dosing mechanism of the used process tool. In order to analyze the process bath we used near-infrared spectroscopy in an online setup as well as ion chromatography as an inline method in a second approach. Using the developed dosing algorithm allows a concentration optimization of HF and HNO3 in dependence of the Si concentrations. This allows a further optimization o...

VAPOR MIXER FOR GELATINIZATION OF STARCH IN LIQUEFYING STATION

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V. V. Ananskikh

2015-01-01

Full Text Available Starch hydrolysis is main technological process in production of starch sweeteners. Acid hydrolysis of starch using hydrochloric acid is carried out very fast but it does not allow to carry out full hydrolysis and to produce products with given carbohydrate composition. Bioconversion of starch allows to eliminate these limitations. At production of starch sweeteners from starch using enzymes starch hydrolysis is carried out in two stages At first starch – starch liquefaction the rapid increase of viscosity takes place which requires intensive mixing. Liquefying station consists of jet-cooker, holder, pressure regulator and evaporator. Jet-cooker of starch is its main part, starch is quickly turns into soluble (gelatinized state and it is partially liquefied by injection of starch suspension by flow of water vapor under pressure not less than 0,8 MPa. Heat and hydraulic calculation were carried out in order to determine constructive sizes of mixer for cooking of starch. The main hydraulic definable parameters are pressure drop in mixer, vapor pressure at mixer inlet, daily capacity of station by glucose syrup M, product consumption (starch suspension, diameter of inlet section of vapor nozzle. The goal of calculation was to determine vapor consumption M1, diameter d2 of outlet section of confuser injector, length l2 of gelatinization section. For heat calculation there was used Shukhov’s formula along with heat balance equation for gelatinization process. The numerical solution obtained with adopted assumptions given in applied mathematical package MATHCAD, for M = 50 t/day gives required daily vapor consumption M1 = 14,446 т. At hydraulic calculation of pressure drop in mixer there was used Bernoulli’s theorem. Solving obtained equations using MATHCAD found diameter of outlet section of consufer d2 = 0,023 м, vapor pressure inside of mixer p2 = 3,966·105 Па, l2 = 0,128 м. Developed method of calculation is used to determine

Vapor pressures and vaporization enthalpy of codlemone by correlation gas chromatography

International Nuclear Information System (INIS)

Schultz, Shannon M.; Harris, Harold H.; Chickos, James S.

2015-01-01

Highlights: • The vaporization enthalpy of codlemone has been evaluated. • The vapor pressure of codlemone has been evaluated from T = (298.15 to T b ) K. • Vapor pressures for the 1-alkanols standards are available from T = (298.15 to 500) K. - Abstract: The vapor pressure and vaporization enthalpy of codlemone (trans, trans 8,10-dodecadien-1-ol), the female sex hormone of the codling moth is evaluated by correlation gas chromatography using a series of saturated primary alcohols as standards. A vaporization enthalpy of (92.3 ± 2.6) kJ · mol −1 and a vapor pressure, p/Pa = (0.083 ± 0.012) were evaluated at T = 298.15 K. An equation for the evaluation of vapor pressure from ambient temperature to boiling has been derived by correlation for codlemone. The calculated boiling temperature of T B = 389 K at p = 267 Pa is within the temperature range reported in the literature. A normal boiling temperature of T B = (549.1 ± 0.1) K is also estimated by extrapolation

Effect of Acid Oxidation on the Dispersion Property of Multiwalled Carbon Nanotubes

Science.gov (United States)

Goh, P. S.; Ismail, A. F.; Aziz, M.

2009-06-01

A means of dispersion of multiwalled carbon nanotube (MWCNT) via mixed acid (HNO3 and H2SO4) oxidation with different treatment durations was investigated through the solubility study of the treated carbon nanotubes in some common solvents. Fourier transformed infrared (FTIR) characterization of the reaction products revealed that the surface of MWCNTs was successfully functionalized with surface acidic groups. The acid-base titration demonstrated that the amount of surface acidic groups increased in parallel with the refluxing duration. The acid modified MWCNTs were found to be well dispersed in polar solvents, such as ethanol and water due to the presence of the hydrophilic acid functional groups on the surface of raw MWCNTs. Such chemical modification of carbon nanotube properties will pave the way towards the realistic applications in the nanotechnology world.

Vapor-phase hydrothermal transformation of HTiOF3 intermediates into {001} faceted anatase single-crystalline nanosheets.

Science.gov (United States)

Liu, Porun; Wang, Yun; Zhang, Haimin; An, Taicheng; Yang, Huagui; Tang, Zhiyong; Cai, Weiping; Zhao, Huijun

2012-12-07

For the first time, a facile, one-pot hydrofluoric acid vapor-phase hydrothermal (HF-VPH) method is demonstrated to directly grow single-crystalline anatase TiO(2) nanosheets with 98.2% of exposed {001} faceted surfaces on the Ti substrate via a distinctive two-stage formation mechanism. The first stage produces a new intermediate crystal (orthorhombic HTiOF(3) ) that is transformed into anatase TiO(2) nanosheets during the second stage. The findings reveal that the HF-VPH reaction environment is unique and differs remarkably from that of liquid-phase hydrothermal processes. The uniqueness of the HF-VPH conditions can be readily used to effectively control the nanostructure growth. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The vapor pressure and enthalpy of vaporization of M-xylene

International Nuclear Information System (INIS)

Rothenberg, S.J.; Seiler, F.A.; Bechtold, W.E.; Eidson, A.F.

1988-01-01

We measured the vapor pressure of m-xylene over the temperature range 273 to 293 deg K with a single-sided capacitance manometer. The enthalpy of vaporization was 42.2 ± 0.1 (SE) kj/ g·mol. Combining our own data with previously published data, we recommend using the values 42.0, 40.6, and 39.1 (± 0.1) (SE) kjg·mol for the enthalpy of vaporization of m-xylene at 300, 340, and 380 deg. K, respectively, and a value for the change in heat capacity on vaporization (ΔCpdeg.) of 35 ± 3 (SE) J/g·mol·K over the temperature range studied. (author)

Double liquid membrane system for the removal of actinides and lanthanides from acidic nuclear wastes

International Nuclear Information System (INIS)

Chiarizia, R.; Danesi, P.R.

1985-01-01

Supported liquid membranes (SLM), consisting of an organic solution of n-octyl-(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) and tributyl-phosphate (TBP) in decalin are able to perform selective separation and concentration of actinide and lanthanide ions from aqueous nitrate feed solutions and synthetic nuclear wastes. In the membrane process a possible strip solution is a mixture of formic acid and hydroxylammonium formate (HAF). The effectiveness of this strip solution is reduced and eventually nullified by the simultaneous transfer through the SLM of nitric acid which accumulates in the strip solution. A possible way to overcome this drawback is to make use of a second SLM consisting of a primary amine which is able to extract only HNO 3 from the strip solution. In this work the results obtained by experimentally studying the membrane system: synthetic nuclear waste/CMPO-TBP membrane/HCOOH-HAF strip solution/primary amine membrane/NaOH solution, are reported. They show that the use of a second liquid membrane is effective in controlling the HNO 3 concentration in the strip solution, thus allowing the actinide and lanthanide ions removal from the feed solution to proceed to completion. 15 refs., 10 figs., 1 tab

Component activities in the system thorium nitrate-nitric acid-water at 25oC

International Nuclear Information System (INIS)

Lemire, R.J.; Brown, C.P.

1982-01-01

The equilibrium composition of the vapor above thorium nitrate-nitric acid-water mixtures has been studied as a function of the concentrations of thorium nitrate and nitric acid using a transpiration technique. At 25 o C, the thorium nitrate concentrations m T ranged from 0.1 to 2.5 molal and the nitric acid concentrations m N from 0.3 to 25 molal. The vapor pressure of the nitric acid was found to increase with increasing thorium nitrate concentration for a constant molality of nitric acid in aqueous solution. At constant m T , the nitric acid vapor pressure was particularly enhanced at low nitric acid concentrations. The water vapor pressures decreased regularly with increasing concentrations of both nitric acid and thorium nitrate. The experimental data were fitted to Scatchard's ion-component model, and to empirical multiparameter functions. From the fitting parameters, and available literature data for the nitric acid-water and thorium nitrate-water systems at 25 o C, expressions were calculated for the variation of water and thorium nitrate activities, as functions of the nitric acid and thorium nitrate concentrations, using the Gibbs-Duhem equation. Calculated values for the thorium nitrate activities were strongly dependent on the form of the function originally used to fit the vapor pressure data. (author)

Sensitivity of the photodissociation of NO2, NO3, HNO3 and H2O2 to the solar radiation diffused by the ground and by atmospheric particles

International Nuclear Information System (INIS)

Mugnai, A.; Petroncelli, P.; Fiocco, G.

1979-01-01

The diffusion of solar radiation by atmospheric molecules and aerosols and by ground albedo affects the photodissociation rates of atmospheric species relevant to the ozone chemistry. In this paper, a previous investigation on the photodissociation of O 3 is extended to NO 2 , NO 3 , HNO 3 , H 2 O 2 . Because of the different character of the absorption spectra of these species, the behaviour of photodissociation profiles with height and their sensitivity to such factors as ground albedo, aerosol loads, solar zenith angle are somewhat different. The results show that the presence of the aerosols usually enhances the photodissociation in the upper troposphere and in the stratosphere, because of scattering, but tends to reduce it at low heights because of the increased extinction. Enhancements in the photodissociation coefficients are as high as 20 to 40% for low values of the albedo and large aerosol loads such as those obtained after a volcanic eruption. On the other hand, at large values of the albedo, the effect of aerosols is mainly in attenuating the radiation going into and coming from the ground and their presence can lead to reduced photolysis even in the stratosphere. (author)

Influence of hydrophobicity on the chemical treatments of graphene

Science.gov (United States)

Rai, Krishna Bahadur; Khadka, Ishwor Bahadur; Kim, Eun Hye; Ahn, Sung Joon; Kim, Hyun Woo; Ahn, Joung Real

2018-01-01

The defect-free transfer of graphene grown by using chemical vapor deposition is essential for its applications to electronic devices. For the reduction of inevitable chemical residues, such as polar molecules and ionized impurities resulting from the transfer process, a hydrophobic polydimethyl-siloxane (PDMS) film was coated on a SiO2/Si wafer. The hydrophobic PDMS film resulted in fewer defects in graphene in comparison to a bare SiO2/Si wafer, as measured with Raman spectroscopy. We also studied the influence of the hydrophobic PDMS film on the chemical doping of graphene. Here, nitric acid (HNO3) was used to make p-type graphene. When graphene was transferred onto a SiO2/Si wafer coated with the hydrophobic PDMS film, fewer defects, compared to those in graphene transferred onto a bare SiO2/Si wafer, were created in grapheme by HNO3 as measured with Raman spectroscopy. The experiments suggest that when graphene is transferred onto a hydrophobic film, the number of defects created by chemical molecules can be reduced.

Mercury determination in non- and biodegradable materials by cold vapor capacitively coupled plasma microtorch atomic emission spectrometry

Energy Technology Data Exchange (ETDEWEB)

Frentiu, Tiberiu, E-mail: ftibi@chem.ubbcluj.ro [Faculty of Chemistry and Chemical Engineering, Babes-Bolyai University, Arany Janos 11, 400028 Cluj-Napoca (Romania); Mihaltan, Alin I., E-mail: alinblaj2005@yahoo.com [National Institute for Research and Development of Optoelectronics Bucharest - Research Institute for Analytical Instrumentation, Donath 67, 400293 Cluj-Napoca (Romania); Ponta, Michaela, E-mail: mponta@chem.ubbcluj.ro [Faculty of Chemistry and Chemical Engineering, Babes-Bolyai University, Arany Janos 11, 400028 Cluj-Napoca (Romania); Darvasi, Eugen, E-mail: edarvasi@chem.ubbcluj.ro [Faculty of Chemistry and Chemical Engineering, Babes-Bolyai University, Arany Janos 11, 400028 Cluj-Napoca (Romania); Frentiu, Maria, E-mail: frentiu.maria@yahoo.com [National Institute for Research and Development of Optoelectronics Bucharest - Research Institute for Analytical Instrumentation, Donath 67, 400293 Cluj-Napoca (Romania); Cordos, Emil, E-mail: emilcordos@gmail.com [National Institute for Research and Development of Optoelectronics Bucharest - Research Institute for Analytical Instrumentation, Donath 67, 400293 Cluj-Napoca (Romania)

2011-10-15

Highlights: {yields} Use of a miniaturized analytical system with microtorch plasma for Hg determination. {yields} Determination of Hg in non- and biodegradable materials using cold vapor generation. {yields} Figures of merit and advantages of the miniaturized system for Hg determination. - Abstract: A new analytical system consisting of a low power capacitively coupled plasma microtorch (20 W, 13.56 MHz, 150 ml min{sup -1} Ar) and a microspectrometer was investigated for the Hg determination in non- and biodegradable materials by cold-vapor generation, using SnCl{sub 2} reductant, and atomic emission spectrometry. The investigated miniaturized system was used for Hg determination in recyclable plastics from electronic equipments and biodegradable materials (shopping bags of 98% biodegradable polyethylene and corn starch) with the advantages of easy operation and low analysis costs. Samples were mineralized in HNO{sub 3}-H{sub 2}SO{sub 4} mixture in a high-pressure microwave system. The detection limits of 0.05 ng ml{sup -1} or 0.08 {mu}g g{sup -1} in solid sample were compared with those reported for other analytical systems. The method precision was 1.5-9.4% for Hg levels of 1.37-13.9 mg kg{sup -1}, while recovery in two polyethylene certified reference materials in the range 98.7 {+-} 4.5% (95% confidence level).

Building blocks for ionic liquids: Vapor pressures and vaporization enthalpies of 1-(n-alkyl)-imidazoles

International Nuclear Information System (INIS)

Emel'yanenko, Vladimir N.; Portnova, Svetlana V.; Verevkin, Sergey P.; Skrzypczak, Andrzej; Schubert, Thomas

2011-01-01

Highlights: → We measured vapor pressures of the 1-(n-alkyl)-imidazoles by transpiration method. → Variations on the alkyl chain length n were C 3 , C 5 -C 7 , and C 9 -C 10 . → Enthalpies of vaporization were derived from (p, T) dependencies. → Enthalpies of vaporization at 298.15 K were linear dependent on the chain length. - Abstract: Vapor pressures of the linear 1-(n-alkyl)-imidazoles with the alkyl chain C 3 , C 5 -C 7 , and C 9 -C 10 have been measured by the transpiration method. The molar enthalpies of vaporization Δ l g H m of these compounds were derived from the temperature dependencies of vapor pressures. A linear correlation of enthalpies of vaporization Δ l g H m (298.15 K) of the 1-(n-alkyl)-imidazoles with the chain length has been found.

Isothermogravimetric determination of the enthalpies of vaporization of 1-alkyl-3-methylimidazolium ionic liquids.