Mechanistic Insights on C-O and C-C Bond Activation and Hydrogen Insertion during Acetic Acid Hydrogenation Catalyzed by Ruthenium Clusters in Aqueous Medium

Energy Technology Data Exchange (ETDEWEB)

Shangguan, Junnan; Olarte, Mariefel V.; Chin, Ya-Huei [Cathy

2016-06-07

Catalytic pathways for acetic acid (CH3COOH) and hydrogen (H2) reactions on dispersed Ru clusters in the aqueous medium and the associated kinetic requirements for C-O and C-C bond cleavages and hydrogen insertion are established from rate and isotopic assessments. CH3COOH reacts with H2 in steps that either retain its carbon backbone and lead to ethanol, ethyl acetate, and ethane (47-95 %, 1-23 %, and 2-17 % carbon selectivities, respectively) or break its C-C bond and form methane (1-43 % carbon selectivities) at moderate temperatures (413-523 K) and H2 pressures (10-60 bar, 298 K). Initial CH3COOH activation is the kinetically relevant step, during which CH3C(O)-OH bond cleaves on a metal site pair at Ru cluster surfaces nearly saturated with adsorbed hydroxyl (OH*) and acetate (CH3COO*) intermediates, forming an adsorbed acetyl (CH3CO*) and hydroxyl (OH*) species. Acetic acid turnover rates increase proportionally with both H2 (10-60 bar) and CH3COOH concentrations at low CH3COOH concentrations (<0.83 M), but decrease from first to zero order as the CH3COOH concentration and the CH3COO* coverages increase and the vacant Ru sites concomitantly decrease. Beyond the initial CH3C(O)-OH bond activation, sequential H-insertions on the surface acetyl species (CH3CO*) lead to C2 products and their derivative (ethanol, ethane, and ethyl acetate) and the competitive C-C bond cleavage of CH3CO* causes the eventual methane formation. The instantaneous carbon selectivities towards C2 species (ethanol, ethane, and ethyl acetate) increase linearly with the concentration of proton-type Hδ+ (derived from carboxylic acid dissociation) and chemisorbed H*. The selectivities towards C2 products decrease with increasing temperature, because of higher observed barriers for C-C bond cleavage than H-insertion. This study offers an interpretation of mechanism and energetics and provides kinetic evidence of carboxylic acid assisted proton-type hydrogen (Hδ+) shuffling during H

Combination of size selective binding ability of 18-crown-6 dissolved in aqueous phase and extractive properties of an amic acid; toward enhancement of rare earths separation

Energy Technology Data Exchange (ETDEWEB)

Safarbali, Reyhaneh; Yaftian, Mohammad Reza; Ghorbanloo, Massomeh [Zanjan Univ. (Iran, Islamic Republic of). PhaseEquilibria Research Lab.; Zamani, Abbasali [Zanjan Univ. (Iran, Islamic Republic of). Environmental Science Research Lab.

2016-11-15

The separation of La(III), Eu(III) and Er(III) ions by an amic acid, N,N-dioctyldiglycolamic acid (HL), dissolved in carbon tetrachloride has been improved in the presence of 18-crown-6 (18C6) in aqueous phase as a selective masking agent. The interaction between the studied metal ions and 18C6 resulted a shift in the extraction curve of the studied metal ions versus pH toward higher pH region. The displacement of the extraction curves was more pronounced for lanthanum ions and was varied as La(III) > Eu(III) > Er(III). This order of complexing ability of 18C6 toward the studied ions was attributed to the size adaptation of the ions and that of the crown ether cavity. The stability constants of the lanthanide-crown ether complexes in aqueous phase were evaluated. The influence of temperature on the extraction of studied metal ions from aqueous phase in the absence and the presence of 18C6 was tested in the range 298-308 K. This investigation allowed evaluating the thermodynamic parameters associated with the extraction process and those of the complexation of cations by 18C6 in the aqueous phase.

Correlation and Prediction of Thermal Properties and Phase Behaviour for a Class of Aqueous Electrolyte Systems

DEFF Research Database (Denmark)

Thomsen, Kaj; Rasmussen, Peter; Gani, Rafiqul

1996-01-01

An extended UNIQUAC model is used to describe phase behaviour (VLE, SLE) and thermal properties (heat of mixing, heat capacity) for aqueous solutions containing ions like (Na+, K+, H+) (Cl-, NO3-, SO42-, OH-, CO3-). A linear temperature dependence of the binary interaction parameters allows good...... agreement with experimental data in the temperature range 0-110 degrees C. Copyright (C) 1996 Elsevier Science Ltd...

A plant wide aqueous phase chemistry model describing pH variations and ion speciation/pairing in wastewater treatment process models

DEFF Research Database (Denmark)

Flores-Alsina, X.; Mbamba, C. Kazadi; Solon, K.

cationic/anionic loads. In this way, the general applicability/flexibility of the proposed approach is demonstrated by implementing the aqueous phase chemistry module in some of the most frequently used WWTP process simulation models. Finally, it is shown how traditional wastewater modelling studies can......, require a major, but unavoidable, additional degree of complexity when representing cationic/anionic behaviour in Activated Sludge (AS)/Anaerobic Digestion (AD) systems (Ikumi et al., 2014). In this paper, a plant-wide aqueous phase chemistry module describing pH variations plus ion speciation...... of Ordinary Differential Equations (ODEs) in order to reduce the overall stiffness of the system, thereby enhancing simulation speed. Additionally, a multi-dimensional version of the Newton-Raphson algorithm is applied to handle the existing multiple algebraic inter-dependencies (Solon et al., 2015...

A plant-wide aqueous phase chemistry module describing pH variations and ion speciation/pairing in wastewater treatment process models

DEFF Research Database (Denmark)

Flores Alsina, Xavier; Kazadi Mbamba, Christian; Solon, Kimberly

2015-01-01

at different cationic/anionic loads. In this way, the general applicability/flexibility of the proposed approach is demonstrated, by implementing the aqueous phase chemistry module in some of the most frequently used WWTP process simulation models. Finally, it is shown how traditional wastewater modelling......, but unavoidable, additional degree of complexity when representing cationic/anionic behaviour in Activated Sludge (AS)/Anaerobic Digestion (AD) systems. In this paper, a plant-wide aqueous phase chemistry module describing pH variations plus ion speciation/pairing is presented and interfaced with industry......) in order to reduce the overall stiffness of the system, thereby enhancing simulation speed. Additionally, a multi-dimensional version of the Newton-Raphson algorithm is applied to handle the existing multiple algebraic inter-dependencies. The latter is reinforced with the Simulated Annealing method...

Effect of pH to adsorption behavior of Pu on bentonite in aqueous environment

International Nuclear Information System (INIS)

Wang Xiaoqiang; Tuo Xianguo; Li Pingchuan; Leng Yangchun; Su Jilong; Yueping

2013-01-01

The effects of pH to the adsorption behavior of Pu in GMZ-bentonite, Lingshou Ca-bentonite, Na-bentonite and bleaching earth were tested by static adsorption experiments in aqueous environment. The results show that the adsorption equilibrium time of Pu is four days in GMZ-bentonite and 5-6 days in bleaching earth, Ca-bentonite and Na-bentonite. In aqueous environment, the adsorption capacity of bentonite to Pu increases with pH in water phase, and it is weak in acidic aqueous environment and strong in alkaline aqueous environment extremely. (authors)

A plant-wide aqueous phase chemistry module describing pH variations and ion speciation/pairing in wastewater treatment process models.

Science.gov (United States)

Flores-Alsina, Xavier; Kazadi Mbamba, Christian; Solon, Kimberly; Vrecko, Darko; Tait, Stephan; Batstone, Damien J; Jeppsson, Ulf; Gernaey, Krist V

2015-11-15

There is a growing interest within the Wastewater Treatment Plant (WWTP) modelling community to correctly describe physico-chemical processes after many years of mainly focusing on biokinetics. Indeed, future modelling needs, such as a plant-wide phosphorus (P) description, require a major, but unavoidable, additional degree of complexity when representing cationic/anionic behaviour in Activated Sludge (AS)/Anaerobic Digestion (AD) systems. In this paper, a plant-wide aqueous phase chemistry module describing pH variations plus ion speciation/pairing is presented and interfaced with industry standard models. The module accounts for extensive consideration of non-ideality, including ion activities instead of molar concentrations and complex ion pairing. The general equilibria are formulated as a set of Differential Algebraic Equations (DAEs) instead of Ordinary Differential Equations (ODEs) in order to reduce the overall stiffness of the system, thereby enhancing simulation speed. Additionally, a multi-dimensional version of the Newton-Raphson algorithm is applied to handle the existing multiple algebraic inter-dependencies. The latter is reinforced with the Simulated Annealing method to increase the robustness of the solver making the system not so dependent of the initial conditions. Simulation results show pH predictions when describing Biological Nutrient Removal (BNR) by the activated sludge models (ASM) 1, 2d and 3 comparing the performance of a nitrogen removal (WWTP1) and a combined nitrogen and phosphorus removal (WWTP2) treatment plant configuration under different anaerobic/anoxic/aerobic conditions. The same framework is implemented in the Benchmark Simulation Model No. 2 (BSM2) version of the Anaerobic Digestion Model No. 1 (ADM1) (WWTP3) as well, predicting pH values at different cationic/anionic loads. In this way, the general applicability/flexibility of the proposed approach is demonstrated, by implementing the aqueous phase chemistry module in some

Separation of four flavonol glycosides from Solanum rostratum Dunal using aqueous two-phase flotation followed by preparative high-performance liquid chromatography.

Science.gov (United States)

Chang, Lin; Shao, Qian; Xi, Xingjun; Chu, Qiao; Wei, Yun

2017-02-01

Aqueous two-phase flotation followed by preparative high-performance liquid chromatography was used to separate four flavonol glycosides from Solanum rostratum Dunal. In the aqueous two-phase flotation section, the effects of sublation solvent, solution pH, (NH 4 ) 2 SO 4 concentration in aqueous solution, cosolvent, N 2 flow rate, flotation time, and volumes of the polyethylene glycol phase on the recovery were investigated in detail, and the optimal conditions were selected: 50 wt% polyethylene glycol 1000 ethanol solvent as the flotation solvent, pH 4, 350 g/L of (NH 4 ) 2 SO 4 concentration in aqueous phase, 40 mL/min of N 2 flow rate, 30 min of flotation time, 10.0 mL of flotation solvent volume, and two times. After aqueous two-phase flotation concentration, the flotation products were purified by preparative high-performance liquid chromatography. The purities of the final products A and B were 98.1 and 99.0%. Product B was the mixture of three compounds based on the analysis of high-performance liquid chromatography at the temperature of 10°C, while product A was hyperoside after the identification by nuclear magnetic resonance. Astragalin, 3'-O-methylquercetin 3-O-β-d-galactopyranoside, and 3'-O-methylquercetin 3-O-β-d-glucopyranoside were obtained with the purity of 93.8, 97.1, and 99.2%, respectively, after the further separation of product B using preparative high-performance liquid chromatography. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

LABORATORY GAS-PHASE DETECTION OF THE CYCLOPROPENYL CATION (c-C{sub 3}H{sub 3} {sup +})

Energy Technology Data Exchange (ETDEWEB)

Zhao, Dongfeng; Doney, Kirstin D.; Linnartz, Harold, E-mail: zhao@strw.leidenuniv.nl [Sackler Laboratory for Astrophysics, Leiden Observatory, University of Leiden, PO Box 9513, NL 2300 RA Leiden (Netherlands)

2014-08-20

The cyclopropenyl cation (c-C{sub 3}H{sub 3} {sup +}) is the smallest aromatic hydrocarbon molecule and considered to be a pivotal intermediate in ion-molecule reactions in space. An astronomical identification has been prohibited so far, because of a lack of gas-phase data. Here we report the first high resolution infrared laboratory gas-phase spectrum of the ν {sub 4} (C-H asymmetric stretching) fundamental band of c-C{sub 3}H{sub 3} {sup +}. The c-C{sub 3}H{sub 3} {sup +} cations are generated in supersonically expanding planar plasma by discharging a propyne/helium gas pulse, yielding a rotational temperature of ∼35 K. The absorption spectrum is recorded in the 3.19 μm region using sensitive continuous-wave cavity ring-down spectroscopy. The analysis of about 130 ro-vibrational transitions results in precise spectroscopic parameters. These constants allow for an accurate comparison with high-level theoretical predictions, and provide the relevant information needed to search for this astrochemically relevant carbo-cation in space.

Integration of carboxyl modified magnetic particles and aqueous two-phase extraction for selective separation of proteins.

Science.gov (United States)

Gai, Qingqing; Qu, Feng; Zhang, Tao; Zhang, Yukui

2011-07-15

Both of the magnetic particle adsorption and aqueous two-phase extraction (ATPE) were simple, fast and low-cost method for protein separation. Selective proteins adsorption by carboxyl modified magnetic particles was investigated according to protein isoelectric point, solution pH and ionic strength. Aqueous two-phase system of PEG/sulphate exhibited selective separation and extraction for proteins before and after magnetic adsorption. The two combination ways, magnetic adsorption followed by ATPE and ATPE followed by magnetic adsorption, for the separation of proteins mixture of lysozyme, bovine serum albumin, trypsin, cytochrome C and myloglobin were discussed and compared. The way of magnetic adsorption followed by ATPE was also applied to human serum separation. Copyright © 2011 Elsevier B.V. All rights reserved.

Extraction of Oxytetracycline Hydrochloride in Aqueous Two-phase System of Acetone and Ammonium Sulfate

International Nuclear Information System (INIS)

Han, J.

2013-01-01

Summary: Aqueous two-phase system (ATPS) is an efficient implement for separation of various substrates, and extracted by an aqueous two-phase system has been successful ly applied in the downstream processing of various biological compounds. In this research, the extraction of oxytetracycline hydrochloride (OTC-HCl) was carried out in an aqueous two-phase system containing acetone and ammonium sulfate solution, which partitioned the antibiotic to the upper phase. The effects of some parameters on the extraction efficiency of OTC-HCl were studied in detail, including temperature, the volume of acetone, the pH value of ammonium sulfate solution, the concentrations of (NH/sub 4/)/sub 2/ SO/sub 4/ and OTC-HCl. The results showed that the volume of acetone, the pH value of ammonium sulfate solution and the concentration of OTC-HCl in feed had significant effects on the extraction efficiency of OTC-HCl, but the effects of temperature on the extraction of OTC-HCl was not obvious. (author)

Extraction of Oxytetracycline Hydrochloride in Aqueous Two-phase System of Acetone and Ammonium Sulfate

Energy Technology Data Exchange (ETDEWEB)

Han, J. [Jiangsu Univ., Zhenjiang (China). Dept. of Food and Biological Engineering

2013-02-15

Summary: Aqueous two-phase system (ATPS) is an efficient implement for separation of various substrates, and extracted by an aqueous two-phase system has been successful ly applied in the downstream processing of various biological compounds. In this research, the extraction of oxytetracycline hydrochloride (OTC-HCl) was carried out in an aqueous two-phase system containing acetone and ammonium sulfate solution, which partitioned the antibiotic to the upper phase. The effects of some parameters on the extraction efficiency of OTC-HCl were studied in detail, including temperature, the volume of acetone, the pH value of ammonium sulfate solution, the concentrations of (NH/sub 4/)/sub 2/ SO/sub 4/ and OTC-HCl. The results showed that the volume of acetone, the pH value of ammonium sulfate solution and the concentration of OTC-HCl in feed had significant effects on the extraction efficiency of OTC-HCl, but the effects of temperature on the extraction of OTC-HCl was not obvious. (author)

High pH mobile phase effects on silica-based reversed-phase high-performance liquid chromatographic columns

NARCIS (Netherlands)

Kirkland, J.J.; Straten, van M.A.; Claessens, H.A.

1995-01-01

Aqueous mobile phases above pH 8 often cause premature column failure, limiting the utility of silica-based columns for applications requiring high pH. Previous studies suggest that covalently bound silane ligands are hydrolyzed and removed by high-pH mobile phases. However, we found that the

Electronic structure tautomerism, and mechanism of H-D exchange in imidazole aqueous solutions

International Nuclear Information System (INIS)

Borisov, Yu.A.; Vorob'eva, N.P.; Abronin, I.A.; Kolomiets, A.F.

1988-01-01

The imidazole electronic structure in a gaseous phase is studied taking into account the influence of solvation effects in aqueous solutions. Possible mechanisms of tautomeric transformations and H-D exchange reactions with water molecules are discussed. Using the quantum chemistry methods, it is shown that the intramolecular mechanism of imidazole isomerization in the gaseous phase and the aqueous solution is unprofitable, and the intermolecular mechanism can proceed through the stage of protonated and carbene form formation

Pinning of phase separation of aqueous solution of hydroxypropylmethylcellulose by gelation

Science.gov (United States)

Kita, Rio; Kaku, Takeshi; Kubota, Kenji; Dobashi, Toshiaki

1999-08-01

Opalescence of the aqueous solution of hydroxypropylmethylcellulose (HPMC) induced by heating has been studied in terms of the phase diagram and the phase separation dynamics. The cloud point curve and the sol-to-gel transition curve intersected with each other at about 55 °C. Just above the cloud-point curve at which the spinodal curve has its minimum, a ring-like scattering pattern appeared corresponding to the spinodal decomposition. Temporal growth of the scattering function in the course of phase separation was studied by a time-resolved light scattering technique. The gelation pinned the phase separation (spinodal decomposition) of the aqueous HPMC solution.

Adsorptive removal of phthalate ester (Di-ethyl phthalate) from aqueous phase by activated carbon: a kinetic study.

Science.gov (United States)

Venkata Mohan, S; Shailaja, S; Rama Krishna, M; Sarma, P N

2007-07-19

Adsorptive studies were carried out on Di-ethyl phthalate (DEP) removal from aqueous phase onto activated carbon. Batch sorption studies were performed and the results revealed that activated carbon demonstrated ability to adsorb DEP. Influence of varying experimental conditions such as DEP concentration, pH of aqueous solution, and dosage of adsorbent were investigated on the adsorption process. Sorption interaction of DEP onto activated carbon obeyed the pseudo second order rate equation. Experimental data showed good fit with both the Langmuir and Freundlich adsorption isotherm models. DEP sorption was found to be dependent on the aqueous phase pH and the uptake was observed to be greater at acidic pH.

Retention of ionisable compounds on high-performance liquid chromatography XVI. Estimation of retention with acetonitrile/water mobile phases from aqueous buffer pH and analyte pKa.

Science.gov (United States)

Subirats, Xavier; Bosch, Elisabeth; Rosés, Martí

2006-07-21

In agreement with our previous studies and those of other authors, it is shown that much better fits of retention time as a function of pH are obtained for acid-base analytes when pH is measured in the mobile phase, than when pH is measured in the aqueous buffer when buffers of different nature are used. However, in some instances it may be more practical to measure the pH in the aqueous buffer before addition of the organic modifier. Thus, an open methodology is presented that allows prediction of chromatographic retention of acid-base analytes from the pH measured in the aqueous buffer. The model presented estimates the pH of the buffer and the pKa of the analyte in a particular acetonitrile/water mobile phase from the pH and pKa values in water. The retention of the analyte can be easily estimated, at a buffer pH close to the solute pKa, from these values and from the retentions of the pure acidic and basic forms of the analyte. Since in many instances, the analyte pKa values in water are not known, the methodology has been also tested by using Internet software, at reach of many chemists, which calculates analyte pKa values from chemical structure. The approach is successfully tested for some pharmaceutical drugs.

Glycine phases formed from frozen aqueous solutions: Revisited

Energy Technology Data Exchange (ETDEWEB)

Surovtsev, N. V. [Institute of Automation and Electrometry, Siberian Branch of Russian Academy of Sciences, Novosibirsk 630090 (Russian Federation); Novosibirsk State University, Novosibirsk 630090 (Russian Federation); Adichtchev, S. V.; Malinovsky, V. K. [Institute of Automation and Electrometry, Siberian Branch of Russian Academy of Sciences, Novosibirsk 630090 (Russian Federation); Ogienko, A. G.; Manakov, A. Yu. [Novosibirsk State University, Novosibirsk 630090 (Russian Federation); Nikolaev Institute of Inorganic Chemistry, Siberian Branch of Russian Academy of Sciences, Novosibirsk 630090 (Russian Federation); Drebushchak, V. A. [Novosibirsk State University, Novosibirsk 630090 (Russian Federation); Institute of Geology and Mineralogy, Siberian Branch of Russian Academy of Sciences, Novosibirsk 630090 (Russian Federation); Ancharov, A. I.; Boldyreva, E. V. [Novosibirsk State University, Novosibirsk 630090 (Russian Federation); Institute of Solid Chemistry and Mechanochemistry, Siberian Branch of Russian Academy of Sciences, Novosibirsk 630090 (Russian Federation); Yunoshev, A. S. [Novosibirsk State University, Novosibirsk 630090 (Russian Federation); Lavrentiev Institute of Hydrodynamics, Siberian Branch of Russian Academy of Sciences, Novosibirsk 630090 (Russian Federation)

2012-08-14

Glycine phases formed when aqueous solutions were frozen and subsequently heated under different conditions were studied by Raman scattering, x-ray diffraction, and differential scanning calorimetry (DSC) techniques. Crystallization of ice I{sub h} was observed in all the cases. On cooling at the rates of 0.5 K/min and 5 K/min, glassy glycine was formed as an intermediate phase which lived about 1 min or less only, and then transformed into {beta}-polymorph of glycine. Quench cooling of glycine solutions (15% w/w) in liquid nitrogen resulted in the formation of a mixture of crystalline water ice I{sub h} and a glassy glycine, which could be preserved at cryogenic temperatures (80 K) for an indefinitely long time. This mixture remained also quite stable for some time after heating above the cryogenic temperature. Subsequent heating under various conditions resulted in the transformation of the glycine glass into an unknown crystalline phase (glycine 'X-phase') at 209-216 K, which at 218-226 K transformed into {beta}-polymorph of glycine. The 'X-phase' was characterized by Raman spectroscopy; it could be obtained in noticeable amounts using a special preparation technique and tentatively characterized by x-ray powder diffraction (P2, a= 6.648 A, b= 25.867 A, c= 5.610 A, {beta}= 113.12 Masculine-Ordinal-Indicator ); the formation of 'X-phase' from the glycine glassy phase and its transformation into {beta}-polymorph were followed by DSC. Raman scattering technique with its power for unambiguous identification of the crystalline and glassy polymorphs without limitation on the crystallite size helped us to follow the phase transformations during quenching, heating, and annealing. The experimental findings are considered in relation to the problem of control of glycine polymorphism on crystallization.

Graphite-supported platinum catalysts: Effects of gas and aqueous phase treatments

Energy Technology Data Exchange (ETDEWEB)

Vleeming, J.H.; Kuster, B.F.M.; Marin, G.B. [Eindhoven Univ. of Technology (Netherlands)] [and others

1997-03-01

The effects on the platinum particle diameter and the available platinum surface area of a graphite-supported platinum catalyst resulting from pretreatments and from performing a selective oxidation reaction are investigated. In the gas phase considerable catalyst sintering occurs only in the presence of oxygen at 773 K due to extensive carbon burn-off, whereas in an aqueous phase platinum particle growth is limited upon oxidative treatment. A hydrogen treatment in aqueous phase at 363 K causes platinum particle growth, aggregate formation, and covering of metal sites. These phenomena become more important with increasing pH. Platinum particle growth and aggregate formation are attributed to platinum particle rather than platinum adatom mobility and is caused by the destruction of the oxygen-containing surface groups on the graphite support, which serve as anchorage sites for the platinum particles. Site covering is caused by products originating from the graphite support, which are formed as a result of the reductive treatments. When performing the aqueous phase oxidation of methyl {alpha}-D-glucopyranoside at 323 K and a pH of 9, catalyst modifications are small under oxidative conditions. Exposure of the catalyst for several hours to methyl {alpha}-D-glucopyranoside under the same conditions but in the absence of oxygen causes site covering. 50 refs., 9 figs., 1 tab.

Compositional evolution of particle-phase reaction products and water in the heterogeneous OH oxidation of model aqueous organic aerosols

Directory of Open Access Journals (Sweden)

M. M. Chim

2017-12-01

Full Text Available Organic compounds present at or near the surface of aqueous droplets can be efficiently oxidized by gas-phase OH radicals, which alter the molecular distribution of the reaction products within the droplet. A change in aerosol composition affects the hygroscopicity and leads to a concomitant response in the equilibrium amount of particle-phase water. The variation in the aerosol water content affects the aerosol size and physicochemical properties, which in turn governs the oxidation kinetics and chemistry. To attain better knowledge of the compositional evolution of aqueous organic droplets during oxidation, this work investigates the heterogeneous OH-radical-initiated oxidation of aqueous methylsuccinic acid (C5H8O4 droplets, a model compound for small branched dicarboxylic acids found in atmospheric aerosols, at a high relative humidity of 85 % through experimental and modeling approaches. Aerosol mass spectra measured by a soft atmospheric pressure ionization source (Direct Analysis in Real Time, DART coupled with a high-resolution mass spectrometer reveal two major products: a five carbon atom (C5 hydroxyl functionalization product (C5H8O5 and a C4 fragmentation product (C4H6O3. These two products likely originate from the formation and subsequent reactions (intermolecular hydrogen abstraction and carbon–carbon bond scission of tertiary alkoxy radicals resulting from the OH abstraction occurring at the methyl-substituted carbon site. Based on the identification of the reaction products, a kinetic model of oxidation (a two-product model coupled with the Aerosol Inorganic–Organic Mixtures Functional groups Activity Coefficients (AIOMFAC model is built to simulate the size and compositional changes of aqueous methylsuccinic acid droplets during oxidation. Model results show that at the maximum OH exposure, the droplets become slightly more hygroscopic after oxidation, as the mass fraction of water is predicted to increase from

Nutrient removal and energy production from aqueous phase of bio-oil generated via hydrothermal liquefaction of algae.

Science.gov (United States)

Shanmugam, Saravanan R; Adhikari, Sushil; Shakya, Rajdeep

2017-04-01

Removal of nutrients (phosphorus and nitrogen) as struvite from bio-oil aqueous phase generated via hydrothermal liquefaction of algae was evaluated in this study. Effect of process parameters such as pH, temperature and reaction time on struvite formation was studied. More than 99% of phosphorus and 40-100% ammonium nitrogen were removed under all experimental conditions. X-ray diffraction analysis confirmed the formation of struvite, and the struvite recovered from bio-oil aqueous phase can be used as a slow-release fertilizer. Biogas production from struvite recovered bio-oil aqueous phase showed 3.5 times higher CH 4 yield (182±39mL/g COD) as compared to non-struvite recovered aqueous phase. The results from this study indicate that both struvite and methane can be produced from bio-oil aqueous phase. Copyright © 2017 Elsevier Ltd. All rights reserved.

High temperature aqueous potassium and sodium phosphate solutions: two-liquid-phase boundaries and critical phenomena, 275-4000C; potential applications for steam generators

International Nuclear Information System (INIS)

Marshall, W.L.

1981-12-01

Two-liquid-phase boundaries at temperatures between 275 and 400 0 C were determined for potassium phosphate and sodium phosphate aqueous solutions for compositions from 0 to 60 wt % dissolved salt. The stoichiometric mole ratios, K/PO 4 or Na/PO 4 , were varied from 1.00 to 2.12 and from 1.00 to 2.16 for the potassium and sodium systems, respectively. Liquid-vapor critical temperatures were also determined for most of the dilute liquid phases that formed. The minimum temperatures (below which a single solution existed) of two-liquid-phase formation were 360 0 C for the potassium system and 279 0 C for the sodium system at mole ratios of 2.00 and 2.16, respectively. For the sodium system at mole ratios greater than 2.16, solids crystallized at lower temperatures as expected from earlier studies. In contrast, potassium solutions that were explored at mole ratios from 2.12 to 3.16 and at temperatures below 360 0 C did not produce solid phases nor liquid-liquid immiscibilities. Aside from the generally unusual observations of two immiscible liquids in an aqueous inorganic salt system, the results could possibly be applied to the use of phosphate additives in steam power generators. 16 refs

Mercury absorption in aqueous hypochlorite

International Nuclear Information System (INIS)

Zhao, L.L.; Rochelle, G.T.

1999-01-01

The absorption of elemental Hg vapor into aqueous hypochlorite was measured in a stirred tank reactor at 25 and 55C. NaOCl strongly absorbs Hg even at high pH. Low pH, high Cl - and high-temperature favor mercury absorption. Aqueous free Cl 2 was the active species that reacted with mercury. However, chlorine desorption was evident at high Cl - and pH 15 M -1 s -1 at 25C and 1.4x10 17 M -1 s -1 at 55C. Gas-phase reaction was observed between Hg and Cl 2 on apparatus surfaces. Strong mercury absorption in water was also detected with Cl 2 present. Results indicate that the chlorine concentration, moisture, and surface area contribute positively to mercury removal. (Copyright (c) 1999 Elsevier Science B.V., Amsterdam. All rights reserved.)

The I{sub c}(H)-T{sub c}(H) phase boundary of superconducting Nb thin films with periodic and quasiperiodic antidot arrays

Energy Technology Data Exchange (ETDEWEB)

Bothner, D.; Kemmler, M.; Cozma, R.; Kleiner, R.; Koelle, D. [Physikalisches Institut and Center for Collective Quantum Phenomena, Universitaet Tuebingen (Germany); Misko, V.; Peeters, F. [Departement Fysica, Universiteit Antwerpen (Belgium); Nori, F. [Advanced Science Institute, RIKEN (Japan)

2011-07-01

The magnetic field dependent critical current I{sub c}(H) of superconducting thin films with artificial defects strongly depends on the symmetry of the defect arrangement. Likewise the critical temperature T{sub c}(H) of superconducting wire networks is heavily influenced by the symmetry of the system. Here we present experimental data on the I{sub c}(H)-T{sub c}(H) phase boundary of Nb thin films with artificial defect lattices of different symmetries. For this purpose we fabricated 60 nm thick Nb films with antidots in periodic (triangular) and five different quasiperiodic arrangements. The parameters of the antidot arrays were varied to investigate the influence of antidot diameter and array density. Experiments were performed with high temperature stability ({delta}T<1 mK) at 0.5{<=}T/T{sub c}{<=}1. From the I-V-characteristics at variable H and T we extract I{sub c}(H) and T{sub c}(H) for different voltage and resistance criteria. The experimental data for the critical current density are compared with results from numerical molecular dynamics simulations.

Unified pH values of liquid chromatography mobile phases.

Science.gov (United States)

Suu, Agnes; Jalukse, Lauri; Liigand, Jaanus; Kruve, Anneli; Himmel, Daniel; Krossing, Ingo; Rosés, Martí; Leito, Ivo

2015-03-03

This work introduces a conceptually new approach of measuring pH of mixed-solvent liquid chromatography (LC) mobile phases. Mobile phase pH is very important in LC, but its correct measurement is not straightforward, and all commonly used approaches have deficiencies. The new approach is based on the recently introduced unified pH (pH(abs)) scale, which enables direct comparison of acidities of solutions made in different solvents based on chemical potential of the proton in the solutions. This work represents the first experimental realization of the pH(abs) concept using differential potentiometric measurement for comparison of the chemical potentials of the proton in different solutions (connected by a salt bridge), together with earlier published reference points for obtaining the pH(abs) values (referenced to the gas phase) or pH(abs)(H₂O) values (referenced to the aqueous solution). The liquid junction potentials were estimated in the framework of Izutsu's three-component method. pH(abs) values for a number of common LC and LC-MS mobile phases have been determined. The pH(abs) scale enables for the first time direct comparison of acidities of any LC mobile phases, with different organic additives, different buffer components, etc. A possible experimental protocol of putting this new approach into chromatographic practice has been envisaged and its applicability tested. It has been demonstrated that the ionization behavior of bases (cationic acids) in the mobile phases can be better predicted by using the pH(abs)(H₂O) values and aqueous pKa values than by using the alternative means of expressing mobile phase acidity. Description of the ionization behavior of acids on the basis of pH(abs)(H₂O) values is possible if the change of their pKa values with solvent composition change is taken into account.

Partition Efficiency of High-Pitch Locular Multilayer Coil for Countercurrent Chromatographic Separation of Proteins Using Small-Scale Cross-Axis Coil Planet Centrifuge and Application to Purification of Various Collagenases with Aqueous-Aqueous Polymer Phase Systems.

Science.gov (United States)

Shinomiya, Kazufusa; Kobayashi, Hiroko; Inokuchi, Norio; Nakagomi, Kazuya; Ito, Yoichiro

2011-01-01

Partition efficiency of the high-pitch locular multilayer coil was evaluated in countercurrent chromatographic (CCC) separation of proteins with an aqueous-aqueous polymer phase system using the small-scale cross-axis coil planet centrifuge (X-axis CPC) fabricated in our laboratory. The separation column was specially made by high-pitch (ca 5 cm) winding of 1.0 mm I.D., 2.0 mm O.D. locular tubing compressed at 2 cm intervals with a total capacity of 29.5 mL. The protein separation was performed using a set of stable proteins including cytochrome C, myoglobin, and lysozyme with the 12.5% (w/w) polyethylene glycol (PEG) 1000 and 12.5% (w/w) dibasic potassium phosphate system (pH 9.2) under 1000 rpm of column revolution. This high-pitch locular tubing yielded substantially increased stationary phase retention than the normal locular tubing for both lower and upper mobile phases. In order to demonstrate the capability of the high-pitch locular tubing, the purification of collagenase from the crude commercial sample was carried out using an aqueous-aqueous polymer phase system. Using the 16.0% (w/w) PEG 1000 - 6.3% (w/w) dibasic potassium phosphate - 6.3% (w/w) monobasic potassium phosphate system (pH 6.6), collagenase I, II, V and X derived from Clostridium hystolyticum were separated from other proteins and colored small molecular weight compounds present in the crude commercial sample, while collagenase N-2 and S-1 from Streptomyces parvulus subsp. citrinus were eluted with impurities at the solvent front with the upper phase. The collagenase from C. hystolyticum retained its enzymatic activity in the purified fractions. The overall results demonstrated that the high-pitch locular multilayer coil is effectively used for the CCC purification of bioactive compounds without loss of their enzymatic activities.

Partition Efficiency of High-Pitch Locular Multilayer Coil for Countercurrent Chromatographic Separation of Proteins Using Small-Scale Cross-Axis Coil Planet Centrifuge and Application to Purification of Various Collagenases with Aqueous-Aqueous Polymer Phase Systems

Science.gov (United States)

Shinomiya, Kazufusa; Kobayashi, Hiroko; Inokuchi, Norio; Nakagomi, Kazuya; Ito, Yoichiro

2010-01-01

Partition efficiency of the high-pitch locular multilayer coil was evaluated in countercurrent chromatographic (CCC) separation of proteins with an aqueous-aqueous polymer phase system using the small-scale cross-axis coil planet centrifuge (X-axis CPC) fabricated in our laboratory. The separation column was specially made by high-pitch (ca 5 cm) winding of 1.0 mm I.D., 2.0 mm O.D. locular tubing compressed at 2 cm intervals with a total capacity of 29.5 mL. The protein separation was performed using a set of stable proteins including cytochrome C, myoglobin, and lysozyme with the 12.5% (w/w) polyethylene glycol (PEG) 1000 and 12.5% (w/w) dibasic potassium phosphate system (pH 9.2) under 1000 rpm of column revolution. This high-pitch locular tubing yielded substantially increased stationary phase retention than the normal locular tubing for both lower and upper mobile phases. In order to demonstrate the capability of the high-pitch locular tubing, the purification of collagenase from the crude commercial sample was carried out using an aqueous-aqueous polymer phase system. Using the 16.0% (w/w) PEG 1000 – 6.3% (w/w) dibasic potassium phosphate – 6.3% (w/w) monobasic potassium phosphate system (pH 6.6), collagenase I, II, V and X derived from Clostridium hystolyticum were separated from other proteins and colored small molecular weight compounds present in the crude commercial sample, while collagenase N-2 and S-1 from Streptomyces parvulus subsp. citrinus were eluted with impurities at the solvent front with the upper phase. The collagenase from C. hystolyticum retained its enzymatic activity in the purified fractions. The overall results demonstrated that the high-pitch locular multilayer coil is effectively used for the CCC purification of bioactive compounds without loss of their enzymatic activities. PMID:21869859

Quantitative analysis of aqueous phase composition of model dentin adhesives experiencing phase separation

Science.gov (United States)

Ye, Qiang; Park, Jonggu; Parthasarathy, Ranganathan; Pamatmat, Francis; Misra, Anil; Laurence, Jennifer S.; Marangos, Orestes; Spencer, Paulette

2013-01-01

There have been reports of the sensitivity of our current dentin adhesives to excess moisture, for example, water-blisters in adhesives placed on over-wet surfaces, and phase separation with concomitant limited infiltration of the critical dimethacrylate component into the demineralized dentin matrix. To determine quantitatively the hydrophobic/hydrophilic components in the aqueous phase when exposed to over-wet environments, model adhesives were mixed with 16, 33, and 50 wt % water to yield well-separated phases. Based upon high-performance liquid chromatography coupled with photodiode array detection, it was found that the amounts of hydrophobic BisGMA and hydrophobic initiators are less than 0.1 wt % in the aqueous phase. The amount of these compounds decreased with an increase in the initial water content. The major components of the aqueous phase were hydroxyethyl methacrylate (HEMA) and water, and the HEMA content ranged from 18.3 to 14.7 wt %. Different BisGMA homologues and the relative content of these homologues in the aqueous phase have been identified; however, the amount of crosslinkable BisGMA was minimal and, thus, could not help in the formation of a crosslinked polymer network in the aqueous phase. Without the protection afforded by a strong crosslinked network, the poorly photoreactive compounds of this aqueous phase could be leached easily. These results suggest that adhesive formulations should be designed to include hydrophilic multimethacrylate monomers and water compatible initiators. PMID:22331596

Discovery of a thermally persistent h.c.p. solid-solution phase in the Ni-W system

International Nuclear Information System (INIS)

Kurz, S. J. B.; Leineweber, A.; Maisel, S. B.; Höfler, M.; Müller, S.; Mittemeijer, E. J.

2014-01-01

Although the accepted Ni-W phase diagram does not reveal the existence of h.c.p.-based phases, h.c.p.-like stacking sequences were observed in magnetron-co-sputtered Ni-W thin films at W contents of 20 to 25 at. %, by using transmission electron microscopy and X-ray diffraction. The occurrence of this h.c.p.-like solid-solution phase could be rationalized by first-principles calculations, showing that the vicinity of the system's ground-state line is populated with metastable h.c.p.-based superstructures in the intermediate concentration range from 20 to 50 at. % W. The h.c.p.-like stacking in Ni-W films was observed to be thermally persistent, up to temperatures as high as at least 850 K, as evidenced by extensive X-ray diffraction analyses on specimens before and after annealing treatments. The tendency of Ni-W for excessive planar faulting is discussed in the light of these new findings

Liquid-liquid equilibrium of water + PEG 8000 + magnesium sulfate or sodium sulfate aqueous two-phase systems at 35°C: experimental determination and thermodynamic modeling

Directory of Open Access Journals (Sweden)

B. D. Castro

2005-09-01

Full Text Available Liquid-liquid extraction using aqueous two-phase systems is a highly efficient technique for separation and purification of biomolecules due to the mild properties of both liquid phases. Reliable data on the phase behavior of these systems are essential for the design and operation of new separation processes; several authors reported phase diagrams for polymer-polymer systems, but data on polymer-salt systems are still relatively scarce. In this work, experimental liquid-liquid equilibrium data on water + polyethylene glycol 8000 + magnesium sulfate and water + polyethylene glycol 8000 + sodium sulfate aqueous two-phase systems were obtained at 35°C. Both equilibrium phases were analyzed by lyophilization and ashing. Experimental results were correlated with a mass-fraction-based NRTL activity coefficient model. New interaction parameters were estimated with the Simplex method. The mean deviations between the experimental and calculated compositions in both equilibrium phases is about 2%.

Influence of aqueous phase on electrochemical biocorrosion tests in diesel/water systems

Energy Technology Data Exchange (ETDEWEB)

Bento, F.M. [Dept. of Soils, Faculty of Agronomy, UFRGS, 7712 Bento Goncalves Avenue, CEP: 91540-001, POA, RS (Brazil); Englert, G.E.; Muller, I.L. [Dept. of Metallurgy, Biocorrosion and Biofilms Lab, UFRGS, 99 Osvaldo Aranha Avenue s.615D, CEP: 90035-190, POA, RS (Brazil); Gaylarde, C.C. [Dept. of Biophisics, UFRGS POA, RS (Brazil)

2004-08-01

Storage tanks containing microbially contaminated diesel oil are susceptible to corrosion. This process may be evaluated electrochemically in the laboratory using simulated storage systems containing diesel oil and an aqueous phase. The simulated aqueous phase must supply mineral nutrients for microbial growth, together with adequate electrical conductivity, without, however, being too corrosive, so as to allow the aggressive nature of the microbial metabolites to be detected. In this investigation, microbial growth was measured in six electrically conductive media overlaid with metropolitan diesel oil containing an additive package. The microorganisms were the filamentous fungi, Hormoconis resinae, Paecilomyces variotii and Aspergillus fumigatus, the bacterium Bacillus subtilis and the yeast Candida silvicola, all previously isolated from contaminated diesel oil. After 60 days incubation with pure or mixed inocula of these microorganisms, pH, conductivity and viable microorganisms were measured. The electrochemical behaviour of carbon steel ASTM 283-93-C was determined in each of the six media (uninoculated) and in selected inoculated medium via measurements of open circuit potential and potentiostatic polarization curves. The uptake of phosphate (corrosion inhibitor), microbial growth, pH, conductivity and anodic and cathodic polarization curves were assessed in the water phase after 30 and 60 days of incubation with each single species Aspergillus fumigatus and Hormoconis resinae and with the consortium. The medium which proved most appropriate was Bushnell-Haas medium modified by the omission of chlorides, which allowed satisfactory microbial growth and had low aggressivity towards the steel. The performance of electrochemical tests in aerated, rather than deaerated, electrolyte solutions is suggested to be important to allow the detection of microbial influence on passive film formation and stability. (Abstract Copyright [2004], Wiley Periodicals, Inc.)

Ettringite and C-S-H Portland cement phases for waste ion immobilization: A review

International Nuclear Information System (INIS)

Gougar, M.L.D.; Scheetz, B.E.; Roy, D.M.

1996-01-01

The formation, structure and chemistry of the ettringite and C-S-H phases of Portland cement have been reviewed as they relate to waste ion immobilization. The purpose of this review was to investigate the use of Portland cement as a host for priority metallic pollutants as identified by the Environmental Protection Agency and as a host for radioactive waste ions as identified in 40 CFR 191. Ettringite acts as host to a number of these ions in both the columnar and channel sections of the crystal structure. Substitutions have been made at the calcium, aluminum, hydroxide and sulfate sites. C-S-H also hosts a number of the waste species in both ionic and salt form. Immobilization mechanisms for C-S-H include sorption, phase mixing and substitution. The following ions have not apparently been reported as specifically immobilized by one of these phases: Ag, Am, Np, Pu, Ra, Tc, Th and Sn; however, some of these ions are immobilized by Portland cement

Solution and solid-phase halogen and C-H hydrogen bonding to perrhenate.

Science.gov (United States)

Massena, Casey J; Riel, Asia Marie S; Neuhaus, George F; Decato, Daniel A; Berryman, Orion B

2015-01-28

(1)H NMR spectroscopic and X-ray crystallographic investigations of a 1,3-bis(4-ethynyl-3-iodopyridinium)benzene scaffold with perrhenate reveal strong halogen bonding in solution, and bidentate association in the solid state. A nearly isostructural host molecule demonstrates significant C-H hydrogen bonding to perrhenate in the same phases.

Equilibrium aluminium hydroxo-oxalate phases during initial clay formation; H +-Al 3+-oxalic acid-Na + system

Science.gov (United States)

Bilinski, Halka; Horvath, Laszlo; Ingri, Nils; Sjöberg, Staffan

1986-09-01

The conditions necessary for initial clay formation have been studied in different model systems comprising different organic acids besides Si and Al. In the present paper the solid phases and the precipitation boundary characterizing the subsystem H +-Al 3+-oxalic acid (H 2L) are discussed. pH and tyndallometric measurements were performed in an ionic medium of 0.6 M Na(Cl) at 25 °C. The two phases Al 3(OH) 7(C 2O 4) · 3H 2O (phase I) and NaAl(OH) 2(C 2O 4) · 3H 2O (phase II) determine the precipitation boundary. The following formation constants for the two phases were deduced: lgβ1 = lg([ Al3+] -3[ H2C2O4] -1[ H+] 9 = -21.87 ± 0.08 and lgβ11 = lg([ Al3+] -1[ H2C2O4] -1[ H+] 4 = -5.61 ± 0.06. Phase I exists in the range [ Al] tot≥ 10 -4.4moldm-3,[ H2C2O4] tot ≥ 10 -4.9moldm-3 and at pH oxalic-rich natural waters. The more soluble sodium phase is unlikely to exist in natural waters. The two phases are metastable relative to crystalline gibbsite and may be considered as the first precipitation step in the transition from aqueous Al oxalates down to stable Al hydroxide. Model calculations illustrating these competing hydrolysis-complexation reactions are discussed in terms of predominance and speciation diagrams. The solid phases have been characterized by X-ray analysis of powders, TGA and IR spectra, and tentative structures are proposed. Phase I seems to be an octahedral layer structure, in which 3/5 of the octahedral sites between two close packed oxygen sheets are occupied by Al 3+ and the oxalate ion acts as a bridge ligand between two aluminium atoms. Phase II forms a more open sheet structure and has ion exchange properties. Powder data for a phase crystallized from the studied solution after a year are also presented. This phase, Na 4Al 2(OH) 2(C 2O 4) 4 · 10H 2O, supports the results from the equilibrium analysis of recent solution data by SJöBERG and ÖHMAN (1985), who have found the dinuclear complex Al 2(OH) 2(C 2O 4) 44- to exist in a

Formation of aqueous-phase α-hydroxyhydroperoxides (α-HHP: potential atmospheric impacts

Directory of Open Access Journals (Sweden)

R. Zhao

2013-06-01

Full Text Available The focus of this work is on quantifying the degree of the aqueous-phase formation of α-hydroxyhydroperoxides (α-HHPs via reversible nucleophilic addition of H2O2 to aldehydes. Formation of this class of highly oxygenated organic hydroperoxides represents a poorly characterized aqueous-phase processing pathway that may lead to enhanced SOA formation and aerosol toxicity. Specifically, the equilibrium constants of α-HHP formation have been determined using proton nuclear-magnetic-resonance (1H NMR spectroscopy and proton-transfer-reaction mass spectrometry (PTR-MS. Significant α-HHP formation was observed from formaldehyde, acetaldehyde, propionaldehyde, glycolaldehyde, glyoxylic acid, and methylglyoxal, but not from methacrolein and ketones. Low temperatures enhanced the formation of α-HHPs but slowed their formation rates. High inorganic salt concentrations shifted the equilibria toward the hydrated form of the aldehydes and slightly suppressed α-HHP formation. Using the experimental equilibrium constants, we predict the equilibrium concentration of α-HHPs to be in the μM level in cloud water, but it may also be present in the mM level in aerosol liquid water (ALW, where the concentrations of H2O2 and aldehydes can be high. Formation of α-HHPs in ALW may significantly affect the effective Henry's law constants of H2O2 and aldehydes but may not affect their gas-phase levels. The photochemistry and reactivity of this class of atmospheric species have not been studied.

Reversible, on-demand generation of aqueous two-phase microdroplets

Science.gov (United States)

Collier, Charles Patrick; Retterer, Scott Thomas; Boreyko, Jonathan Barton; Mruetusatorn, Prachya

2017-08-15

The present invention provides methods of on-demand, reversible generation of aqueous two-phase microdroplets core-shell microbeads, microparticle preparations comprising the core-shell microbeads, and drug delivery formulation comprising the microparticle preparations. Because these aqueous microdroplets have volumes comparable to those of cells, they provide an approach to mimicking the dynamic microcompartmentation of biomaterial that naturally occurs within the cytoplasm of cells. Hence, the present methods generate femtoliter aqueous two-phase droplets within a microfluidic oil channel using gated pressure pulses to generate individual, stationary two-phase microdroplets with a well-defined time zero for carrying out controlled and sequential phase transformations over time. Reversible phase transitions between single-phase, two-phase, and core-shell microbead states are obtained via evaporation-induced dehydration and water rehydration.

Design of functional guanidinium ionic liquid aqueous two-phase systems for the efficient purification of protein

Energy Technology Data Exchange (ETDEWEB)

Ding, Xueqin; Wang, Yuzhi, E-mail: wyzss@hnu.edu.cn; Zeng, Qun; Chen, Jing; Huang, Yanhua; Xu, Kaijia

2014-03-01

Graphical abstract: - Highlights: • A series of novel cationic functional hexaalkylguanidinium ionic liquids and anionic functional tetraalkylguanidinium ionic liquids have been synthesized. • Functional guanidinium ionic liquid aqueous two-phase systems have been first designed for the purification of protein. • Mechanisms and performances of the process were researched. • Simple, green, safety and presents better purified ability than ordinary process. • A potential efficient platform for protein purification and related studies. - Abstract: A series of novel cationic functional hexaalkylguanidinium ionic liquids and anionic functional tetraalkylguanidinium ionic liquids have been devised and synthesized based on 1,1,3,3-tetramethylguanidine. The structures of the ionic liquids (ILs) were confirmed by {sup 1}H nuclear magnetic resonance ({sup 1}H NMR) and 13C nuclear magnetic resonance (13C NMR) and the production yields were all above 90%. Functional guanidinium ionic liquid aqueous two-phase systems (FGIL-ATPSs) have been first designed with these functional guanidinium ILs and phosphate solution for the purification of protein. After phase separation, proteins had transferred into the IL-rich phase and the concentrations of proteins were determined by measuring the absorbance at 278 nm using an ultra violet visible (UV–vis) spectrophotometer. The advantages of FGIL-ATPSs were compared with ordinary ionic liquid aqueous two-phase systems (IL-ATPSs). The proposed FGIL-ATPS has been applied to purify lysozyme, trypsin, ovalbumin and bovine serum albumin. Single factor experiments were used to research the effects of the process, such as the amount of ionic liquid (IL), the concentration of salt solution, temperature and the amount of protein. The purification efficiency reaches to 97.05%. The secondary structure of protein during the experimental process was observed upon investigation using UV–vis spectrophotometer, Fourier-transform infrared

Nitrogen doping efficiency during vapor phase epitaxy of 4H-SiC

Energy Technology Data Exchange (ETDEWEB)

Rowland, L.B.; Brandt, C.D. [Northrop Grumman Science and Technology Center, Pittsburgh, PA (United States); Burk, A.A. Jr. [Northrop Grumman Advanced Technology Lab., Baltimore, MD (United States)

1998-06-01

This work examines the interrelationships among doping efficiency, mole fraction, and Si/C ratio for intentional doping of 4H-SiC during vapor phase epitaxy using N{sub 2}. For four Si/C ratios, the doping concentration increased linearly as a function of increasing N{sub 2} partial pressure with a slope of 1.0 {+-} 0.03. Variation of propane mole fraction while the SiH{sub 4} and N{sub 2} mole fractions were kept constant revealed two different modes of nitrogen incorporation, corresponding to carbon-rich and silicon-rich conditions. (orig.) 14 refs.

In-cloud multiphase behaviour of acetone in the troposphere: gas uptake, Henry's law equilibrium and aqueous phase photooxidation.

Science.gov (United States)

Poulain, Laurent; Katrib, Yasmine; Isikli, Estelle; Liu, Yao; Wortham, Henri; Mirabel, Philippe; Le Calvé, Stéphane; Monod, Anne

2010-09-01

Acetone is ubiquitous in the troposphere. Several papers have focused in the past on its gas phase reactivity and its impact on tropospheric chemistry. However, acetone is also present in atmospheric water droplets where its behaviour is still relatively unknown. In this work, we present its gas/aqueous phase transfer and its aqueous phase photooxidation. The uptake coefficient of acetone on water droplets was measured between 268 and 281K (γ=0.7 x 10(-2)-1.4 x 10(-2)), using the droplet train technique coupled to a mass spectrometer. The mass accommodation coefficient α (derived from γ) was found in the range (1.0-3.0±0.25) x 10(-2). Henry's law constant of acetone was directly measured between 283 and 298K using a dynamic equilibrium system (H((298K))=(29±5)Matm(-1)), with the Van't Hoff expression lnH(T)=(5100±1100)/T-(13.4±3.9). A recommended value of H was suggested according to comparison with literature. The OH-oxidation of acetone in the aqueous phase was carried out at 298K, under two different pH conditions: at pH=2, and under unbuffered conditions. In both cases, the formation of methylglyoxal, formaldehyde, hydroxyacetone, acetic acid/acetate and formic acid/formate was observed. The formation of small amounts of four hydroperoxides was also detected, and one of them was identified as peroxyacetic acid. A drastic effect of pH was observed on the yields of formaldehyde, one hydroperoxide, and, (to a lesser extent) acetic acid/acetate. Based on the experimental observations, a chemical mechanism of OH-oxidation of acetone in the aqueous phase was proposed and discussed. Atmospheric implications of these findings were finally discussed. Copyright © 2010 Elsevier Ltd. All rights reserved.

Formation of the second organic phase during uranyl nitrate extraction from aqueous solution by 30% tributylphosphate solution in paraffin

International Nuclear Information System (INIS)

Yhrkin, V.G.

1996-01-01

For extraction systems aqueous solution of uranyl nitrate-30% solution of tributylphosphate in individual paraffins from C 13 to C 17 the influence of the second organic phase of uranyl nitrate concentration in aqueous and organic phases, the length of hydrocarbon chain of paraffin hydrocarbon and temperature from 25 to 50 deg C on formation conditions has been defected. A special method of achieving the conditions of organic phase stratification from three-phase region, involving definition of equilibrium phases composition by density and refractive index, has been elaborated for more precise definition of organic phase homogeneity region. It has been revealed that without addition of nitric acid to uranyl nitrate solution the organic phase homogeneity limits can be achieved solely on paraffins C 15 , C 16 and C 17 and only under conditions similar to equeous phase saturation in terms of uranyl nitrate. 16 refs., 2 figs

Compact and highly stable quantum dots through optimized aqueous phase transfer

Science.gov (United States)

Tamang, Sudarsan; Beaune, Grégory; Poillot, Cathy; De Waard, Michel; Texier-Nogues, Isabelle; Reiss, Peter

2011-03-01

A large number of different approaches for the aqueous phase transfer of quantum dots have been proposed. Surface ligand exchange with small hydrophilic thiols, such as L-cysteine, yields the lowest particle hydrodynamic diameter. However, cysteine is prone to dimer formation, which limits colloidal stability. We demonstrate that precise pH control during aqueous phase transfer dramatically increases the colloidal stability of InP/ZnS quantum dots. Various bifunctional thiols have been applied. The formation of disulfides, strongly diminishing the fluorescence QY has been prevented through addition of appropriate reducing agents. Bright InP/ZnS quantum dots with a hydrodynamic diameter <10 nm and long-term stability have been obtained. Finally we present in vitro studies of the quantum dots functionalized with the cell-penetrating peptide maurocalcine.

Radionuclides retention in C-S-H, main phases of cement matrices for low and intermediate-level wastes

International Nuclear Information System (INIS)

Badillo A, V. E.; Lopez R, C.; Vidal M, J.; Gutierrez B, O.

2014-10-01

Knowing that the behavior of cementitious materials based on hydraulic binder called cement is essentially determined by the physicochemical evolution of the cement paste (water + cement) which constitutes it, the evolution of the cement paste in contact with different aqueous solutions is studied since one of the main risks in safety of systems is composed of surface and groundwater, which contribute to the alteration of the different barriers and represent the main way of radionuclides transport. The calcium silicates CSH are the main phases that compose the systems based on Portland cement. The hydrates calcium silicates possess a high degree of structural complexity which includes crystalline, partially crystalline and amorphous phases. In this study the microstructures of the CSH phases as well as the retention of radionuclide Sr (II) are studied through the 87m Sr in formulations of water/cement w/c = 0.55; experimental values of K d low around 20 ml g -1 are obtained in function of hydration time of the cement paste in equilibrium with aqueous solutions. (Author)

Buckminsterfullerene's (C60) octanol-water partition coefficient (Kow) and aqueous solubility.

Science.gov (United States)

Jafvert, Chad T; Kulkarni, Pradnya P

2008-08-15

To assess the risk and fate of fullerene C60 in the environment, its water solubility and partition coefficients in various systems are useful. In this study, the log Kow of C60 was measured to be 6.67, and the toluene-water partition coefficient was measured at log Ktw = 8.44. From these values and the respective solubilities of C60 in water-saturated octanol and water-saturated toluene, C60's aqueous solubility was calculated at 7.96 ng/L(1.11 x 10(-11) M) for the organic solvent-saturated aqueous phase. Additionally, the solubility of C60 was measured in mixtures of ethanol-water and tetrahydrofuran-water and modeled with Wohl's equation to confirm the accuracy of the calculated solubility value. Results of a generator column experiment strongly support the hypothesis that clusters form at aqueous concentrations below or near this calculated solubility. The Kow value is compared to those of other hydrophobic organic compounds, and bioconcentration factors for C60 were estimated on the basis of Kow.

Aqueous-phase photochemical oxidation and direct photolysis of vanillin - a model compound of methoxy phenols from biomass burning

Science.gov (United States)

Li, Y. J.; Huang, D. D.; Cheung, H. Y.; Lee, A. K. Y.; Chan, C. K.

2014-03-01

We present here experimental results on aqueous-phase (A) photochemical oxidation (with UV and OH radicals generated from H2O2 photolysis) and (B) direct photolysis (with only UV irradiation) of a methoxy phenol, vanillin (VL), as a model compound from biomass burning. Both on-line aerosol mass spectrometric (AMS) characterization and off-line chemical analyses were performed. AMS analyses of dried atomized droplets of the bulk reacting mixtures showed that VL almost entirely evaporates during the drying process. Large amounts of organic mass remained in the particle phase after reactions under both conditions. Under condition (A), AMS measured organic mass first increased rapidly and then decreased, attributable to the formation of non-volatile products and subsequent formation of smaller and volatile products, respectively. The oxygen-to-carbon (O : C) ratio of the products reached 1.5 after about 80 min, but dropped substantially thereafter. In contrast, organic mass increased slowly under condition (B). The O : C ratio reached 1.0 after 180 min. In off-line analyses, small oxygenates were detected under condition (A), while hydroxylated products and dimers of VL were detected under condition (B). Particle hygroscopic growth factor (GF) and cloud condensation nuclei (CCN) activity of the reacting mixtures were found to depend on both organic volume fraction and the degree of oxygenation of organics. Results show that (1) aqueous-phase processes can lead to the retention of a large portion of the organic mass in the particle phase; (2) once retained, this portion of organic mass significantly changes the hygroscopicity and CCN activity of the aerosol particles; (3) intensive photochemical oxidation gave rise to an O : C ratio as high as 1.5 but the ratio decreased as further oxidation led to smaller and more volatile products; and (4) polymerization occurred with direct photolysis, resulting in high-molecular-weight products of a yellowish color. This study

Aqueous-phase photochemical oxidation and direct photolysis of vanillin - a model compound of methoxy-phenols from biomass burning

Science.gov (United States)

Li, Y. J.; Huang, D. D.; Cheung, H. Y.; Lee, A. K. Y.; Chan, C. K.

2013-10-01

We present here experimental results on aqueous-phase (A) photochemical oxidation (with UV and OH radicals generated from H2O2 photolysis) and (B) direct photolysis (with only UV irradiation) of a methoxy-phenol, vanillin (VL), as a model compound from biomass burning. Both on-line aerosol mass spectrometric (AMS) characterization and off-line chemical analyses were performed. AMS analyses of dried atomized droplets of the bulk reacting mixtures showed that VL almost entirely evaporates during the drying process. Large amounts of organic mass remained in the particle phase after reactions under both conditions. Under condition (A), AMS measured organic mass first increased rapidly and then decreased, attributable to the formation of non-volatile products and subsequent formation of smaller and volatile products, respectively. The oxygen-to-carbon (O:C) ratio of the products reached 1.5 after about 80 min, but dropped substantially thereafter. In contrast, organic mass increased slowly under condition (B). The O:C ratio reached 1.0 after 180 min. In off-line analyses, small oxygenates were detected under condition (A), while hydroxylated products and dimers of VL were detected under condition (B). Particle hygroscopic growth factor (GF) and cloud condensation nuclei (CCN) activity of the reacting mixtures were found to be dependent on both organic volume fraction and the degree of oxygenation of organics. Results show that (1) aqueous-phase processes can lead to the retention of a large portion of the organic mass in the particle phase; (2) once retained, this portion of organic mass significantly changes the hygroscopicity and CCN activity of the aerosol particles; (3) intensive photochemical oxidation gave rise to an O:C ratio as high as 1.5 but the ratio decreased as further oxidation led to smaller and more volatile products; and (4) polymerization occurred with direct photolysis, resulting in high-molecular-weight products of a yellowish color. This study

Gas-phase reactivity of lanthanide cations with fluorocarbons: C-F versus C-H and C-C bond activation

International Nuclear Information System (INIS)

Cornehl, H.H.; Hornung, G.; Schwarz, H.

1996-01-01

The gas-phase reactivity of the fluorinated hydrocarbons CF 4 , CHF 3 , CH 3 F, C 2 F 6 , 1,1-C 2 H 4 F 2 , and C 6 F 6 with the lanthanide cations Ce + , Pr + , Sm + , Ho + , Tm + , and Yb + and the reactivity of C 6 H 5 F with all lanthanide cations Ln + (Ln = La-Lu, with the exception of Pm + ) have been examined by Fourier-transform ion cyclotron resonance mass spectrometry. The perfluorinated compounds tetrafluoromethane and hexafluoroethane as well as trifluoromethane do not react with any lanthanide cation. Selective activation of the strong C-F bonds in fluoromethane, 1,1-difluoroethane, hexafluorobenzene, and fluorobenzene appears as a general reaction scheme along the 4f row. Experimental evidence is given for a 'harpoon'-like mechanism for the F atom abstraction process which operates via an initial electron transfer from the lanthanide cation to the fluorinated substrate in the encounter complex Ln + RF. The most reactive lanthanides La + , Ce + , Gd + , and Tb + and also the formal closed-shell species Lu + exhibit additional C-H and C-C bond activation pathways in the reaction with fluorobenzene, namely dehydrohalogenation as well as loss of a neutral acetylene molecule. In the case of Tm + and Yb + the formation of neutral LnF 3 is observed in a multistep process via C-C coupling and charge transfer. 17 refs., 2 figs., 2 tabs

New lipid family that forms inverted cubic phases in equilibrium with excess water: molecular structure-aqueous phase structure relationship for lipids with 5,9,13,17-tetramethyloctadecyl and 5,9,13,17-tetramethyloctadecanoyl chains.

Science.gov (United States)

Yamashita, Jun; Shiono, Manzo; Hato, Masakatsu

2008-10-02

With a view to discovering a new family of lipids that form inverted cubic phases, the aqueous phase behavior of a series of lipids with isoprenoid-type hydrophobic chains has been examined over a temperature range from -40 to 65 degrees C by using optical microscopy, DSC (differential scanning calorimetry), and SAXS (small-angle X-ray scattering) techniques. The lipids examined are those with 5,9,13,17-tetramethyloctadecyl and 5,9,13,17-tetramethyloctadecanoyl chains linked to a series of headgroups, that is, erythritol, pentaerythritol, xylose, and glucose. All of the lipid/water systems displayed a "water + liquid crystalline phase" two-phase coexistence state when sufficiently diluted. The aqueous phase structures of the most diluted liquid crystalline phases in equilibrium with excess water depend both on the lipid molecular structure and on the temperature. Given an isoprenoid chain, the preferred phase consistently follows a phase sequence of an H II (an inverted hexagonal phase) to a Q II (an inverted bicontinuous cubic phase) to an L alpha (a lamellar phase) as A* (cross-section area of the headgroup) increases. For a given lipid/water system, the phase sequence observed as the temperature increases is L alpha to Q II to H II. The present study allowed us to find four cubic phase-forming lipid species, PEOC 18+4 [mono- O-(5,9,13,17-tetramethyloctadecyl)pentaerythritol], beta-XylOC 18+4 [1- O-(5,9,13,17-tetramethyloctadecyl)-beta- d-xylopyranoside], EROCOC 17+4 [1- O-(5,9,13,17-tetramethyloctadecanoyl)erythritol], and PEOCOC 17+4 [mono- O-(5,9,13,17-tetramethyloctadecanoyl)pentaerythritol]. The values of T K (hydrated solid-liquid crystalline phase transition temperature) of the cubic phase-forming lipids are all below 0 degrees C. Quantitative analyses of the lipid molecular structure-aqueous phase structure relationship in terms of the experimentally evaluated "surfactant parameter" allow us to rationally select an optimum combination of hydrophilic

Crystalline phase, microstructure, and aqueous stability of zirconolite-barium borosilicate glass-ceramics for immobilization of simulated sulfate bearing high-level liquid waste

Science.gov (United States)

Wu, Lang; Xiao, Jizong; Wang, Xin; Teng, Yuancheng; Li, Yuxiang; Liao, Qilong

2018-01-01

The crystalline phase, microstructure, and aqueous stability of zirconolite-barium borosilicate glass-ceramics with different content (0-30 wt %) of simulated sulfate bearing high-level liquid waste (HLLW) were evaluated. The sulfate phase segregation in vitrification process was also investigated. The results show that the glass-ceramics with 0-20 wt% of HLLW possess mainly zirconolite phase along with a small amount baddeleyite phase. The amount of perovskite crystals increases while the amount of zirconolite crystals decreases when the HLLW content increases from 20 to 30 wt%. For the samples with 20-30 wt% HLLW, yellow phase was observed during the vitrification process and it disappeared after melting at 1150 °C for 2 h. The viscosity of the sample with 16 wt% HLLW (HLLW-16) is about 27 dPa·s at 1150 °C. The addition of a certain amount (≤20 wt %) of HLLW has no significant change on the aqueous stability of glass-ceramic waste forms. After 28 days, the 90 °C PCT-type normalized leaching rates of Na, B, Si, and La of the sample HLLW-16 are 7.23 × 10-3, 1.57 × 10-3, 8.06 × 10-4, and 1.23 × 10-4 g·m-2·d-1, respectively.

Chelate-Modified Fenton Reaction for the Degradation of Trichloroethylene in Aqueous and Two-Phase Systems

Energy Technology Data Exchange (ETDEWEB)

Lewis, Scott [Univ of KY, dept of chemical and materials engineering; lynch, Andrew [Univ of KY, dept of chemical and materials engineering; Bachas, Leonidas [Univ of KY, Dept of Chemistry; hampson, Steve [Univ of KY Center for Applied Energy Research - KY Research Consortium of Energy and Environment; Ormsbee, Lindelle [Univ of KY Center for Applied Energy Research - KY Research Consortium of Energy and Environment; Bhattacharyya, Dibakar [Univ of KY, dept of chemical and materials engineering

2008-06-01

The Standard Fenton reaction has been used for In-Situ Chemical Oxidation (ISCO) of toxic organics in groundwater. However, it requires low pH operating conditions, and thus has limitations for in situ applications. In addition, hydroxyl radicals are rapidly consumed by hydroxyl scavengers found in the subsurface. These problems are alleviated through the chelate-modified Fenton (hydroxyl radical) reaction, which includes the addition of nontoxic chelate (L) such as citrate or gluconic acid. This chelate allows the reaction to take place at bear neutral pH and control hydrogen peroxide consumption by binding to Fe(II), forming an FeL complex. The chelate also binds to Fe(III), preventing its precipitation as ferric hydroxide and thus prevents problems associated with injection well plugging. The rate of TCE dechlorination in chelate-modified Fenton systems is a function of pH, H2O2 concentration, and FE:L ratio. The primary objective of this research is to model and apply this process to the destruction of trichloroethylene (TCE) present in both the aqueous and organic (in the form of droplets) phases. Experimentation proved the chelate-modified Fenton reaction effectively dechlorinates TCE in both the aqueous and organic phases at near-neutral pH. Other focuses of this work include determining the effect of [L]:[Fe] ratios on H2O2 and TCE degradation as well as reusability of the FE citrate solution under repeated H2O2 injections. Generalized models were developed to predict the concentration of TCE in the aqueous phase and TCE droplet radius as a function of time using established hydroxyl radial kinetics and mass transfer relationships.

Design of functional guanidinium ionic liquid aqueous two-phase systems for the efficient purification of protein.

Science.gov (United States)

Ding, Xueqin; Wang, Yuzhi; Zeng, Qun; Chen, Jing; Huang, Yanhua; Xu, Kaijia

2014-03-07

A series of novel cationic functional hexaalkylguanidinium ionic liquids and anionic functional tetraalkylguanidinium ionic liquids have been devised and synthesized based on 1,1,3,3-tetramethylguanidine. The structures of the ionic liquids (ILs) were confirmed by (1)H nuclear magnetic resonance ((1)H NMR) and 13C nuclear magnetic resonance (13C NMR) and the production yields were all above 90%. Functional guanidinium ionic liquid aqueous two-phase systems (FGIL-ATPSs) have been first designed with these functional guanidinium ILs and phosphate solution for the purification of protein. After phase separation, proteins had transferred into the IL-rich phase and the concentrations of proteins were determined by measuring the absorbance at 278 nm using an ultra violet visible (UV-vis) spectrophotometer. The advantages of FGIL-ATPSs were compared with ordinary ionic liquid aqueous two-phase systems (IL-ATPSs). The proposed FGIL-ATPS has been applied to purify lysozyme, trypsin, ovalbumin and bovine serum albumin. Single factor experiments were used to research the effects of the process, such as the amount of ionic liquid (IL), the concentration of salt solution, temperature and the amount of protein. The purification efficiency reaches to 97.05%. The secondary structure of protein during the experimental process was observed upon investigation using UV-vis spectrophotometer, Fourier-transform infrared spectroscopy (FT-IR) and circular dichroism spectrum (CD spectrum). The precision, stability and repeatability of the process were investigated. The mechanisms of purification were researched by dynamic light scattering (DLS), determination of the conductivity and transmission electron microscopy (TEM). It was suggested that aggregation and embrace phenomenon play a significant role in the purification of proteins. All the results show that FGIL-ATPSs have huge potential to offer new possibility in the purification of proteins. Copyright © 2014 Elsevier B.V. All rights

Sulfur isotope fractionation during oxidation of sulfur dioxide: gas-phase oxidation by OH radicals and aqueous oxidation by H2O2, O3 and iron catalysis

Directory of Open Access Journals (Sweden)

J. N. Crowley

2012-01-01

Full Text Available The oxidation of SO2 to sulfate is a key reaction in determining the role of sulfate in the environment through its effect on aerosol size distribution and composition. Sulfur isotope analysis has been used to investigate sources and chemical processes of sulfur dioxide and sulfate in the atmosphere, however interpretation of measured sulfur isotope ratios is challenging due to a lack of reliable information on the isotopic fractionation involved in major transformation pathways. This paper presents laboratory measurements of the fractionation factors for the major atmospheric oxidation reactions for SO2: Gas-phase oxidation by OH radicals, and aqueous oxidation by H2O2, O3 and a radical chain reaction initiated by iron. The measured fractionation factor for 34S/32S during the gas-phase reaction is αOH = (1.0089±0.0007−((4±5×10−5 T(°C. The measured fractionation factor for 34S/32S during aqueous oxidation by H2O2 or O3 is αaq = (1.0167±0.0019−((8.7±3.5 ×10−5T(°C. The observed fractionation during oxidation by H2O2 and O3 appeared to be controlled primarily by protonation and acid-base equilibria of S(IV in solution, which is the reason that there is no significant difference between the fractionation produced by the two oxidants within the experimental error. The isotopic fractionation factor from a radical chain reaction in solution catalysed by iron is αFe = (0.9894±0.0043 at 19 °C for 34S/32S. Fractionation was mass-dependent with regards to 33S/32S for all the reactions investigated. The radical chain reaction mechanism was the only measured reaction that had a faster rate for the light isotopes. The results presented in this study will be particularly useful to determine the importance of the transition metal-catalysed oxidation pathway compared to other oxidation pathways, but other main oxidation pathways can not be distinguished based on stable sulfur isotope measurements alone.

Differentiation of surface properties of chlorococcalean algae by means of aqueous two phase systems

Directory of Open Access Journals (Sweden)

Jan Burczyk

2014-01-01

Full Text Available Algal cells belonging to various strains of Chlorococcales (Chlorophyta have been partitioned in aqueous two-phase systems containing ionogenic polymers, DEAE-dextran or SDS-dextran, at various pH values. Strain-specific differences of partition type which have been found in the phase systems used can be useful for distinguishing of algal cells.

Cheese whey valorisation: Production of valuable gaseous and liquid chemicals from lactose by aqueous phase reforming

International Nuclear Information System (INIS)

Remón, J.; Ruiz, J.; Oliva, M.; García, L.; Arauzo, J.

2016-01-01

Highlights: • Aqueous phase reforming: a promising strategy for cheese whey valorisation. • In-depth understanding of the effect of the operating conditions on the process. • Process optimisation for the selective production of valuable gas and liquid products. • High P, T, lactose concentration and spatial time favour gas production. • High T, low spatial time and the use of diluted solutions maximise liquids production. - Abstract: Cheese effluent management has become an important issue owing to its high biochemical oxygen demand and chemical oxygen demand values. Given this scenario, this work addresses the valorisation of lactose (the largest organic constituent of this waste) by aqueous phase reforming, analysing the influence of the most important operating variables (temperature, pressure, lactose concentration and mass of catalyst/lactose mass flow rate ratio) as well as optimising the process for the production of either gaseous or liquid value-added chemicals. The carbon converted into gas, liquid and solid products varied as follows: 5–41%, 33–97% and 0–59%, respectively. The gas phase was made up of a mixture of H_2 (8–58 vol.%), CO_2 (33–85 vol.%), CO (0–15 vol.%) and CH_4 (0–14 vol.%). The liquid phase consisted of a mixture of aldehydes: 0–11%, carboxylic acids: 0–22%, monohydric alcohols: 0–23%, polyhydric-alcohols: 0–48%, C3-ketones: 4–100%, C4-ketones: 0–18%, cyclic-ketones: 0–15% and furans: 0–85%. H_2 production is favoured at high pressure, elevated temperature, employing a high amount of catalyst and a concentrated lactose solution. Liquid production is preferential using diluted lactose solutions. At high pressure, the production of C3-ketones is preferential using a high temperature and a low amount of catalyst, while a medium temperature and a high amount of catalyst favours the production of furans. The production of alcohols is preferential using medium temperature and pressure and a low amount of

Influence of concentration of H2O2 on the phase stability of TiO2-anatase

International Nuclear Information System (INIS)

Montanhera, M.A.; Pereira, E.A.; Paula, F.R.; Spada, E.R.; Faria, R.M.

2014-01-01

Titanium dioxide (TiO 2 ) is a semiconductor what has attracted increasing attention because of its physical and chemical properties. In this work, we report the preparation of TiO 2 nanoparticles by dissolving of titanium oxysulfate (TiOSO 4 ) in aqueous solution containing hydrogen peroxide (H 2 O 2 ) and subsequent thermal treatment of the precipitated complex. The results of X-ray diffractometry showed that the first stage of heat treatment at 600°C generates the anatase phase at all concentrations of H 2 O 2 investigated. On the other hand, when treated at 825 deg C, prepared samples with lower concentrations of H 2 O 2 (0.009 and 0.017 mol/L) showed only the rutile phase and for concentrations starting from 0.088 mol/L, is obtained only anatase phase. When the heat treatment is performed at 900°C, phase-pure anatase is obtained only for concentrations higher than 0.122 mol/L. The stability of the phase anatase is related to the crystallite size obtained of the first stage of heat treatment. When the heat treatment is performed at 900°C, phase-pure anatase is obtained only at higher concentrations than 0.122 mol/L. The stability of the phase anatase is related to the crystallite sizes obtained in the first step of heat treatment. (author)

Subcritical hydrothermal liquefaction of barley straw in fresh water and recycled aqueous phase

DEFF Research Database (Denmark)

Zhu, Zhe; Toor, Saqib; Rosendahl, Lasse

2014-01-01

This project focuses on the investigation of addition of aqueous phase in the production of biofuel from biomass through hydrothermal liquefaction (HTL) technology. Hydrothermal liquefaction is a wet thermal conversion process, which can convert all kinds of biomass to fuels. In this study, barley...... straw was first liquefied in fresh distilled water with the presence of K2CO3 catalyst at 300 C as the reference run. Afterwards, the aqueous phase which is obtained from liquefaction process in the previous run was recycled and used as the reaction medium from the second to the fourth run....... With the addition of recycling aqueous phase in HTL process, it is expected that the amount of the waste water and energy consumption can be reduced. The effect of water recirculation on product yield and properties was investigated in this study. The results showed that bio-oil yield was 34.85 wt% when the barley...

Effect of Aqueous Phase Recycling in Continuous Hydrothermal Liquefaction

DEFF Research Database (Denmark)

Klemmer, Maika; Madsen, René Bjerregaard; Houlberg, Kasper

2016-01-01

was observed with a maximum increase in the first recycle experiment. However, the recycling of the aqueous phase also resulted in lower heating values and higher water contents in the oil fraction. Based on these findings, recycling the aqueous phase is a trade-off between improved yields and reduced burn...... qualities of the biocrude. That said, recycling also lowers carbon discharge to the aqueous fraction, which may contribute significantly to reducing the environmental footprint of an industrial HTL plant....

Linear free energy relationships between aqueous phase hydroxyl radical reaction rate constants and free energy of activation.

Science.gov (United States)

Minakata, Daisuke; Crittenden, John

2011-04-15

The hydroxyl radical (HO(•)) is a strong oxidant that reacts with electron-rich sites on organic compounds and initiates complex radical chain reactions in aqueous phase advanced oxidation processes (AOPs). Computer based kinetic modeling requires a reaction pathway generator and predictions of associated reaction rate constants. Previously, we reported a reaction pathway generator that can enumerate the most important elementary reactions for aliphatic compounds. For the reaction rate constant predictor, we develop linear free energy relationships (LFERs) between aqueous phase literature-reported HO(•) reaction rate constants and theoretically calculated free energies of activation for H-atom abstraction from a C-H bond and HO(•) addition to alkenes. The theoretical method uses ab initio quantum mechanical calculations, Gaussian 1-3, for gas phase reactions and a solvation method, COSMO-RS theory, to estimate the impact of water. Theoretically calculated free energies of activation are found to be within approximately ±3 kcal/mol of experimental values. Considering errors that arise from quantum mechanical calculations and experiments, this should be within the acceptable errors. The established LFERs are used to predict the HO(•) reaction rate constants within a factor of 5 from the experimental values. This approach may be applied to other reaction mechanisms to establish a library of rate constant predictions for kinetic modeling of AOPs.

Two-liquid-phase boundaries and critical phenomena at 275 to 4000C for high-temperature aqueous potassium phosphate and sodium phosphate solutions. Potential applications for steam generators

International Nuclear Information System (INIS)

Marshall, W.L.

1982-01-01

Two-liquid-phase boundaries at temperatures between 275 and 400 0 C were determined for potassium phosphate and sodium phosphate aqueous solutions for compositions from 0 to 60 wt % dissolved salt. The stoichiometric mole ratios, K/PO 4 or Na/PO 4 , were varied from 1.00 to 2.12 and from 1.00 to 2.16 for the potassium and sodium systems, respectively. Liquid-vapor critical temperatures were also determined for most of the dilute liquid phases that formed. The minimum temperatures (below which a single solution existed) of two-liquid-phase formation were 360 0 C for the potassium system and 279 0 C for the sodium system at mole ratios of 2.00 and 2.16, respectively. For the sodium system at mole ratios greater than 2.16, solids crystallized at lower temperatures as expected from earlier studies. In contrast, potassium solutions that were explored at mole ratios from 2.12 to 3.16 and at temperatures below 360 0 C did not produce solid phases or liquid-liquid immisibilities. Aside from the generally unusual observations of two immiscible liquids in an aqueous inorganic salt system, the results could possibly be applied to the use of phosphate additives in steam power generators

Hydrogen Generation from Sugars via Aqueous-Phase Reforming

International Nuclear Information System (INIS)

Randy D Cortright

2006-01-01

Virent Energy Systems, Inc. is commercializing the Aqueous Phase Reforming (APR) process that allows the generation of hydrogen-rich gas streams from biomass-derived compounds such as glycerol, sugars, and sugar alcohols. The APR process is a unique method that generates hydrogen from aqueous solutions of these oxygenated compounds in a single step reactor process compared to the three or more reaction steps required for hydrogen generation via conventional processes that utilize non-renewable fossil fuels. The key breakthrough of the APR process is that the reforming of these aqueous solutions is done in the liquid phase. The patented APR process occurs at temperatures (150 C to 270 C) where the water-gas shift reaction is favorable, making it possible to generate hydrogen with low amounts of CO in a single chemical reactor. Furthermore, the APR process occurs at pressures (typically 15 to 50 bar) where the hydrogen-rich effluent can be effectively purified using either membrane technology or pressure swing adsorption technology. The utilization of biomass-based compounds allows the APR process to be a carbon neutral method to generate hydrogen. In the near term, the feed-stock of interest is waste glycerol that is being generated in large quantities as a byproduct in the production of bio-diesel. Virent has developed the APR system for on-demand generation of hydrogen-rich fuel gas from either glycerol or sorbitol (the sugar alcohol formed by hydrogenation of glucose) to fuel a stationary internal combustion engine driven generator (10 kW). Under a USDOE funded project, Virent is currently developing the APR process to generate high yields of hydrogen from corn-derived glucose. This project objective is to achieve the DOE 2010 cost target for distributed production from renewable liquid fuels of 3.60 dollars/gge (gasoline gallon equivalent) delivered. (authors)

UV-C radiation based methods for aqueous metoprolol elimination

Energy Technology Data Exchange (ETDEWEB)

Rivas, F.J., E-mail: fjrivas@unex.es [Departamento de Ingenieria Quimica y Quimica Fisica, Universidad de Extremadura, Facultad de Ciencias, Edificio Jose Luis Sotelo, Avenida de Elvas S/N, 06071 Badajoz (Spain); Gimeno, O.; Borralho, T.; Carbajo, M. [Departamento de Ingenieria Quimica y Quimica Fisica, Universidad de Extremadura, Facultad de Ciencias, Edificio Jose Luis Sotelo, Avenida de Elvas S/N, 06071 Badajoz (Spain)

2010-07-15

The endocrine disruptor metoprolol has been oxidised in aqueous solution by means of the systems UV-C, UV-C/H{sub 2}O{sub 2}, UV-C/percarbonate, UV-C/monopersulfate, UV-C/TiO{sub 2}, UV-C/H{sub 2}O{sub 2}/TiO{sub 2} and photo-Fenton. From simple photolysis experiments the quantum yield of metoprolol has been calculated (roughly 5 x 10{sup -3} mol Einstein{sup -1} at circumneutral pH). Addition of free radicals promoters significantly enhanced the metoprolol depletion rate. Mineralization degree was negligible when no promoter was added, while low values were achieved in the presence of either inorganic peroxides or titanium dioxide. The combination of radiation, hydrogen peroxide and TiO{sub 2} increased the mineralization level up to values in the proximity of 45-50% under the best conditions investigated. The photo-Fenton process was the best system in terms of total oxidation (mineralization degree 70%) when optimum conditions were applied.

UV-C radiation based methods for aqueous metoprolol elimination

International Nuclear Information System (INIS)

Rivas, F.J.; Gimeno, O.; Borralho, T.; Carbajo, M.

2010-01-01

The endocrine disruptor metoprolol has been oxidised in aqueous solution by means of the systems UV-C, UV-C/H 2 O 2 , UV-C/percarbonate, UV-C/monopersulfate, UV-C/TiO 2 , UV-C/H 2 O 2 /TiO 2 and photo-Fenton. From simple photolysis experiments the quantum yield of metoprolol has been calculated (roughly 5 x 10 -3 mol Einstein -1 at circumneutral pH). Addition of free radicals promoters significantly enhanced the metoprolol depletion rate. Mineralization degree was negligible when no promoter was added, while low values were achieved in the presence of either inorganic peroxides or titanium dioxide. The combination of radiation, hydrogen peroxide and TiO 2 increased the mineralization level up to values in the proximity of 45-50% under the best conditions investigated. The photo-Fenton process was the best system in terms of total oxidation (mineralization degree 70%) when optimum conditions were applied.

Carbohydrates-tailored phase tunable systems composed of ionic liquids and water

International Nuclear Information System (INIS)

Chen Yuhaun; Wang Yige; Cheng Qingyan; Liu Xiaoli; Zhang Suojiang

2009-01-01

Carbohydrates were found to have substantial effects on tailoring phase tunable of ionic liquids (ILs) and water. Phase behaviors of 1-alkyl-3-methylimidazolium derivatives [C n mim]X (n = 2 to 10, X = Cl - , Br - , BF 4 - )-carbohydrate-H 2 O were systemically investigated. For hydrophilic ILs, 1-alkyl-3-methylimidazolium tetrafluoroborate [C n mim]BF 4 (n = 3, 4), the homogeneous aqueous solution can be induced to separate two aqueous phases by addition of carbohydrate. For hydrophobic ILs, [C n mim]BF 4 (n = 5 to 10), the mutual solubility with water can be lowered by addition of carbohydrate. While 1-alkyl-3-methyl imidazolium chloride ([C n mim]Cl, n = 2 to 10) and 1-alkyl-3-methyl imidazolium bromide ([C n mim]Br, n = 2 to 10) aqueous solutions never form aqueous two-phase systems (ATPSs) with carbohydrate in the investigated temperatures ranging from (242.15 to 373.15) K. The high partitioning behavior of phenol in [C n mim]BF 4 (n = 3 to 10) (1) + carbohydrate (2) + H 2 O (3) shows that carbohydrate-tailored {IL + H 2 O} systems are feasible to be used as extraction systems, especially in biological and environmental engineering.

Solar light-facilitated oxytetracycline removal from the aqueous phase utilizing a H2O2/ZnWO4/CaO catalytic system

Directory of Open Access Journals (Sweden)

Pankaj Raizada

2017-09-01

Full Text Available A CaO-supported ZnWO4 nanocomposite (ZnWO4/CaO was successfully synthesized using a novel hydrothermal method and was characterized by scanning electron microscopy (SEM, tunnelling electron microscopy (TEM, X-ray diffraction (XRD, electron diffraction X-ray (EDX, Fourier transform infrared spectroscopy (FTIR and UV–visible (UV–vis spectral analysis. The ZnWO4/CaO composites exhibited rod-like morphologies with variable lengths from 45 nm to 147 nm and diameters from 26 nm to 36 nm. The catalytic efficiency of the synthesized ZnWO4/CaO composites was displayed for the photodegradation of oxytetracycline (OTC antibiotic from the aqueous phase. The synergistic degradation of OTC was investigated in the presence of H2O2 and ZnWO4/CaO. The rate of photodegradation followed pseudo-first-order kinetics. The antibiotic removal was strongly influenced by the catalyst loading, H2O2 concentration, pH and OTC concentration. Using a solar/H2O2/ZnWO4/CaO catalytic system, 85% COD removal was attained for OTC degradation in 210 min. The oxidative degradation occurred through hydroxyl radicals. The prepared nanocomposites possessed high recyclability and were easily separated from the aqueous solution by a simple sedimentation process.

Investigation of the promoting effect of Mn on a Pt/C catalyst for the steam and aqueous phase reforming of glycerol

Energy Technology Data Exchange (ETDEWEB)

Bossola, Filippo; Pereira-Hernández, Xavier Isidro; Evangelisti, Claudio; Wang, Yong; Dal Santo, Vladimiro

2017-05-01

The catalytic performances in steam reforming (SR) and aqueous phase reforming (APR) of glycerol of a bimetallic Pt-Mn catalyst supported on activated carbon are investigated and correlated with the surface properties of the catalyst. Under SR conditions, Mn showed a significant promoting effect over Pt/C, both in terms of hydrogen production rate and conversion, with a higher selectivity toward the glycerol dehydration products. Upon addition of Mn the amount of strong Lewis acid sites increased, promoting the dehydration of glycerol and favoring the CAO over CAC cleavage at expenses of hydrogen selectivity. Conversely, under APR conditions, a slightly higher hydrogen selectivity and only minimal enhancement in hydrogen production were found, while the products selectivity was comparable to Pt/C. Most of Mn leached into the aqueous media, but the remaining (<5% of the fresh parent sample) might be alloyed with Pt and promote the CO desorption from neighbor Pt sites.

Hydrogen evolution from aqueous-phase photocatalytic reforming of ethylene glycol over Pt/TiO{sub 2} catalysts: Role of Pt and product distribution

Energy Technology Data Exchange (ETDEWEB)

Li, Fuying [State Key Laboratory of Photocatalysis on Energy and Environment, Research Institute of Photocatalysis, Fuzhou University, Fuzhou 350002 (China); College of Resources and Chemical Engineering, Sanming University, Sanming 365004 (China); Gu, Quan [Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shanxi Normal University, Xi’an 710062 (China); Niu, Yu [College of Resources and Chemical Engineering, Sanming University, Sanming 365004 (China); School of Chemical Engineering, Fuzhou University, Fuzhou 350116 (China); Wang, Renzhang [College of Resources and Chemical Engineering, Sanming University, Sanming 365004 (China); Tong, Yuecong; Zhu, Shuying; Zhang, Hualei [State Key Laboratory of Photocatalysis on Energy and Environment, Research Institute of Photocatalysis, Fuzhou University, Fuzhou 350002 (China); Zhang, Zizhong, E-mail: z.zhang@fzu.edu.cn [State Key Laboratory of Photocatalysis on Energy and Environment, Research Institute of Photocatalysis, Fuzhou University, Fuzhou 350002 (China); Wang, Xuxu [State Key Laboratory of Photocatalysis on Energy and Environment, Research Institute of Photocatalysis, Fuzhou University, Fuzhou 350002 (China)

2017-01-01

Highlights: • Photocatalytic EG reforming generates many hydrocarbons besides H{sub 2}, CO{sub 2} and CO. • Pt loading greatly improves the photocatalytic activity of TiO{sub 2} for EG reforming. • Half amount of the produced H{sub 2} over Pt/TiO{sub 2} originates from EG reforming. - Abstract: Pt nanoparticles were loaded on anatase TiO{sub 2} by the photodeposition method to investigate their photocatalytic activity for H{sub 2} evolution in an aqueous solution containing a certain amount of ethylene glycol (EG) as the sacrificial agent. The surface properties and chemical states of the Pt/TiO{sub 2} sample were characterized by X-ray powder diffraction analysis, Brunauer–Emmett–Teller surface area analysis, transmission electron microscopy, X-ray photoelectron spectroscopy, electron paramagnetic resonance, and electrochemical resistance. The aqueous-phase photocatalytic EG reforming using Pt/TiO{sub 2} and anatase TiO{sub 2} generated not only H{sub 2} and CO{sub 2}, but also CO, CH{sub 4}, C{sub 2}H{sub 6}, and C{sub 2}H{sub 4}. Moreover, the amount of formate and acetate complexes in the solution increased gradually. The EG adsorption and gas-phase intermediates during photocatalytic reaction processes were investigated by the in situ FTIR spectrum. Finally, the photocatalytic EG reforming reaction mechanism was elucidated. This helped to better understand the role of a sacrificial agent in a photocatalytic hydrogen production.

Superior lithium-ion insertion/extraction properties of a novel LiFePO4/C/graphene material used as a cathode in aqueous solution.

Science.gov (United States)

Duan, Wenyuan; Zhao, Mingshu; Shen, Junfang; Zhao, Suixin; Song, Xiaoping

2017-09-28

Herein, olivine LiFePO 4 covered with graphene and carbon layers is prepared via a sol-gel method, followed by calcination, and the resultant composite is used as a cathode material in aqueous rechargeable lithium-ion batteries (ARLBs). The phase structure and morphology of the composite are characterized via X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM) and specific surface area analysis (BET). The ARLB system is fabricated using LiFePO 4 /C/graphene as the cathode and a zinc anode in 1 mol L -1 ZnSO 4 ·7H 2 O and saturated LiNO 3 aqueous solution without dissolved oxygen, which delivers a capacity of 153 mA h g -1 at 0.5C rate. Even at a 50C rate, it maintains a capacity of 95 mA h g -1 after 200 cycles. The excellent rate capabilities show that this cathode material exhibits good electrochemical performance and this novel ARLB has great potential in the fields of energy storage and high power sources.

Chemical alteration of calcium silicate hydrates in saline groundwater. Mechanism of sorption of Na on C-S-H and effect of NaCl on leaching of Ca from C-S-H

International Nuclear Information System (INIS)

Sugiyama, Daisuke; Fujita, Tomonari

2004-01-01

In the concept for TRU waste disposal in Japan, cement is a potential waste packaging and backfilling material and is expected to provide chemical containment. In the presence of some reactive ions in a saline groundwater, the chemical properties of cement materials should be affected. In this study, the mechanism of sorption of sodium (Na) on C-S-H and the effect of sodium chloride (NaCl) concentration on dissolution of Calcium Silicate Hydrate (C-S-H) are discussed by measuring the sorption isotherm of sodium onto C-S-H gel (Ca/Si = 0.65-1.2). Based on the experimental results, it is showed that sodium sorbs by substitution for Ca in C-S-H phases and leaching of Ca from C-S-H is enhanced in NaCl solution ( -1 mol dm -3 ). The results of sorption experiments are reasonably well modelled by the ion-exchange model assuming some calcium sites with different ion-exchange log K values. It is also suggested that the dissolution of C-S-H can be modelled reasonably well by considering the effect of ionic strength on activity coefficients of aqueous species for high Ca/Si ratio of C-S-H, and the effect of exchange of sodium with calcium of C-S-H on leaching of Ca becomes obvious for lower Ca/Si ratio of C-S-H. (author)

submitter Aqueous phase oxidation of sulphur dioxide by ozone in cloud droplets

CERN Document Server

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

2016-01-01

The growth of aerosol due to the aqueous phase oxidation of sulfur dioxide by ozone was measured in laboratory-generated clouds created in the Cosmics Leaving OUtdoor Droplets (CLOUD) chamber at the European Organization for Nuclear Research (CERN). Experiments were performed at 10 and −10 °C, on acidic (sulfuric acid) and on partially to fully neutralised (ammonium sulfate) seed aerosol. Clouds were generated by performing an adiabatic expansion – pressurising the chamber to 220 hPa above atmospheric pressure, and then rapidly releasing the excess pressure, resulting in a cooling, condensation of water on the aerosol and a cloud lifetime of approximately 6 min. A model was developed to compare the observed aerosol growth with that predicted using oxidation rate constants previously measured in bulk solutions. The model captured the measured aerosol growth very well for experiments performed at 10 and −10 °C, indicating that, in contrast to some previous studies, the oxidation rates of SO2 in ...

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.

Aqueous Two-Phase Extraction of Polyphenols Using a Microchannel System – Process Optimization and Intensification

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Ivana Rukavina

2011-01-01

Full Text Available Polyphenols are one of the most numerous and widespread groups of compounds in the plant world. Nowadays, organic solvents such as methanol, ethanol, acetone, dimethylformamide, ethyl acetate and diethylether are mainly used for the extraction of polyphenols. These solvents require special process conditions and special care in the disposal of the used solvents. In this paper, the extraction of polyphenols from the model solution was performed using the aqueous two-phase system which contains 80.90 % water and represents low burden on the environment. The aqueous solution of gallic acid (GA was used as a model solution of polyphenols. The extraction was performed in the aqueous two-phase system containing PEG6000/H2O/(NH42SO4 in a macroextractor (V=10 mL and microextractor (V=14 ƒμL. The influence of the process parameters, the concentration of gallic acid, pH and composition of the aqueous two-phase system was investigated in order to maximize the partition coefficient. The method of multifactor experimental planning was used to optimize the extraction process and the results were statistically analysed using the evolutionary operation method (EVOP. Optimal operating conditions of the extraction process were pH=6.50, γGA=4.50 g/L, the mass fraction of polyethylene glycol (PEG wPEG=0.1037 g/g and the mass fraction of ammonium sulphate (AMS wAMS=0.0925 g/g. Under these conditions the maximal partition coefficient of K=5.54 and the extraction efficiency of E=89.11 % were achieved and successfully applied for total phenol extraction from white wine in the macro- and microextractor. Approximately the same partition coefficients and extraction efficiency were achieved in the microextractor within a 60-fold shorter residence time.

A Novel Aqueous Two Phase System Composed of Surfactant and Xylitol for the Purification of Lipase from Pumpkin (Cucurbita moschata) Seeds and Recycling of Phase Components.

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Amid, Mehrnoush; Manap, Mohd Yazid; Hussin, Muhaini; Mustafa, Shuhaimi

2015-06-17

Lipase is one of the more important enzymes used in various industries such as the food, detergent, pharmaceutical, textile, and pulp and paper sectors. A novel aqueous two-phase system composed of surfactant and xylitol was employed for the first time to purify lipase from Cucurbita moschata. The influence of different parameters such as type and concentration of surfactants, and the composition of the surfactant/xylitol mixtures on the partitioning behavior and recovery of lipase was investigated. Moreover, the effect of system pH and crude load on the degree of purification and yield of the purified lipase were studied. The results indicated that the lipase was partitioned into the top surfactant rich phase while the impurities partitioned into the bottom xylitol-rich phase using an aqueous two phase system composed of 24% (w/w) Triton X-100 and 20% (w/w) xylitol, at 56.2% of tie line length (TLL), (TTL is one of the important parameters in this study and it is determined from a bimodal curve in which the tie-line connects two nodes on the bimodal, that represent concentration of phase components in the top and bottom phases) and a crude load of 25% (w/w) at pH 8.0. Recovery and recycling of components was also measured in each successive step process. The enzyme was successfully recovered by the proposed method with a high purification factor of 16.4 and yield of 97.4% while over 97% of the phase components were also recovered and recycled. This study demonstrated that the proposed novel aqueous two phase system method is more efficient and economical than the traditional aqueous two phase system method for the purification and recovery of the valuable enzyme lipase.

A Novel Aqueous Two Phase System Composed of Surfactant and Xylitol for the Purification of Lipase from Pumpkin (Cucurbita moschata Seeds and Recycling of Phase Components

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Mehrnoush Amid

2015-06-01

Full Text Available Lipase is one of the more important enzymes used in various industries such as the food, detergent, pharmaceutical, textile, and pulp and paper sectors. A novel aqueous two-phase system composed of surfactant and xylitol was employed for the first time to purify lipase from Cucurbita moschata. The influence of different parameters such as type and concentration of surfactants, and the composition of the surfactant/xylitol mixtures on the partitioning behavior and recovery of lipase was investigated. Moreover, the effect of system pH and crude load on the degree of purification and yield of the purified lipase were studied. The results indicated that the lipase was partitioned into the top surfactant rich phase while the impurities partitioned into the bottom xylitol-rich phase using an aqueous two phase system composed of 24% (w/w Triton X-100 and 20% (w/w xylitol, at 56.2% of tie line length (TLL, (TTL is one of the important parameters in this study and it is determined from a bimodal curve in which the tie-line connects two nodes on the bimodal, that represent concentration of phase components in the top and bottom phases and a crude load of 25% (w/w at pH 8.0. Recovery and recycling of components was also measured in each successive step process. The enzyme was successfully recovered by the proposed method with a high purification factor of 16.4 and yield of 97.4% while over 97% of the phase components were also recovered and recycled. This study demonstrated that the proposed novel aqueous two phase system method is more efficient and economical than the traditional aqueous two phase system method for the purification and recovery of the valuable enzyme lipase.

POLYELECTROLYTE MULTILAYER STAMPING IN AQUEOUS PHASE AND NON-CONTACT MODE

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Mehrotra, Sumit; Lee, Ilsoon; Liu, Chun; Chan, Christina

2011-01-01

Polyelectrolyte multilayer (PEM) transfer printing has been previously achieved by stamping under dry conditions. Here, we show for the first time, that PEM can be transferred from a stamp to the base substrate under aqueous conditions whereby the two surfaces are in a non-contact mode. Degradable multilayers of (PAA/PEG)10.5 followed by non-degradable multilayers of (PDAC/SPS)80.5 were fabricated under acidic pH conditions on either PDMS or glass (stamp), and subsequently transferred over top of another multilayer prepared on a different substrate (base substrate), with a spacing of ~ 200 μm between the stamping surface and the base substrate. This multilayer transfer was performed under physiological pH conditions. This process is referred to herein as non-contact, aqueous-phase multilayer (NAM) transfer. NAM transfer can be useful for applications such as fabricating three-dimensional (3-D) cellular scaffolds. We attempted to create a 3-D cellular scaffold using NAM transfer, and characterized the scaffolds with conventional and fluorescence microscopy. PMID:21860540

Gas-phase nitrosation of ethylene and related events in the C2H4NO+ landscape.

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Gerbaux, Pascal; Dechamps, Noemie; Flammang, Robert; Nam, Pham Cam; Nguyen, Minh Tho; Djazi, Fayçal; Berruyer, Florence; Bouchoux, Guy

2008-06-19

The C2H4NO(+) system has been examined by means of quantum chemical calculations using the G2 and G3B3 approaches and tandem mass spectrometry experiments. Theoretical investigation of the C2H4NO(+) potential-energy surface includes 19 stable C2H4NO(+) structures and a large set of their possible interconnections. These computations provide insights for the understanding of the (i) addition of the nitrosonium cation NO(+) to the ethylene molecule, (ii) skeletal rearrangements evidenced in previous experimental studies on comparable systems, and (iii) experimental identification of new C2H4NO(+) structures. It is predicted from computation that gas-phase nitrosation of ethylene may produce C2H4(*)NO(+) adducts, the most stable structure of which is a pi-complex, 1, stabilized by ca. 65 kJ/mol with respect to its separated components. This complex was produced in the gas phase by a transnitrosation process involving as reactant a complex between water and NO(+) (H2O.NO(+)) and the ethylene molecule and fully characterized by collisional experiments. Among the other C 2H 4NO (+) structures predicted by theory to be protected against dissociation or isomerization by significant energy barriers, five were also experimentally identified. These finding include structures CH3CHNO(+) (5), CH 3CNOH (+) ( 8), CH3NHCO(+) (18), CH3NCOH(+) (19), and an ion/neutral complex CH2O...HCNH(+) (12).

Quantification and speciation of volatile fatty acids in the aqueous phase.

Science.gov (United States)

Lee, Jechan; Kim, Jieun; Oh, Jeong-Ik; Lee, Sang-Ryong; Kwon, Eilhann E

2017-11-01

This study lays great emphasis on establishing a reliable analytical platform to quantify and specify volatile fatty acids (VFAs) in the aqueous phase by derivatizing VFAs into their corresponding alkyl esters via thermally-induced rapid esterification (only 10 s reaction time). To this end, reaction conditions for the thermally-induced rapid esterification are optimized. A volumetric ratio of 0.5 at 400 °C for VFA/methanol is identified as the optimal reaction conditions to give ∼90% volatile fatty acid methyl ester (VFAME) yield. To maintain a high yield of VFAMEs, this study suggests that dilution of the sample to an optimum concentration (∼500 ppm for each VFA) is required. Derivatization of VFAs into VFAMEs via the thermally-induced rapid esterification is more reliable to quantify and specify VFAs in the aqueous phase than conventional colorimetric method. Copyright © 2017 Elsevier Ltd. All rights reserved.

Effect of pH on the corrosion behaviour of SUS321 in the ammonia aqueous solution

International Nuclear Information System (INIS)

Park, Sang Yoon; Jeong, Y. H.; Baek, J. H.; Choi, B. K.; Lee, M. H.; Choi, B. S.; Yoon, J. H.; Lee, D. J.

2003-02-01

The corrosion characteristics of SUS321 for pressure vessel of SMART in pure water, ammonia aqueous solutions of pH 8.5 ∼ 11.5 at 300 .deg. C were evaluated by using static autoclaves. SUS321 specimen in the high temperature ammonia aqueous solution has weight gain or loss by the 4 reactions. And it depends on the refreshing period of the aqueous solution. So additional experiments by recirculating loop system were required to evaluate the corrosion behaviour of SUS321 in the ammonia aqueous solution

Aqueous two-phase system purification for superoxide dismutase induced by menadione from Phanerochaete chrysosporium.

Science.gov (United States)

Kavakcıoğlu, Berna; Tongul, Burcu; Tarhan, Leman

2017-03-01

In the present work, the partitioning behavior of menadione-induced superoxide dismutase (SOD; EC 1.15.1.1), an antioxidant enzyme that has various applications in the medical and cosmetic industries, from the white rot fungus Phanerochaete chrysosporium has been characterized on different types of aqueous two-phase systems (ATPSs) (poly(ethylene glycol)/polypropylene glycol (PEG/PPG)-dextran, PEG-salt and PPG-salt). PEG-salt combinations were found most optimal systems for the purification of SOD. The best partition conditions were found using the PEG-3350 24% and K 2 HPO 4 5% (w/w) with pH 7.0 at 25 °C. The partition coefficient of total SOD activity and total protein concentration observed in this system were 0.17 and 6.65, respectively, with the recovery percentage as 78.90% in the bottom phase and 13.17% in the top phase. The highest purification fold for SOD from P. chrysosporium was found as 6.04 in the bottom phase of PEG 3350%24 - K 2 HPO 4 %5 (w/w) system with pH 7.0. SOD purified from P. chrysosporium was determined to be a homodimer in its native state with a molecular weight of 60  ± 4 kDa. Consequently, simple and only one step PEG-salt ATPS system was developed for SOD purification from P. chrysosporium.

The potential/pH diagram of silver in aqueous ammonium salt solution

NARCIS (Netherlands)

Sluyters, J.H.; Wijnen, M.D.; Hul, H.J. van den

1961-01-01

The potential/pH diagram of silver in aqueous ammonium salt solution at 25°C has been calculated and verified experimentally. Calculations were carried out on the basis of the standard potential of the silver/silver-ion couple, the dissociation constants of the silver mono- and di-ammonia

Different Diversity and Distribution of Archaeal Community in the Aqueous and Oil Phases of Production Fluid From High-Temperature Petroleum Reservoirs

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Bo Liang

2018-04-01

Full Text Available To get a better knowledge on how archaeal communities differ between the oil and aqueous phases and whether environmental factors promote substantial differences on microbial distributions among production wells, we analyzed archaeal communities in oil and aqueous phases from four high-temperature petroleum reservoirs (55–65°C by using 16S rRNA gene based 454 pyrosequencing. Obvious dissimilarity of the archaeal composition between aqueous and oil phases in each independent production wells was observed, especially in production wells with higher water cut, and diversity in the oil phase was much higher than that in the corresponding aqueous phase. Statistical analysis further showed that archaeal communities in oil phases from different petroleum reservoirs tended to be more similar, but those in aqueous phases were the opposite. In the high-temperature ecosystems, temperature as an environmental factor could have significantly affected archaeal distribution, and archaeal diversity raised with the increase of temperature (p < 0.05. Our results suggest that to get a comprehensive understanding of petroleum reservoirs microbial information both in aqueous and oil phases should be taken into consideration. The microscopic habitats of oil phase, technically the dispersed minuscule water droplets in the oil could be a better habitat that containing the indigenous microorganisms.

Solvent extraction separations of trivalent lanthanide and actinide ions using an aqueous aminomethanediphosphonic acid

International Nuclear Information System (INIS)

Jensen, M. P.

1998-01-01

The possibility of separating the trivalent lanthanides, represented by EU 3+ , and actinides, represented by Cf 3+ , using HDEHP in toluene and an aqueous phase containing N-piperidinomethane-1,1-diphosphotic acid, PMDPA, has been investigated. This modified aqueous phase offers potential advantages over the diethylenetriaminepentaacetic acid based TALSPEAK process because of the improved complexation properties of PMDPA in acidic solutions, and the ability to decompose PMDPA before disposal. Extraction experiments were conducted at 25 C in 2 M NaClO 4 between -log [H + ] 1 and 2. The studies enabled us to derive the aqueous phase speciation, the stability constants of the aqueous complexes, and the Cf/Eu separation factors. Despite the presence of an amino group in PMDPA that should favor the retention of the actinides in the aqueous phase, the Cf/Eu separation factors are near unity under the conditions studied

Preparation, characterization and application of a reversed phase liquid chromatography/hydrophilic interaction chromatography mixed-mode C18-DTT stationary phase.

Science.gov (United States)

Wang, Qing; Long, Yao; Yao, Lin; Xu, Li; Shi, Zhi-Guo; Xu, Lanying

2016-01-01

A mixed-mode chromatographic stationary phase, C18-DTT (dithiothreitol) silica (SiO2) was prepared through "thiol-ene" click chemistry. The obtained material was characterized by fourier transform infrared spectroscope, nitrogen adsorption analysis and contact angle analysis. Chromatographic performance of the C18-DTT was systemically evaluated by studying the effect of acetonitrile content, pH, buffer concentration of the mobile phase and column temperature. It was demonstrated that the novel stationary phase possessed reversed phase liquid chromatography (RPLC)/hydrophilic interaction liquid chromatography (HILIC) mixed-mode property. The stop-flow test revealed that C18-DTT exhibited excellent compatibility with 100% aqueous mobile phase. Additionally, the stability and column-to-column reproducibility of the C18-DTT material were satisfactory, with relative standard deviations of retention factor of the tested analytes (verapamil, fenbufen, guanine, tetrandrine and nicotinic acid) in the range of 1.82-3.72% and 0.85-1.93%, respectively. Finally, the application of C18-DTT column was demonstrated in the separation of non-steroidal anti-inflammatory drugs, aromatic carboxylic acids, alkaloids, nucleo-analytes and polycyclic aromatic hydrocarbons. It had great resolving power in the analysis of various compounds in HILIC and RPLC chromatographic conditions and was a promising RPLC/HILIC mixed-mode stationary phase. Copyright © 2015 Elsevier B.V. All rights reserved.

Segregative phase separation in aqueous mixtures of polydisperse biopolymers

NARCIS (Netherlands)

Edelman, M.W.

2003-01-01

Keywords: biopolymer, gelatine, dextran, PEO, phase separation, polydispersity, molar mass distribution, SEC-MALLS, CSLM The temperature-composition phase diagram of aqueous solutions of gelatine and dextran, which show liquid/liquid phase segregation, were explored at temperatures above the

Internally consistent thermodynamic data for aqueous species in the system Na-K-Al-Si-O-H-Cl

Science.gov (United States)

Miron, George D.; Wagner, Thomas; Kulik, Dmitrii A.; Heinrich, Christoph A.

2016-08-01

A large amount of critically evaluated experimental data on mineral solubility, covering the entire Na-K-Al-Si-O-H-Cl system over wide ranges in temperature and pressure, was used to simultaneously refine the standard state Gibbs energies of aqueous ions and complexes in the framework of the revised Helgeson-Kirkham-Flowers equation of state. The thermodynamic properties of the solubility-controlling minerals were adopted from the internally consistent dataset of Holland and Powell (2002; Thermocalc dataset ds55). The global optimization of Gibbs energies of aqueous species, performed with the GEMSFITS code (Miron et al., 2015), was set up in such a way that the association equilibria for ion pairs and complexes, independently derived from conductance and potentiometric data, are always maintained. This was achieved by introducing reaction constraints into the parameter optimization that adjust Gibbs energies of complexes by their respective Gibbs energy effects of reaction, whenever the Gibbs energies of reactant species (ions) are changed. The optimized thermodynamic dataset is reported with confidence intervals for all parameters evaluated by Monte Carlo trial calculations. The new thermodynamic dataset is shown to reproduce all available fluid-mineral phase equilibria and mineral solubility data with good accuracy and precision over wide ranges in temperature (25-800 °C), pressure (1 bar to 5 kbar) and composition (salt concentrations up to 5 molal). The global data optimization process adopted in this study can be readily repeated any time when extensions to new chemical elements and species are needed, when new experimental data become available, or when a different aqueous activity model or equation of state should be used. This work serves as a proof of concept that our optimization strategy is feasible and successful in generating a thermodynamic dataset reproducing all fluid-mineral and aqueous speciation equilibria in the Na-K-Al-Si-O-H-Cl system within

C18, C8, and perfluoro reversed phases on diamond for solid-phase extraction.

Science.gov (United States)

Saini, Gaurav; Wiest, Landon A; Herbert, David; Biggs, Katherine N; Dadson, Andrew; Vail, Michael A; Linford, Matthew R

2009-04-17

In spite of advances in solid-phase extraction (SPE) technology there are certain disadvantages to current SPE silica-based, column packings. The pH range over which extraction can occur is limited and each column is generally only used once. New diamond-based reversed SPE phases (C(18), C(8), and perfluorinated) were developed in our laboratories. Studies were done which show that these phases do not have the same limitations as traditional silica-based stationary phases. The synthesis and properties of these diamond-based phases are presented, and the stability, percent recovery, and column capacity are given for the C(18) phase.

Eh-pH diagrams of the V-H2O system at 25,60 and 1000C

International Nuclear Information System (INIS)

Silva, F.T. da; Ogasawara, T.; Cassa, J.C.S.

1987-01-01

Free energies of the formation of vanadium ions in aqueous solutions at elevated temperatures were determined. Eh-pH diagrams at 25 0 C, 60 0 C and 100 0 C at different vanadium concentrations, using microcomputers were calculated and obtained. The effects of temperature and vanadium concentration on the predominance of vanadium species were examined. The Eh-pH diagrams for the V-H 2 O system were evaluated by comparisons with experimental data. (Author) [pt

The C-S-H gel of Portland cement mortars: Part I. The interpretation of energy-dispersive X-ray microanalyses from scanning electron microscopy, with some observations on C-S-H, AFm and AFt phase compositions

International Nuclear Information System (INIS)

Famy, C.; Brough, A.R.; Taylor, H.F.W.

2003-01-01

Scanning electron microscopy (SEM) microanalyses of the calcium-silicate-hydrate (C-S-H) gel in Portland cement pastes rarely represent single phases. Essential experimental requirements are summarised and new procedures for interpreting the data are described. These include, notably, plots of Si/Ca against other atom ratios, 3D plots to allow three such ratios to be correlated and solution of linear simultaneous equations to test and quantify hypotheses regarding the phases contributing to individual microanalyses. Application of these methods to the C-S-H gel of a 1-day-old mortar identified a phase with Al/Ca=0.67 and S/Ca=0.33, which we consider to be a highly substituted ettringite of probable composition C 6 A 2 S-bar 2 H 34 or {Ca 6 [Al(OH) 6 ] 2 ·24H 2 O}(SO 4 ) 2 [Al(OH) 4 ] 2 . If this is true for Portland cements in general, it might explain observed discrepancies between observed and calculated aluminate concentrations in the pore solution. The C-S-H gel of a similar mortar aged 600 days contained unsubstituted ettringite and an AFm phase with S/Ca=0.125

Bioligand-mediated partitioning of radionuclides to the aqueous phase

International Nuclear Information System (INIS)

Johnsson, A.; Pedersen, K.; Oedegaard-Jensen, A.; Jakobsson, A.M.; Ekberg, C.

2008-01-01

The aqueous-phase partitioning of 59 Fe, 147 Pm, 234 Th and 241 Am by complexing compounds from subsurface bacteria has previously been studied in the presence of quartz sand. In this study the aqueous-phase partitioning of pico- to submicromolar amounts of 59 Fe, 147 Pm, 234 Th and 241 Am was analyzed in the presence of TiO 2 and exudates from three species of subsurface bacteria: Pseudomonas fluorescens, Pseudomonas stutzeri, and Shewanella putrefaciens. All were grown under aerobic conditions and P. stutzeri and S. putrefaciens were grown under anaerobic conditions as well. The supernatants of the aerobic and anaerobic cultures were collected and radionuclide was added. TiO 2 , with BET surface area of 49.9 m 2 x g -1 , was added to the supernatant radionuclide mix, and the pH was adjusted to approximately 8. After incubation, the amount of radionuclide in the liquid phase of the samples and controls was analyzed using scintillation method. Two types of values were calculated: solution% = the activity maintained in solution relative to the total activity, and Q-values = the quotient between the activity in samples and the activity in controls. Aerobic supernatants had solution% values between 89% and 100% for 59 Fe and between 18 and 43% for 234 Th. The solution% values for 241 Am and 147 Pm were less than 2% overall, but the Q-values were between 34 and 115 times more 241 Am in bacterial supernatants than in controls. The corresponding values for 147 Pm ranged from 6 to 20 times more than in the control. The solution% values for all elements in the presence of anaerobic supernatants were below 2%, but the Q-values clustered around 7 for 59 Fe and ranging from 2 to 29 for 234 Th, indicated that anaerobic supernatants partitioned these elements to the aqueous phase. Both aerobic and anaerobic supernatants tested positive for complexing compounds when analyzed, using the Chrome Azurol S assay. Complexation with excreted organic ligands is most likely the reason

Phase diagrams of NaOCl-Na3PO4-H2O ternary system. Jiaensosan natrium-rinsan natrium-mizu sanseibun soheiko jotaizu

Energy Technology Data Exchange (ETDEWEB)

Hamano, A. (Sasebo College of Tehcnology, Nagasaki (Japan)); Kito, K. (Nippon Steel Chemical Co. Ltd., Tokyo (Japan))

1993-10-30

Sodium chlorate (NaOCl) aqueous solution is used widely as a bleach. Attempts have been made to extract crystals from this aqueous solution, but only with difficulty because of instability of the generated crystals. Generating Na3PO4 and solid solution has been attempted as a method to stabilize the crystals. The present study has prepared a phase equilibrium diagram for three components of NaOCl-Na3PO4-H2O at 5[degree]C and 10[degree]C for theoretical elucidation thereof. In the prepared diagram, the conjugate lines linking the saturated solution with the solution containing solid phase have not crossed at one point, but scattered on the solid phase line. This has made clear that no double salt has been generated, but solid solution has been produced. The mol ratio of NaOCl in the generated solid solution was 0.071 to 0.447 at 15[degree]C and 0.026 to 0.6 at 5[degree]C indicating that solid solution with composition of wider range than in literatures reported conventionally has been produced. 8 refs., 2 figs., 2 tabs.

Radionuclides retention in C-S-H, main phases of cement matrices for low and intermediate-level wastes; Retencion de radionuclidos en C-S-H, principales fases de matrices de cemento para desechos de bajo y medio nivel

Energy Technology Data Exchange (ETDEWEB)

Badillo A, V. E.; Lopez R, C.; Vidal M, J. [ININ, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico); Gutierrez B, O., E-mail: veronica.badillo@inin.gob.mx [Instituto Tecnologico de Toluca, Av. Tecnologico s/n, Exrancho La Virgen, Metepec, Estado de Mexico (Mexico)

2014-10-15

Knowing that the behavior of cementitious materials based on hydraulic binder called cement is essentially determined by the physicochemical evolution of the cement paste (water + cement) which constitutes it, the evolution of the cement paste in contact with different aqueous solutions is studied since one of the main risks in safety of systems is composed of surface and groundwater, which contribute to the alteration of the different barriers and represent the main way of radionuclides transport. The calcium silicates CSH are the main phases that compose the systems based on Portland cement. The hydrates calcium silicates possess a high degree of structural complexity which includes crystalline, partially crystalline and amorphous phases. In this study the microstructures of the CSH phases as well as the retention of radionuclide Sr (II) are studied through the {sup 87m}Sr in formulations of water/cement w/c = 0.55; experimental values of K d low around 20 ml g{sup -1} are obtained in function of hydration time of the cement paste in equilibrium with aqueous solutions. (Author)

(Solid + liquid) isothermal evaporation phase equilibria in the aqueous ternary system (Li{sub 2}SO{sub 4} + MgSO{sub 4} + H{sub 2}O) at T = 308.15 K

Energy Technology Data Exchange (ETDEWEB)

Wang Shiqiang [Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008 (China); Graduate University of Chinese Academy of Sciences, Beijing 100039 (China); Deng Tianlong [Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, Xining 810008 (China); College of Materials, Chemistry and Chemical Engineering, Chengdu University Technology, Chengdu 610059 (China)], E-mail: dtl@cdut.edu.cn

2008-06-15

The solubility and the density in the aqueous ternary system (Li{sub 2}SO{sub 4} + MgSO{sub 4} + H{sub 2}O) at T = 308.15 K were determined by the isothermal evaporation. Our experimental results permitted the construction of the phase diagram and the plot of density against composition. It was found that there is one eutectic point for (Li{sub 2}SO{sub 4} . H{sub 2}O + MgSO{sub 4} . 7H{sub 2}O), two univariant curves, and two crystallization regions corresponding to lithium sulphate monohydrate (Li{sub 2}SO{sub 4} . H{sub 2}O) and epsomite (MgSO{sub 4} . 7H{sub 2}O). The system belongs to a simple co-saturated type, and neither double salts nor solid solution was found. Based on the Pitzer ion-interaction model and its extended HW models of aqueous electrolyte solution, the solubility of the ternary system at T = 308.15 K has been calculated. The predicted solubility agrees well with the experimental values.

Thermal stability of nanocomposite CrC/a-C:H thin films

International Nuclear Information System (INIS)

Gassner, G.; Mayrhofer, P.H.; Patscheider, J.; Mitterer, C.

2007-01-01

The thermal stability of low-friction Me-C/a-C:H coatings is important for their potential applications in the tool and automotive industry. Recently we showed that CrC x /a-C:H coatings prepared by unbalanced magnetron sputtering of a Cr target in Ar + CH 4 glow discharges exhibit a nanocomposite structure where metastable fcc CrC nanocrystals are encapsulated by an a-C:H phase. Here, we present the structural evolution of these nanocomposite CrC/a-C:H coatings during annealing. High-temperature X-ray diffraction in vacuum and differential scanning calorimetry (DSC) combined with thermo-gravimetric analysis in Ar atmosphere indicate decomposition of the formed metastable fcc CrC phase and subsequent formation of Cr 3 C 2 and Cr 7 C 3 and structural transformation of the a-C:H matrix phase towards higher sp 2 bonding contents at temperatures above 450 deg. C. Combined DSC and mass spectrometer analysis as well as elemental profiling after annealing in vacuum by elastic recoil detection analysis relate this transformation to the loss of bonded hydrogen at temperatures above 200 deg. C. Due to these structural changes the coefficient of friction depends on the annealing temperature of the nanocomposite a-C:H coatings and shows a minimum of ∼ 0.13 for T = 200 deg. C. The more complex tribochemical reactions, influenced by the hydrogen loss from the coating during in-situ high temperatures ball-on disc tests, result in coefficient of friction values below 0.05 for T < 120 deg. C

PHASE CHANGES ON 4H AND 6H SIC AT HIGH TEMPERATURE OXIDATION

Directory of Open Access Journals (Sweden)

Jan Setiawan

2016-10-01

Full Text Available ABSTRACT PHASE CHANGES ON 4H AND 6H SIC AT HIGH TEMPERATURE OXIDATION. The oxidation on two silicon carbide contain 6H phase and contains 6H and 4H phases has been done.  Silicon carbide is ceramic non-oxide with excellent properties that potentially used in industry.  Silicon carbide is used in nuclear industry as structure material that developed as light water reactor (LWR fuel cladding and as a coating layer in the high temperature gas-cooled reactor (HTGR fuel.  In this study silicon carbide oxidation simulation take place in case the accident in primary cooling pipe is ruptured.  Sample silicon carbide made of powder that pressed into pellet with diameter 12.7 mm and thickness 1.0 mm, then oxidized at temperature 1000 oC, 1200 oC dan 1400 oC for 1 hour.  The samples were weighted before and after oxidized.  X-ray diffraction con-ducted to the samples using Panalytical Empyrean diffractometer with Cu as X-ray source.  Diffraction pattern analysis has been done using General Structure Analysis System (GSAS software. This software was resulting the lattice parameter changes and content of SiC phases.  The result showed all of the oxidation samples undergoes weight gain.  The 6S samples showed the highest weight change at oxidation temperature 1200 oC, for the 46S samples showed increasing tendency with the oxidation temperature.  X-ray diffraction pattern analysis showed the 6S samples contain dominan phase 6H-SiC that matched to ICSD 98-001-5325 card.  Diffraction pattern on 6S showed lattice parameter, composition and crystallite size changes.  Lattice parameters changes had smaller tendency from the model and before oxidation.  However, the lowest silicon carbide composition or the highest converted into other phases up to 66.85 %, occurred at oxidation temperature 1200 oC.  The 46S samples contains two polytypes silicon car-bide.  The 6H-SiC phases matched by ICSD 98-016-4972 card and 4H-SiC phase matched by ICSD 98

Bioconversion of apigenin-7-O-β-glucoside in aqueous two-phase system

Directory of Open Access Journals (Sweden)

Ilić Sanja M.

2005-01-01

Full Text Available The study is concerned with the conversion of apigenin-7-O-β-glucoside into apigenin in polyethylene glycol 6000 / dextran 20000 aqueous two-phase system by β-glucosidase. Apigenin was separated from apigenin-7-O-β-glucoside and β-glucosidase by their partition into opposite phases. In 14% PEG / 22.5% DEX aqueous two-phase system obtained yield of apigenin in top phase was 108%.

Aqueous-phase reforming of crude glycerol : effect of impurities on hydrogen production

NARCIS (Netherlands)

Boga, Dilek A.; Liu, Fang; Bruijnincx, Pieter C. A.; Weckhuysen, Bert M.

2016-01-01

The aqueous-phase reforming (APR) of a crude glycerol that originates from an industrial process and the effect of the individual components of crude glycerol on APR activity have been studied over 1 wt% Pt/Mg-Al) O, 1 wt% Pt/Al2O3, 5 wt% Pt/Al2O3 and 5 wt% Pt/C catalysts at 29 bar and 225 degrees

NCI calculations for understanding a physical phase transition in (C6H14N2)[Mn(H2O)6](SeO4)2

Science.gov (United States)

Naïli, Houcine; François, Michel; Norquist, Alexander J.; Rekik, Walid

2017-12-01

An organically templated manganese selenate, (C6H14N2)[Mn(H2O)6](SeO4)2, has been synthesized by slow evaporation and crystallographically characterized. The title compound crystallizes at room temperature in the monoclinic centrosymmetric space group P21/n, with the following unit cell parameters: a = 7.2373(4) Å; b = 12.5600(7) Å; c = 10.1945(7) Å; β = 91.155(4)°, V = 926.50(10) Å3and Z = 2. Its crystal structure is built of manganese(II) cations coordinated by six water molecules in octahedral geometry, disordered dabcodiium cations and selenate anions, resulting in an extensive hydrogen-bonding network. Differential scanning calorimetry (DSC) measurement indicated that the precursor undergoes a reversible phase transition at about 216 and 218 K during the cooling and heating processes respectively. Below this temperature the title compound is noncentrosymmetric with space group P21 and lattice parameters a = 7.2033(8) Å; b = 12.4981(13) Å; c = 10.0888(11) Å; β = 91.281(2)°, V = 908.04(17) Å3 and Z = 2. The disorder-order transformation of the C atoms of (C6H14N2)2+ cation may drive the structural phase transition. The low temperature phase obtained by breaking symmetry presents a fully ordered structure. The noncovalent interaction (NCI) method was used not only to locate, quantify, and visualize intermolecular interactions in the high and low temperature phases but also to confirm the phase transition detected by DSC measurement. The thermal decomposition of this new compound proceeds through four stages giving rise to the manganese oxide as final product at 850 °C.

Memory effect of calcined layered samarium hydroxy chlorides in aqueous solution

International Nuclear Information System (INIS)

Lee, Byung Il; Byeon, Song Ho

2015-01-01

The decomposition and recovery behavior of layered samarium hydroxychloride (Sm 2 (OH) 5 Cl·nH 2 O, LSmH) has been closely studied in various conditions. Although the heat treatment of LSmH at 700 °C completely collapsed typical layered structure, the calcined LSmH (c-LSmH) recovered its layered characteristics and consequently its ability to intercalate anions into the interlayer space when it was rehydroxylated and rehydrated in aqueous solutions containing organic and inorganic anions. This phenomenon is similar to the memory effect observed in classical layered double hydroxides (LDHs), where LDHs calcined to a mixture of metal oxides can recover their layered structures in aqueous solutions. In contrast, the recovery reaction of c-LSmH in water without any counter anions was unsuccessful and instead resulted in the formation of Sm(OH) 3 . Such a difference was interpreted on the basis of the salt effect on Sm 2 (OH) 5 Cl·nH 2 O–Sm(OH) 3 phase equilibria in water

PHASE-TRANSITIONS IN THE BILAYERS OF VESICLES FORMED FROM BINARY-MIXTURES OF SYMMETRICAL DI-N-ALKYLPHOSPHATES IN AQUEOUS-SOLUTIONS

NARCIS (Netherlands)

BLANDAMER, MJ; BRIGGS, B; CULLIS, PM; ENGBERTS, JBFN; WAGENAAR, A; SMITS, E; HOEKSTRA, D; KACPERSKA, A

1994-01-01

Vesicles in aqueous solutions were prepared from binary equimolar mixtures of di-n-alkyl-phosphates (sodium and potassium), (R(1)O)(2)PO(2)(-)M(+) and (R(2)O)(2)PO(2)(-)M(+). When the number of carbon atoms in R(1) and R(2) differs by two and when R(1) or R(2) = C12H25, C14H29, C16H33 and C18H37 the

Enantioseparation of Racemic Flurbiprofen by Aqueous Two-Phase Extraction With Binary Chiral Selectors of L-dioctyl Tartrate and L-tryptophan.

Science.gov (United States)

Chen, Zhi; Zhang, Wei; Wang, Liping; Fan, Huajun; Wan, Qiang; Wu, Xuehao; Tang, Xunyou; Tang, James Z

2015-09-01

A novel method for chiral separation of flurbiprofen enantiomers was developed using aqueous two-phase extraction (ATPE) coupled with biphasic recognition chiral extraction (BRCE). An aqueous two-phase system (ATPS) was used as an extracting solvent which was composed of ethanol (35.0% w/w) and ammonium sulfate (18.0% w/w). The chiral selectors in ATPS for BRCE consideration were L-dioctyl tartrate and L-tryptophan, which were screened from amino acids, β-cyclodextrin derivatives, and L-tartrate esters. Factors such as the amounts of L-dioctyl tartrate and L-tryptophan, pH, flurbiprofen concentration, and the operation temperature were investigated in terms of chiral separation of flurbiprofen enantiomers. The optimum conditions were as follows: L-dioctyl tartrate, 80 mg; L-tryptophan, 40 mg; pH, 4.0; flurbiprofen concentration, 0.10 mmol/L; and temperature, 25 °C. The maximum separation factor α for flurbiprofen enantiomers could reach 2.34. The mechanism of chiral separation of flurbiprofen enantiomers is discussed and studied. The results showed that synergistic extraction has been established by L-dioctyl tartrate and L-tryptophan, which enantioselectively recognized R- and S-enantiomers in top and bottom phases, respectively. Compared to conventional liquid-liquid extraction, ATPE coupled with BRCE possessed higher separation efficiency and enantioselectivity without the use of any other organic solvents. The proposed method is a potential and powerful alternative to conventional extraction for separation of various enantiomers. © 2015 Wiley Periodicals, Inc.

Influence of the composition of the aqueous phase on the behavior of the system FeCl3-HCl-DPE

International Nuclear Information System (INIS)

Ramirez, F. de M.; Jimenez-Reyes, M.

1981-07-01

We studied the influence of the aqueous phase composition upon an extraction system in which, at room temperature (20 0 C +- 3 0 C) using the dissolvents FeCl 3 -HCl-di-isopropyl ether the third phase phenomena is present after one minute of agitation. Our results showed that principally the hydrochloric acid dissolvent produced each of the three phases at given concentration levels as well as determined the nature of the chemical composition in each phase. (author)

Development of oxygen and pH sensors for aqueous systems

International Nuclear Information System (INIS)

Stvartak, C.; Alcock, C.B.; Li, B.; Wang, L.; Fergus, J.W.; Bakshi, N.

1994-04-01

Corrosion science has long recognized that two of the most important parameters in characterizing the corrosivity of an aqueous environment are oxygen chemical potential and pH. These parameters not only determine the thermodynamic driving forces for various corrosion reactions, but also characterize the rates of these reactions and hence the lifetime of a particular component. The primary goal of this project is to develop an electrochemical oxygen and pH sensor for continuous use in the cycle chemistry control of power plants. In the past year, electrochemical sensors with a metal/metal oxide or metal/metal hydride internal reference electrode and a fluoride-based electrolyte tube have been developed and tested in this laboratory. The corrosion tests showed that the LaF 3 -based solid electrolyte was very stable both chemically and physically in water. Furthermore, its electrical conductivity is 4 to 5 orders of magnitude higher than that of stabilized zirconia below 573 K (300 degree C), which is the main advantage of a fluoride-based electrolyte at low temperatures. With this electrolyte and the selected internal oxygen reference electrode (Ag/Ag 2 O), the electrochemical probe demonstrated Nernstian responses to the oxygen chemical potential and pH of the aqueous solution with good reproducibility. A similar cell with Zr/ZrH 1+x as the internal hydrogen reference electrode showed promising pH sensing characteristics. It is proposed that these two cells be combined to form a double-headed electrochemical probe to determine oxygen chemical potential and pH in the solution simultaneously

Mechanisms of catalytic cleavage of benzyl phenyl ether in aqueous and apolar phases

Energy Technology Data Exchange (ETDEWEB)

He, Jiayue; Lu, Lu; Zhao, Chen; Mei, Donghai; Lercher, Johannes A.

2014-03-01

Catalytic pathways for the cleavage of ether bonds in benzyl phenyl ether (BPE) in liquid phase using Ni- and zeolite-based catalysts are explored. In the absence of catalysts, the C-O bond is selectively cleaved in water by hydrolysis, forming phenol and benzyl alcohol as intermediates, followed by alkylation. The hydronium ions catalyzing the reactions are provided by the dissociation of water at 523 K. Upon addition of HZSM-5, rates of hydrolysis and alkylation are markedly increased in relation to proton concentrations. In the presence of Ni/SiO₂, the selective hydrogenolysis dominates for cleaving the C_aliphatic-O bond. Catalyzed by the dual-functional Ni/HZSM-5, hydrogenolysis occurs as the major route rather than hydrolysis (minor route). In apolar undecane, the non-catalytic thermal pyrolysis route dominates. Hydrogenolysis of BPE appears to be the major reaction pathway in undecane in the presence of Ni/SiO₂ or Ni/HZSM-5, almost completely suppressing radical reactions. Density functional theory (DFT) calculations strongly support the proposed C-O bond cleavage mechanisms on BPE in aqueous and apolar phases. These calculations show that BPE is initially protonated and subsequently hydrolyzed in the aqueous phase. Finally, DFT calculations suggest that the radical reactions in non-polar solvents lead to primary benzyl and phenoxy radicals in undecane, which leads to heavier condensation products as long as metals are absent for providing dissociated hydrogen.

The salting-out effect and phase separation in aqueous solutions of tri-sodium citrate and 1-butyl-3-methylimidazolium bromide

International Nuclear Information System (INIS)

Sadeghi, Rahmat; Golabiazar, Roonak; Shekaari, Hemayat

2010-01-01

The aim of this work is to obtain further evidence about the salting-out effect produced by the addition of tri-sodium citrate to aqueous solutions of water miscible ionic liquid 1-butyl-3-methylimidazolium bromide ([C 4 mim][Br]) by evaluating the effect of tri-sodium citrate on the thermodynamic properties of aqueous solutions of this ionic liquid. Experimental measurements of density and sound velocity at different temperatures ranging from (288.15 to 308.15) K, the refractive index at 308.15 K and the liquid-liquid phase diagram at different temperatures ranging from (288.15 to 338.15) K for aqueous solutions containing 1-butyl-3-methylimidazolium bromide ([C 4 mim][Br]) and tri-sodium citrate (Na 3 Cit) are taken. The apparent molar volume of transfer of [C 4 mim][Br] from water to aqueous solutions of Na 3 Cit have positive values and it increases by increasing salt molality. Although at high IL molality, the apparent molar isentropic compressibility shows similar behaviour with that of the apparent molar volume. However at low concentrations of IL, the apparent molar isentropic compressibility of transfer of [C 4 mim][Br] from water to aqueous solutions of Na 3 Cit have negative values. The effects of temperature and the addition of Na 3 Cit and [C 4 mim][Br] on the liquid-liquid phase diagram of the investigated system have been studied. It was found that an increase in temperature caused the expansion of the one-phase region. The presence of Na 3 Cit triggers a salting-out effect, leading to significant upward shifts of the liquid-liquid de-mixing temperatures of the system. The effect of temperature on the phase-forming ability in the system investigated has been studied based on a salting-out coefficient obtained from fitting the binodal values to a Setschenow-type equation for each temperature. Based on cloud point values, the energetics of the clouding process have been estimated and it was found that both of entropy and enthalpy are the driving forces

Extraction Equilibrium of Acrylic Acid by Aqueous Two-Phase Systems Using Hydrophilic Ionic Liquids

International Nuclear Information System (INIS)

Lee, Yong Hwa; Lee, Woo Youn; Kim, Ki-Sub; Hong, Yeon Ki

2014-01-01

As an effective method for extraction of acrylic acid, aqueous two-phase systems based on morpholinium ionic liquids were used in this study. Effects of the alkyl chain length of cation in morpholinium ionic liquids on phase diagram and extraction efficiencies were investigated. Experimental results show that aqueous two phase systems can be formed by adding appropriate amount of morpholinium ionic liquids to aqueous K 2 HPO 4 solutions. It can be found that the ability of morpholinium ionic liquids for phase separation followed the order [HMMor][Br]>[OMMor][Br]>[BMMor][Br]>[EMMor][Br]. There was little difference between binodal curves of imidazolium ionic liquids and those of morpholinium ionic liquids. 50-90% of the extraction efficiency was observed for acrylic acid by aqueous two phase extraction of acrylic acid with morpholinium ionic liquids. It can be concluded that morpholinium ionic liquids/K 2 HPO 4 were effective for aqueous two phases extraction of acrylic acid comparing to imidazolium ionic liquids/K 2 HPO 4 systems because of their lower cost

Liquid Phase Micro-Extraction of Linear Alkylbenzene Sulfonate Anionic Surfactants in Aqueous Samples

Directory of Open Access Journals (Sweden)

Jan Åke Jönsson

2011-10-01

Full Text Available Hollow fiber liquid phase micro-extraction (LPME of linear alkylbenzene sulfonates (LAS from aqueous samples was studied. Ion pair extraction of C10, C11, C12 and C13 homologues was facilitated with trihexylamine as ion-pairing agent, using di-n-hexylether as solvent for the supported liquid membrane (SLM. Effects of extraction time, acceptor buffer concentration, stirring speed, sample volume, NaCl and humic acids were studied. At 10–50 µg L−1 linear R2-coefficients were 0.99 for C10 and C11 and 0.96 for C12. RSD was typically ~15%. Three observations were especially made. Firstly, LPME for these analytes was unusually slow with maximum enrichment observed after 15–24 h (depending on sample volume. Secondly, the enrichment depended on LAS sample concentration with 35–150 times enrichment below ~150 µg L−1 and 1850–4400 times enrichment at 1 mg L−1. Thirdly, lower homologues were enriched more than higher homologues at low sample concentrations, with reversed conditions at higher concentrations. These observations may be due to the fact that LAS and the amine counter ion themselves influence the mass transfer at the water-SLM interface. The observations on LPME of LAS may aid in LPME application to other compounds with surfactant properties or in surfactant enhanced membrane extraction of other compounds.

The phase transport and reactions of γ-irradiated aqueous-ionic liquids

International Nuclear Information System (INIS)

Howett, S.; Joseph, J.; Noel, J.J.; Wren, J.C.

2010-01-01

A novel technology based on the transfer of chemical species across water/ionic liquid interfaces via specific complexation reactions is currently being considered for the separation and sequestration of metal ion contaminants from radioactive waste effluents in the nuclear fuel cycle. An ideal solvent for these applications should have a high intrinsic selectivity for a targeted metal or group of metals (e.g., trans-Pu actinides, lanthanides, or other fission products), an efficient switching mechanism (between complexation and decomplexation), and a high immiscibility with aqueous solutions. These characteristics must be maintained in the chemical, radiation, and mass transport environments present during the separation process. Ionic liquids (ILs) have an almost negligible vapour pressure and high thermal stability. Their ability to dissolve a wide range of substrate molecules and potential to be highly resilient in radiation fields make ILs particularly promising media. The separation efficiency of the biphasic system will depend on many parameters, including the aqueous oxidation state of the targeted metal ion, and the thermodynamics and kinetics of interfacial transport and metal-ligand complex formation at the water/IL interface or in the IL phase. The most uncertain and unstudied area for these applications is the effect of ionizing radiation on the stability and separation efficiency of the biphasic system. The present study investigates the effect of γ-radiation on gas/IL and water/IL interfacial stability and mass transfer with trihexyltetradecylphosphonium bis(trifluoromethyl-sulfonyl)imide, a phosphonium-based IL. The IL, in contact with either gas or water, was irradiated at a dose rate of 6.4 kGy·h -1 . Gas-phase samples were analyzed by gas chromatography-mass spectrometry (GC-MS) and the changes in the IL and aqueous phases were monitored by conductivity measurements and Raman spectroscopy. In this paper we discuss these observations and their

Analysis of Solid and Aqueous Phase Products from Hydrothermal Carbonization of Whole and Lipid-Extracted Algae

Directory of Open Access Journals (Sweden)

Amber Broch

2013-12-01

Full Text Available Microalgae have tremendous potential as a feedstock for production of liquid biofuels, particularly biodiesel fuel via transesterification of algal lipids. However, biodiesel production results in significant amounts of algal residues, or “lipid extracted algae” (LEA. Suitable utilization of the LEA residue will improve the economics of algal biodiesel. In the present study, we evaluate the hydrothermal carbonization (HTC of whole and lipid extracted algal (Spirulina maxima feedstocks in order to produce a solid biofuel (hydrochar and value-added co-products in the aqueous phase. HTC experiments were performed using a 2-L Parr reactor (batch type at 175–215 °C with a 30-min holding time. Solid, aqueous and gaseous products were analyzed using various laboratory methods to evaluate the mass and carbon balances, and investigate the existence of high value chemicals in the aqueous phase. The HTC method is effective in creating an energy dense, solid hydrochar from both whole algae and LEA at lower temperatures as compared to lignocellulosic feedstocks, and is effective at reducing the ash content in the resulting hydrochar. However, under the treatment temperatures investigated, less than 1% of the starting dry algae mass was recovered as an identified high-value chemical in the aqueous phase.

Purification of Active Myrosinase from Plants by Aqueous Two-Phase Counter-Current Chromatography

Science.gov (United States)

Wade, Kristina L.; Ito, Yoichiro; Ramarathnam, Aarthi; Holtzclaw, W. David; Fahey, Jed W.

2014-01-01

Introduction Myrosinase (thioglucoside glucohydrolase; E.C. 3.2.1.147), is a plant enzyme of increasing interest and importance to the biomedical community. Myrosinase catalyses the formation of isothiocyanates such as sulforaphane (frombroccoli) and 4-(α-l-rhamnopyranosyloxy)benzyl isothiocyanate (from moringa), which are potent inducers of the cytoprotective phase-2 response in humans, by hydrolysis of their abundant glucosinolate (β-thioglucoside N-hydroxysulphate) precursors. Objective To develop an aqueous two-phase counter-current chromatography (CCC) system for the rapid, three-step purification of catalytically active myrosinase. Methods A high-concentration potassium phosphate and polyethylene glycol biphasic aqueous two-phase system (ATPS) is used with a newly developed CCC configuration that utilises spiral-wound, flat-twisted tubing (with an ovoid cross-section). Results Making the initial crude plant extract directly in the ATPS and injecting only the lower phase permitted highly selective partitioning of the myrosinase complex before a short chromatography on a spiral disk CCC. Optimum phase retention and separation of myrosinase from other plant proteins afforded a 60-fold purification. Conclusion Catalytically active myrosinase is purified from 3-day broccoli sprouts, 7-day daikon sprouts, mustard seeds and the leaves of field-grown moringa trees, in a CCC system that is predictably scalable. PMID:25130502

Purification of active myrosinase from plants by aqueous two-phase counter-current chromatography.

Science.gov (United States)

Wade, Kristina L; Ito, Yoichiro; Ramarathnam, Aarthi; Holtzclaw, W David; Fahey, Jed W

2015-01-01

Myrosinase (thioglucoside glucohydrolase; E.C. 3.2.1.147), is a plant enzyme of increasing interest and importance to the biomedical community. Myrosinase catalyses the formation of isothiocyanates such as sulforaphane (from broccoli) and 4-(α-l-rhamnopyranosyloxy)benzyl isothiocyanate (from moringa), which are potent inducers of the cytoprotective phase-2 response in humans, by hydrolysis of their abundant glucosinolate (β-thioglucoside N-hydroxysulphate) precursors. To develop an aqueous two-phase counter-current chromatography (CCC) system for the rapid, three-step purification of catalytically active myrosinase. A high-concentration potassium phosphate and polyethylene glycol biphasic aqueous two-phase system (ATPS) is used with a newly developed CCC configuration that utilises spiral-wound, flat-twisted tubing (with an ovoid cross-section). Making the initial crude plant extract directly in the ATPS and injecting only the lower phase permitted highly selective partitioning of the myrosinase complex before a short chromatography on a spiral disk CCC. Optimum phase retention and separation of myrosinase from other plant proteins afforded a 60-fold purification. Catalytically active myrosinase is purified from 3-day broccoli sprouts, 7-day daikon sprouts, mustard seeds and the leaves of field-grown moringa trees, in a CCC system that is predictably scalable. Copyright © 2014 John Wiley & Sons, Ltd.

Improving the treatment of non-aqueous phase TCE in low permeability zones with permanganate

International Nuclear Information System (INIS)

Chokejaroenrat, Chanat; Comfort, Steve; Sakulthaew, Chainarong; Dvorak, Bruce

2014-01-01

Graphical abstract: - Highlights: • Transport experiments used transmissive and low permeability zones (LPZs). • 14 C-labeled TCE was used to quantify oxidation of DNAPL in LPZs by permanganate. • Stabilization aids prevented MnO 2 rind formation. • DNAPL oxidation improved when xanthan and stabilization aids were used. - Abstract: Treating dense non-aqueous phase liquids (DNAPLs) embedded in low permeability zones (LPZs) is a particularly challenging issue for injection-based remedial treatments. Our objective was to improve the sweeping efficiency of permanganate (MnO 4 − ) into LPZs to treat high concentrations of TCE. This was accomplished by conducting transport experiments that quantified the penetration of various permanganate flooding solutions into a LPZ that was spiked with non-aqueous phase 14 C-TCE. The treatments we evaluated included permanganate paired with: (i) a shear-thinning polymer (xanthan); (ii) stabilization aids that minimized MnO 2 rind formation and (iii) a phase-transfer catalyst. In addition, we quantified the ability of these flooding solutions to improve TCE destruction under batch conditions by developing miniature LPZ cylinders that were spiked with 14 C-TCE. Transport experiments showed that MnO 4 − alone was inefficient in penetrating the LPZ and reacting with non-aqueous phase TCE, due to a distinct and large MnO 2 rind that inhibited the TCE from further oxidant contact. By including xanthan with MnO 4 − , the sweeping efficiency increased (90%) but rind formation was still evident. By including the stabilization aid, sodium hexametaphosphate (SHMP) with xanthan, permanganate penetrated 100% of the LPZ, no rind was observed, and the percentage of TCE oxidized increased. Batch experiments using LPZ cylinders allowed longer contact times between the flooding solutions and the DNAPL and results showed that SHMP + MnO 4 − improved TCE destruction by ∼16% over MnO 4 − alone (56.5% vs. 40.1%). These results support

Propene Hydroformylation by Supported Aqueous-phase Rh-NORBOS Catalysts

DEFF Research Database (Denmark)

Riisager, Anders; Eriksen, Kim Michael; Hjortkjær, Jes

2003-01-01

The gas-phase hydroformylation reaction of propene using supported aqueous-phase (SAP) Rh-NORBOS modified catalysts in a continuous flow reactor has been examined. SAP catalysts supported on six different support materials were made by wet impregnation using solutions of the precursor complex Rh(...

Improving the treatment of non-aqueous phase TCE in low permeability zones with permanganate.

Science.gov (United States)

Chokejaroenrat, Chanat; Comfort, Steve; Sakulthaew, Chainarong; Dvorak, Bruce

2014-03-15

Treating dense non-aqueous phase liquids (DNAPLs) embedded in low permeability zones (LPZs) is a particularly challenging issue for injection-based remedial treatments. Our objective was to improve the sweeping efficiency of permanganate (MnO4(-)) into LPZs to treat high concentrations of TCE. This was accomplished by conducting transport experiments that quantified the penetration of various permanganate flooding solutions into a LPZ that was spiked with non-aqueous phase (14)C-TCE. The treatments we evaluated included permanganate paired with: (i) a shear-thinning polymer (xanthan); (ii) stabilization aids that minimized MnO2 rind formation and (iii) a phase-transfer catalyst. In addition, we quantified the ability of these flooding solutions to improve TCE destruction under batch conditions by developing miniature LPZ cylinders that were spiked with (14)C-TCE. Transport experiments showed that MnO4(-) alone was inefficient in penetrating the LPZ and reacting with non-aqueous phase TCE, due to a distinct and large MnO2 rind that inhibited the TCE from further oxidant contact. By including xanthan with MnO4(-), the sweeping efficiency increased (90%) but rind formation was still evident. By including the stabilization aid, sodium hexametaphosphate (SHMP) with xanthan, permanganate penetrated 100% of the LPZ, no rind was observed, and the percentage of TCE oxidized increased. Batch experiments using LPZ cylinders allowed longer contact times between the flooding solutions and the DNAPL and results showed that SHMP+MnO4(-) improved TCE destruction by ∼16% over MnO4(-) alone (56.5% vs. 40.1%). These results support combining permanganate with SHMP or SHMP and xanthan as a means of treating high concentrations of TCE in low permeable zones. Copyright © 2014 Elsevier B.V. All rights reserved.

Sol-gel transitions and liquid crystal phase transitions in concentrated aqueous suspensions of colloidal gibbsite platelets

NARCIS (Netherlands)

Mourad, M.C.D.; Byelov, D.V.; Petukhov, A.V.; de Winter, D.A.M.; Verkleij, A.J.; Lekkerkerker, H.N.W.

2009-01-01

In this paper, we present a comprehensive study of the sol-gel transitions and liquid crystal phase transitions in aqueous suspensions of positively charged colloidal gibbsite platelets at pH 4-5 over a wide range of particle concentrations (50-600 g/L) and salt concentrations (10-4-10-1 M NaCl). A

Extraction of rare earth metals (3) from aqueous solutions containing thorium and uranyl nitrates

International Nuclear Information System (INIS)

Pyartman, A.K.; Kopyrin, A.A.; Berinskij, A.E.; Keskinov, V.A.

2000-01-01

Isotherms of extraction of rare earth metals (3) from aqueous solutions containing thorium and uranyl nitrates by solutions of tributylphosphate (TBP) and diisooctylmethylphosphonate (DIOMP) in kerosene at 298.15 Deg C and pH 1 are presented. Equations for description of interphase distribution of components of the systems considered are suggested. These equations describe distribution of components adequately in the systems of thorium nitrate (uranyl nitrate) - rare earth nitrates - (TBP, DIOMP) in the case of wide variation of phase compositions. Dependences of separation factors on composition of aqueous phase are considered [ru

Speciation in the aqueous H+/H2VO4-/H2O2/citrate system of biomedical interest.

Science.gov (United States)

Gorzsás, András; Getty, Kendra; Andersson, Ingegärd; Pettersson, Lage

2004-09-21

The speciation in the quaternary aqueous H+/H2VO4-/H2O2/citrate (Cit3-) and H+/H2VO4-/Cit3-/L-(+)-lactate (Lac-) systems has been determined at 25 degrees C in the physiological medium of 0.150 M Na(Cl). A combination of 51V NMR integral intensities and chemical shift (Bruker AMX500) as well as potentiometric data (glass electrode) have been collected and evaluated with the computer program LAKE, which is able to treat multimethod data simultaneously. The pKa-values for citric acid have been determined as 2.94, 4.34 and 5.61. Altogether six vanadate-citrate species have been found in the ternary H+/H2VO4-/Cit3- system in the pH region 2-10, only two of which are mononuclear. Reduction of vanadium(V) becomes more pronounced at pH acidic solutions limited the final model to pH > 4. In the quaternary H+/H2VO4-/Cit3-/Lac- system, two mixed-ligand species have been determined, with the compositions V2CitLac2- and V2CitLac3- (pKa = 5.0). To our knowledge, this is the first time such complexes have been reported for vanadium(V). 51V NMR chemical shifts, compositions and formation constants are given, and equilibrium conditions are illustrated in distribution diagrams as well as the fit of the model to the experimental data. When suitable, structural proposals are given, based on 13C NMR measurements and available literature data of related compounds.

Simultaneous Extraction, Enrichment and Removal of Dyes from Aqueous Solutions Using a Magnetic Aqueous Micellar Two-Phase System

Directory of Open Access Journals (Sweden)

Shuanggen Wu

2017-12-01

Full Text Available The magnetic aqueous micellar two-phase system (MAMTPS has the advantages combined of magnetic solid phase extraction (MSPE and aqueous micellar two-phase system (AMTPS. Thus, MAMTPS based on Fe3O4 magnetic nanoparticles (MNPs and a nonionic surfactant Triton X-114 (TX-114 was developed for the extraction, enrichment and removal of three dyes (Congo red, methyl blue, and methyl violet from aqueous solutions in this study. The MNPs Fe3O4@NH2 was screened as the optimal MNPs benefiting the extraction. Then, the influencing factors of MNPs amount, TX-114 concentration, vibration time, and extraction temperature were investigated in detail. The results showed that the extraction efficiencies of three dyes almost reached 100% using MAMTPS under the optimal conditions; MAMTPS had higher extraction ability than the individual MSPE or AMTPS. Thus, MAMTPS had the advantages of simple operation, high extraction ability, easy recycling of MNPs, and short phase-separation time, which showspotential for use in the extraction and analysis of contaminants from water samples.

Heteroaggregation of graphene oxide with minerals in aqueous phase.

Science.gov (United States)

Zhao, Jian; Liu, Feifei; Wang, Zhenyu; Cao, Xuesong; Xing, Baoshan

2015-03-03

Upon release into waters, sediments, and soils, graphene oxide (GO) may interact with fine mineral particles. We investigated the heteroaggregation of GO with different minerals, including montmorillonite, kaolinite, and goethite, in aqueous phase. GO significantly enhanced the dispersion of positively charged goethite (>50%) via heteroaggregation, while there was no interaction between GO and negatively charged montmorillonite or kaolinite. Electrostatic attraction was the dominant force in the GO-goethite heteroaggregation (pH 4.0-8.5), and the dissolved Fe ions (formation of multilayered GO-goethite complex with high configurational stability. These findings are useful for understanding the interaction of GO with mineral surfaces, and potential fate and toxicity of GO under natural conditions in aquatic environments, as well as in soils and sediments.

Phase equilibria in a system of aqueous arginine with an octane solution of sulfonic acid

Science.gov (United States)

Kuvaeva, Z. I.; Koval'chuk, I. V.; Vodop'yanova, L. A.; Soldatov, V. S.

2013-05-01

The extraction of arginine (Arg) from aqueous salt (0.1 M NaCl) solutions with a sulfo extractant in a wide range of pH values and amino acid concentrations was studied. The 0.1 M solution of dinonylnaphthalenesulfonic acid (HD) in octane was used as an extractant. The degree of extraction was found to be high at pH 0.8-9.0. This can be explained by the effect of additional intermolecular interactions in the extractant phase involving the guanidine group of Arg.

Fundamental thermochemical properties of amino acids: gas-phase and aqueous acidities and gas-phase heats of formation.

Science.gov (United States)

Stover, Michele L; Jackson, Virgil E; Matus, Myrna H; Adams, Margaret A; Cassady, Carolyn J; Dixon, David A

2012-03-08

The gas-phase acidities of the 20 L-amino acids have been predicted at the composite G3(MP2) level. A broad range of structures of the neutral and anion were studied to determine the lowest energy conformer. Excellent agreement is found with the available experimental gas-phase deprotonation enthalpies, and the calculated values are within experimental error. We predict that tyrosine is deprotonated at the CO(2)H site. Cysteine is predicted to be deprotonated at the SH but the proton on the CO(2)H is shared with the S(-) site. Self-consistent reaction field (SCRF) calculations with the COSMO parametrization were used to predict the pK(a)'s of the non-zwitterion form in aqueous solution. The differences in the non-zwitterion pK(a) values were used to estimate the free energy difference between the zwitterion and nonzwitterion forms in solution. The heats of formation of the neutral compounds were calculated from atomization energies and isodesmic reactions to provide the first reliable set of these values in the gas phase. Further calculations were performed on five rare amino acids to predict their heats of formation, acidities, and pK(a) values.

Aqueous phase partitioning of hexachlorocyclohexane (HCH) isomers by biosurfactant produced by Pseudomonas aeruginosa WH-2

International Nuclear Information System (INIS)

Sharma, Suman; Singh, Partapbir; Raj, Mayil; Chadha, Bhupinder Singh; Saini, Harvinder Singh

2009-01-01

The different isomers of technical-grade hexachlorocyclohexane (t-HCH) including the insecticidal γ-isomer, commonly known as lindane, have been reported to be toxic, carcinogenic and endocrine disrupters. The spatial arrangements of the chlorine atoms on different isomers and low aqueous phase solubility contribute to their persistence in environment, β-HCH being the most resistance to transformation. The biosurfactant preparation of Pseudomonas aeruginosa isolate WH-2 was evaluated for its ability to improve the aqueous phase partitioning of different isomers of HCH-muck. Further, the ability of biosurfactant preparation to emulsify HCH and n-hexadecane was checked under different conditions, usually characteristic of sites contaminated with pollutants viz. wide range of pH, temperature, and salinity. The data obtained from this study will be helpful in designing suitable bioremediation strategies for huge stock piles of HCH-muck and sites polluted by reckless use/disposal of HCH-isomers.

Radiation-stimulated phase in titanium dihydride TiH1.95

International Nuclear Information System (INIS)

Khidirov, I.; Mukhtarova, N.N.; Baktibaev, K.O.; Getmanskiy, V.V.

2001-01-01

In titanium dihydride TiH 1.95 γ-irradiation has been shown by X-ray and neutron-diffraction methods to stimulate the phase transition FCC→VCT at doses ≥3·10 10 R and irradiation temperature ≅100 d eg C. The space group of the formed phase is D 4h 17 -14/mmm, its lattice parameters a m =0.3161 nm, c m =0.4418 nm are related to parameters of the initial (FCC) phase by relations a m ≅a k /2 1/2 , c m ≅a k . It was established that the phase obtained is metastable, it relaxes at the temperatures ≥37 d eg C and transforms into the stable FCC phase that corresponds to the equilibrium phase diagram of Ti-H system. The temperature of the phase transition increases by influence of γ-quanta, the radiation-stimulated phase differs from thermostimulated one by a larger unit cell and a smaller degree of tetragonal distortion. (author)

Studies of the pressure-induced phase transition of C sub 3 N sub 6 H sub 6

CERN Document Server

Ma Hong An; Cui Qi Liang; Pan Yue Wu; Zhu Pin Wen; Guo Wei; Chen Li Xue; Ren Guo Zheng; Zou Guang Tian; LiuJing

2002-01-01

In situ high pressure energy dispersive X-ray diffraction experiments have been carried out on C sub 3 N sub 6 H sub 6 by using diamond anvil cell (DAC) device with synchrotron radiation source. Two structural phase transitions of C sub 3 N sub 6 H sub 6 have been observed within 14.7 GPa pressure range, from monoclinic to triclinic structure at 1.3 GPa and from triclinic to orthorhombic structure at 8.2 GPa, respectively

Measuring the density and viscosity of H2S-loaded aqueous methyldiethanolamine solution

International Nuclear Information System (INIS)

Shokouhi, Mohammad; Ahmadi, Reza

2016-01-01

Highlights: • Measurement solubility of H 2 S in 46.78 mass% MDEA aqueous solutions. • Measurement density of H 2 S loaded of MDEA aqueous solution. • Measurement viscosity of H 2 S loaded of MDEA aqueous solution. • Correlation of the density and viscosity of H 2 S loaded of MDEA aqueous solution using modified setchenow equation. - Abstract: The density and viscosity of H 2 S-loaded aqueous 46.78 mass% methyldiethanolamine solution were experimentally measured accompanied with the solubility of H 2 S at temperatures (313.15, 328.15 and 343.15) K, pressures from vapor pressure of fresh solution up to 1.0 MPa and loadings up to 1.00 mol of H 2 S per 1 mol of amine. All experimental trials have been carried out using the new setup developed in our laboratory. It was observed that both density and viscosity of mixtures decrease by increasing temperature and density increase by increasing acid gas solubility (loading) by about 4.7%, whereas viscosity has a complicated behavior with H 2 S solubility. Viscosity decreases by increasing acid gas solubility (loading) at 313.15 K by about 20.6% and at 328.15 K by about 15.0%, but it is comparable at 343.15 K in terms of H 2 S solubility. Finally, the experimental density and viscosity data correlated using Modified Setchenow equation.

Synthesis of a mixed-model stationary phase derived from glutamine for HPLC separation of structurally different biologically active compounds: HILIC and reversed-phase applications.

Science.gov (United States)

Aral, Tarık; Aral, Hayriye; Ziyadanoğulları, Berrin; Ziyadanoğulları, Recep

2015-01-01

A novel mixed-mode stationary phase was synthesised starting from N-Boc-glutamine, aniline and spherical silica gel (4 µm, 60 Å). The prepared stationary phase was characterized by IR and elemental analysis. The new stationary phase bears an embedded amide group into phenyl ring, highly polar a terminal amide group and non-polar groups (phenyl and alkyl groups). At first, this new mixed-mode stationary phase was used for HILIC separation of four nucleotides and five nucleosides. The effects of different separation conditions, such as pH value, mobile phase and temperature, on the separation process were investigated. The optimum separation for nucleotides was achieved using HILIC isocratic elution with aqueous mobile phase and acetonitrile with 20°C column temperature. Under these conditions, the four nucleotides could be separated and detected at 265 nm within 14 min. Five nucleosides were separated under HILIC isocratic elution with aqueous mobile phase containing pH=3.25 phosphate buffer (10mM) and acetonitrile with 20°C column temperature and detected at 265 nm within 14 min. Chromatographic parameters as retention factor, selectivity, theoretical plate number and peak asymmetry factor were calculated for the effect of temperature and water content in mobile phase on the separation process. The new column was also tested for nucleotides and nucleosides mixture and six analytes were separated in 10min. The chromatographic behaviours of these polar analytes on the new mixed-model stationary phase were compared with those of HILIC columns under similar conditions. Further, phytohormones and phenolic compounds were separated in order to see influence of the new stationary phase in reverse phase conditions. Eleven plant phytohormones were separated within 13 min using RP-HPLC gradient elution with aqueous mobile phase containing pH=2.5 phosphate buffer (10mM) and acetonitrile with 20°C column temperature and detected at 230 or 278 nm. The best separation

PARTITION EFFICIENCY OF NEWLY DESIGNED LOCULAR MULTILAYER COIL FOR COUNTERCURRENT CHROMATOGRAPHIC SEPARATION OF PROTEINS USING SMALL-SCALE CROSS-AXIS COIL PLANET CENTRIFUGE WITH AQUEOUS-AQUEOUS POLYMER PHASE SYSTEMS.

Science.gov (United States)

Shinomiya, Kazufusa; Ito, Yoichiro

2009-01-01

Countercurrent chromatographic performance of the locular multilayer coil separation column newly designed in our laboratory was evaluated in terms of theoretical plate number, peak resolution and retention of the stationary phase in protein separation with an aqueous polymer phase system using the small-scale cross-axis coil planet centrifuge (X-axis CPC) fabricated in our laboratory. The locular column was made from 1.0 mm I.D., 2.0 mm O.D. or 1.5 mm I.D., 2.5 mm O.D. PTFE tubing compressed with a pair of hemostat at 2 or 4 cm intervals. The protein separation was performed using a set of stable proteins including cytochrome C, myoglobin and lysozyme with the 12.5% (w/w) polyethylene glycol 1000 and 12.5% (w/w) dibasic potassium phosphate system under 1000 rpm of column revolution. The 1.5 mm I.D., 2.5 mm O.D. locular tubing compressed at 2 cm intervals yielded better partition efficiencies than the non-clamped tubing using both lower and upper mobile phases with satisfactory retention of the stationary phase. The overall results suggest that the newly designed locular multilayer coil is useful to the preparative separation of proteins with aqueous-aqueous polymer phase system using our small-scale X-axis CPC.

Gas-phase Absorptions of {{\\rm{C}}}_{42}{{\\rm{H}}}_{18}^{+} near 8300 Å below 10 K: Astronomical Implications

Science.gov (United States)

Campbell, E. K.; Maier, J. P.

2017-11-01

The gas-phase electronic spectrum of {{{C}}}42{{{H}}}18+ ({{HBC}}+) with an origin band at 8281 \\mathringA has been measured below 10 {{K}} by photofragmentation of helium complexes ({{{C}}}42{{{H}}}18+{--}{{He}}n) in a radiofrequency trap. {{HBC}}+ is a medium-sized polycyclic aromatic hydrocarbon (PAH) cation, and using an ion trapping technique it has been possible to record a high-quality gas-phase spectrum to directly compare with astronomical observations. No diffuse interstellar bands (DIBs) have been reported at the wavelengths of the strongest absorption bands in the {{{C}}}42{{{H}}}18+ spectrum. Measurement of absolute absorption cross sections in the ion trap allows upper limits to the column density of this ion to be {10}12 {{cm}}-2, indicating that even PAH cations of this size, which are believed to be stable in the interstellar medium, should be excluded as candidates for at least the strong DIBs.

Purification and characterization of a collagenase from Penicillium sp. UCP 1286 by polyethylene glycol-phosphate aqueous two-phase system.

Science.gov (United States)

de Albuquerque Wanderley, Maria Carolina; Wanderley Duarte Neto, José Manoel; Campos Albuquerque, Wendell Wagner; de Araújo Viana Marques, Daniela; de Albuquerque Lima, Carolina; da Cruz Silvério, Sara Isabel; de Lima Filho, José Luiz; Couto Teixeira, José António; Porto, Ana Lúcia Figueiredo

2017-05-01

Collagenases are proteolytic enzymes capable of degrading both native and denatured collagen, reported to be applied in industrial, medical and biotechnological sectors. Liquid-liquid extraction using aqueous two-phase system (ATPS) is one of the most promising bioseparation techniques, which can substitute difficult solid-liquid separation processes, offering many advantages over conventional methods including low-processing time, low-cost material and low-energy consumption. The collagenase produced by Penicillium sp. UCP 1286 showed a stronger affinity for the bottom salt-rich phase, where the highest levels of collagenolytic activity were observed at the center point runs, using 15.0% (w/w) PEG 3350 g/mol and 12.5% (w/w) phosphate salt at pH 7.0 and concentration. The enzyme was characterized by thermal stability, pH tolerance and effect of inhibitors, showing optimal collagenolytic activity at 37 °C and pH 9.0 and proved to be a serine protease. ATPS showed high efficiency in the collagenase purification, confirmed by a single band in SDS/PAGE, and can in fact be applied as a quick and inexpensive alternative method. Copyright © 2017 Elsevier Inc. All rights reserved.

The salting-out effect and phase separation in aqueous solutions of tri-sodium citrate and 1-butyl-3-methylimidazolium bromide

Energy Technology Data Exchange (ETDEWEB)

Sadeghi, Rahmat, E-mail: rsadeghi@uok.ac.i [Department of Chemistry, University of Kurdistan, Sanandaj (Iran, Islamic Republic of); Golabiazar, Roonak [Department of Chemistry, University of Kurdistan, Sanandaj (Iran, Islamic Republic of); Shekaari, Hemayat [Department of Chemistry, Faculty of Science, University of Mohaghegh Ardabili, Ardabil (Iran, Islamic Republic of)

2010-04-15

The aim of this work is to obtain further evidence about the salting-out effect produced by the addition of tri-sodium citrate to aqueous solutions of water miscible ionic liquid 1-butyl-3-methylimidazolium bromide ([C{sub 4}mim][Br]) by evaluating the effect of tri-sodium citrate on the thermodynamic properties of aqueous solutions of this ionic liquid. Experimental measurements of density and sound velocity at different temperatures ranging from (288.15 to 308.15) K, the refractive index at 308.15 K and the liquid-liquid phase diagram at different temperatures ranging from (288.15 to 338.15) K for aqueous solutions containing 1-butyl-3-methylimidazolium bromide ([C{sub 4}mim][Br]) and tri-sodium citrate (Na{sub 3}Cit) are taken. The apparent molar volume of transfer of [C{sub 4}mim][Br] from water to aqueous solutions of Na{sub 3}Cit have positive values and it increases by increasing salt molality. Although at high IL molality, the apparent molar isentropic compressibility shows similar behaviour with that of the apparent molar volume. However at low concentrations of IL, the apparent molar isentropic compressibility of transfer of [C{sub 4}mim][Br] from water to aqueous solutions of Na{sub 3}Cit have negative values. The effects of temperature and the addition of Na{sub 3}Cit and [C{sub 4}mim][Br] on the liquid-liquid phase diagram of the investigated system have been studied. It was found that an increase in temperature caused the expansion of the one-phase region. The presence of Na{sub 3}Cit triggers a salting-out effect, leading to significant upward shifts of the liquid-liquid de-mixing temperatures of the system. The effect of temperature on the phase-forming ability in the system investigated has been studied based on a salting-out coefficient obtained from fitting the binodal values to a Setschenow-type equation for each temperature. Based on cloud point values, the energetics of the clouding process have been estimated and it was found that both of

Transmission of 3H-compounds corresponding to the senescence signal in soybean

International Nuclear Information System (INIS)

Nooden, L.D.; Finkelstein, D.; Wetzel, P.

1987-01-01

To detect compounds transmitted from the pods to the leaves, the pods of explants at various stages were injected with 3 H-acetate and incubated for 24 hr. To avoid 3 H contamination, the leaf blades, pods, and stem were each vented separately with air (pods, leaves) or water (stem). The leaf blades were extracted with MeOH/CHCl 3 /formic acid/H 2 O (12:2:1:2 v/v), and after reduction to an aqueous phase, the 3 H was partitioned. Most 3 H entered the acid ether (50%) and aqueous (30%) phases with much less in the neutral and basic phases. The most 3 H was transmitted during mid and late podfill when the pods induce senescence. When chromatographed on TLC (silica gel) with n-BuOH/HAc/H 2 O) (450:112:188 v/v), the acid ether phase gave one sharp peak of 3 H, while the aqueous phase produced a broad peak. Most (80%) of the former peak, which corresponded to IAA and ABA, could be resolved from these compounds by reverse phase HPLC on a C 8 column with a MeOH/gradient. Thus, some compounds are transmitted from the pods to the leaves during induction of monocarpic senescence, and at least the acid ether-soluble compounds are of limited heterogeneity

Investigation on the formation of a third phase in the extraction of Pu(IV) nitrate with tributyl phosphate

International Nuclear Information System (INIS)

Yu Enjiang; Liu Liming; Huang Huaian

1986-01-01

The formation of a third phase is studied in the system Pu(IV) nitratenitric acid-TBP-alkane diluent (or kerosine). The maximum concentration (solubility, S Pu ) of Pu(IV) in the equilibrium organic phase at which still no third phase is formed is measured as a function of the nitric acid concentration in the equilibrium aqueous phase C H , the temperature, and the molecular size of n-alkane duluent. Results show that maxima of S Pu at 6 to 7 M nitric acid are observed at 17 deg C, 26 deg C and 35 deg C while not at 40 deg C. Minima on the S Pu vs. C H curves at 0.5 to 2 M mitric acid have been observed at 17 deg C and 26 deg C. It is found that the molecular size of n-alkane diluents has a very pronounced effect on S Pu . The effect of aqueous equilibrium Pu(IV) concentration on the formation of a third phase is investigated, when the equilibrium HNO 3 concentration is 3.5 M. It is shown that the plutonium concentration of the third phase is increased with increasing aqueous equilibrium Pu(IV) concentration. The effect of the addition of lauryl alcohol on the S Pu is preliminarily studied

Tube Radial Distribution Flow Separation in a Microchannel Using an Ionic Liquid Aqueous Two-Phase System Based on Phase Separation Multi-Phase Flow.

Science.gov (United States)

Nagatani, Kosuke; Shihata, Yoshinori; Matsushita, Takahiro; Tsukagoshi, Kazuhiko

2016-01-01

Ionic liquid aqueous two-phase systems were delivered into a capillary tube to achieve tube radial distribution flow (TRDF) or annular flow in a microspace. The phase diagram, viscosity of the phases, and TRDF image of the 1-butyl-3-methylimidazolium chloride and NaOH system were examined. The TRDF was formed with inner ionic liquid-rich and outer ionic liquid-poor phases in the capillary tube. The phase configuration was explained using the viscous dissipation principle. We also examined the distribution of rhodamine B in a three-branched microchannel on a microchip with ionic liquid aqueous two-phase systems for the first time.

Aqueous suspensions of {alpha}Al{sub 2}O{sub 3}/SiC mixed systems

Energy Technology Data Exchange (ETDEWEB)

Pagnoux, C.; Baklouti, S.; Chartier, T.; Baumard, J.F. [ENSCI, Limoges (France). LMCTS

1997-12-31

The preparation of aqueous {alpha}-Al{sub 2}O{sub 3}, {alpha}-SiO{sub 2} and {alpha}-SiC suspensions with polyelectrolytes, respectively the NH{sub 4}{sup +} salt of polymethacrylic acid (PMA-NH{sub 4}{sup +}) and acidic form polyethylene imine (PEI-H{sup +}) is investigated. It is based on the adsorption of these polyelectrolytes which in turn depends mainly on the nature of the polyelectrolyte, and the charge density which develops on the powder surface in water. Good dispersion and stability of dispersions are then obtained through electrostatic and steric stabilization. As an application, the preparation of an Al{sub 2}O{sub 3}-SiC aqueous mixed slurry was investigated as a preliminary step for processing of Al{sub 2}O{sub 3}/SiC nanocomposites. (orig.) 2 refs.

Acetanilide interaction with hydriodic acid in aqueous solutions at 20 and 40 deg C

International Nuclear Information System (INIS)

Erkasov, R.Sh.; Nurakhmetov, N.I.

1990-01-01

Isothermal method was used to study acetanilide solubility in aqueous solutions of hydriodic acid at 20 and 40 deg C. formation of two new anhydrous compounds of 2:1 and 1:1 compositions (anilide: acid molar ratio) was established. Temperature and concentration boundaries of solid phase formation were established for these compounds. Their IR spectroscopic investigation was conducted

A propofol microemulsion with low free propofol in the aqueous phase: formulation, physicochemical characterization, stability and pharmacokinetics.

Science.gov (United States)

Cai, WeiHui; Deng, WanDing; Yang, HuiHui; Chen, XiaoPing; Jin, Fang

2012-10-15

The purpose of this study was to develop a propofol microemulsion with a low concentration of free propofol in the aqueous phase. Propofol microemulsions were prepared based on single-factor experiments and orthogonal design. The optimal microemulsion was evaluated for pH, osmolarity, particle size, zeta potential, morphology, free propofol in the aqueous phase, stability, and pharmacokinetics in beagle dogs, and comparisons made with the commercial emulsion, Diprivan(®). The pH and osmolarity of the microemulsion were similar to those of Diprivan(®). The average particle size was 22.6±0.2 nm, and TEM imaging indicated that the microemulsion particles were spherical in appearance. The concentration of free propofol in the microemulsion was 21.3% lower than that of Diprivan(®). Storage stability tests suggested that the microemulsion was stable long-term under room temperature conditions. The pharmacokinetic profile for the microemulsion showed rapid distribution and elimination compared to Diprivan(®). We conclude that the prepared microemulsion may be clinically useful as a potential carrier for propofol delivery. Copyright © 2012 Elsevier B.V. All rights reserved.

Fabricating eco-friendly nanocomposites of SiC with morphologically-different nano-carbonaceous phases 

DEFF Research Database (Denmark)

Candelario, Victor M.; Moreno, Rodrigo; Guiberteau, Fernando

2018-01-01

A route based on aqueous colloidal processing followed by liquid-phase assisted spark-plasma-sintering (SPS) is described for fabricating eco-friendly nanocomposites of SiC with nano-carbonaceous phases (nanotubes, nanoplatelets, or nanoparticles). To this end, the conditions optimizing the aqueo...

Improving the treatment of non-aqueous phase TCE in low permeability zones with permanganate

Energy Technology Data Exchange (ETDEWEB)

Chokejaroenrat, Chanat, E-mail: chanat@sut.ac.th [Department of Civil Engineering, University of Nebraska, Lincoln, NE 68588-0531 (United States); School of Environmental Engineering, Institute of Engineering, Suranaree University of Technology, Nakhon Ratchasima 30000 (Thailand); Comfort, Steve, E-mail: scomfort1@unl.edu [School of Natural Resources, University of Nebraska, Lincoln, NE 68583-0915 (United States); Sakulthaew, Chainarong, E-mail: cvtcns@ku.ac.th [School of Natural Resources, University of Nebraska, Lincoln, NE 68583-0915 (United States); Department of Veterinary Technology, Kasetsart University, Bangkok 10900 (Thailand); Dvorak, Bruce, E-mail: bdvorak1@unl.edu [Department of Civil Engineering, University of Nebraska, Lincoln, NE 68588-0531 (United States)

2014-03-01

Graphical abstract: - Highlights: • Transport experiments used transmissive and low permeability zones (LPZs). • {sup 14}C-labeled TCE was used to quantify oxidation of DNAPL in LPZs by permanganate. • Stabilization aids prevented MnO{sub 2} rind formation. • DNAPL oxidation improved when xanthan and stabilization aids were used. - Abstract: Treating dense non-aqueous phase liquids (DNAPLs) embedded in low permeability zones (LPZs) is a particularly challenging issue for injection-based remedial treatments. Our objective was to improve the sweeping efficiency of permanganate (MnO{sub 4}{sup −}) into LPZs to treat high concentrations of TCE. This was accomplished by conducting transport experiments that quantified the penetration of various permanganate flooding solutions into a LPZ that was spiked with non-aqueous phase {sup 14}C-TCE. The treatments we evaluated included permanganate paired with: (i) a shear-thinning polymer (xanthan); (ii) stabilization aids that minimized MnO{sub 2} rind formation and (iii) a phase-transfer catalyst. In addition, we quantified the ability of these flooding solutions to improve TCE destruction under batch conditions by developing miniature LPZ cylinders that were spiked with {sup 14}C-TCE. Transport experiments showed that MnO{sub 4}{sup −} alone was inefficient in penetrating the LPZ and reacting with non-aqueous phase TCE, due to a distinct and large MnO{sub 2} rind that inhibited the TCE from further oxidant contact. By including xanthan with MnO{sub 4}{sup −}, the sweeping efficiency increased (90%) but rind formation was still evident. By including the stabilization aid, sodium hexametaphosphate (SHMP) with xanthan, permanganate penetrated 100% of the LPZ, no rind was observed, and the percentage of TCE oxidized increased. Batch experiments using LPZ cylinders allowed longer contact times between the flooding solutions and the DNAPL and results showed that SHMP + MnO{sub 4}{sup −} improved TCE destruction by �

Variation in pH of Model Secondary Organic Aerosol during Liquid-Liquid Phase Separation.

Science.gov (United States)

Dallemagne, Magda A; Huang, Xiau Ya; Eddingsaas, Nathan C

2016-05-12

The majority of atmospheric aerosols consist of both organic and inorganic components. At intermediate relative humidity (RH), atmospheric aerosol can undergo liquid-liquid phase separation (LLPS) in which the organic and inorganic fractions segregate from each other. We have extended the study of LLPS to the effect that phase separation has on the pH of the overall aerosols and the pH of the individual phases. Using confocal microscopy and pH sensitive dyes, the pH of internally mixed model aerosols consisting of polyethylene glycol 400 and ammonium sulfate as well as the pH of the organic fraction during LLPS have been directly measured. During LLPS, the pH of the organic fraction was observed to increase to 4.2 ± 0.2 from 3.8 ± 0.1 under high RH when the aerosol was internally mixed. In addition, the high spatial resolution of the confocal microscope allowed us to characterize the composition of each of the phases, and we have observed that during LLPS the organic shell still contains large quantities of water and should be characterized as an aqueous organic-rich phase rather than simply an organic phase.

LC-ESI-MSD fast determination of residual mitomycin C in hen aqueous humour after corneal refractive surgery.

Science.gov (United States)

Nozal, M J; Bernal, J L; Martín, M T; Bernal, J; Torres, R M; Merayo, J

2006-01-23

A simple, fast and reliable method has been developed for the assay of traces of mitomycin C (MMC) in hen aqueous humour samples. The determination was carried out by high-performance liquid chromatography with electrospray ionization mass spectrometric detection. In isocratic elution analysis, the mobile phase was a mixture of water-acetonitrile (78:22, v/v) and the chromatographic column was C(18) at 35 degrees C. The method has been validated over a range from 0.1 to 250 microg L(-1) in hen aqueous humour with correlation coefficients higher than 0.999. Limit of detection and limit of quantification for MMC based in signal to noise ratio of 3 and 10, respectively, were 20 and 71 ng L(-1). The developed method allows the analysis of MMC in hen aqueous humour samples obtained at different times and conditions in order to evaluate and compare the efficacy of the drug administration.

The impact of ionic liquid fluorinated moieties on their thermophysical properties and aqueous phase behaviour.

Science.gov (United States)

Neves, Catarina M S S; Kurnia, Kiki A; Shimizu, Karina; Marrucho, Isabel M; Rebelo, Luís Paulo N; Coutinho, João A P; Freire, Mara G; Lopes, José N Canongia

2014-10-21

In this work, we demonstrate that the presence of fluorinated alkyl chains in Ionic Liquids (ILs) is highly relevant in terms of their thermophysical properties and aqueous phase behaviour. We have measured and compared the density and viscosity of pure 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate, [C2C1im][FAP], with that of pure 1-ethyl-3-methylimidazolium hexafluorophosphate, [C2C1im][PF6], at atmospheric pressure and in the (288.15 to 363.15) K temperature range. The results show that the density of [C2C1im][PF6] is lower than that of [C2C1im][FAP], while the viscosity data reveal the opposite trend. The fluid phase behaviour of aqueous solutions of the two ILs was also evaluated under the same conditions and it was found that the mutual solubilities of [C2C1im][FAP] and water are substantially lower than those verified with [C2C1im][PF6]. The experimental data were lastly interpreted at a molecular level using Molecular Dynamics (MD) simulation results revealing that the interactions between the IL ions and the water molecules are mainly achieved via the six fluorine atoms of [PF6](-) and the three analogues in [FAP](-). The loss of three interaction centres when replacing [PF6](-) by [FAP](-), coupled with the bulkiness and relative inertness of the three perfluoroethyl groups, reduces its mutual solubility with water and also contributes to a lower viscosity displayed by the pure [FAP]-based IL as compared to that of the [PF6]-based compound.

Treatment of aqueous phase of bio-oil by granular activated carbon and evaluation of biogas production.

Science.gov (United States)

Shanmugam, Saravanan R; Adhikari, Sushil; Wang, Zhouhang; Shakya, Rajdeep

2017-01-01

Hydrothermal liquefaction of wet biomass such as algae is a promising thermochemical process for the production of bio-oil. Bio-oil aqueous phase generated during liquefaction process is rich in complex organics and can be utilized for biogas production following its pre-treatment with granular activated carbon. In our study, use of 30% activated carbon resulted in higher chemical oxygen demand (COD) reduction (53±0.3%) from aqueous phase. Higher CH 4 production (84±12mL/gCOD) was also observed in 30% carbon-treated aqueous phase fed cultures, whereas only 32±6mLCH 4 /gCOD was observed in control (non-carbon treated) cultures. The results from this study indicate that almost 67±0.3% initial COD of aqueous phase can be reduced using a combination of both carbon treatment and biogas production. This study shows that aqueous phase can be utilized for CH 4 production. Copyright © 2016 Elsevier Ltd. All rights reserved.

Tritium distribution ratios between the 30 % tributyl phosphate(TBP)-normal dodecane(nDD) organic phase and uranyl nitrate-nitric acid aqueous phase

International Nuclear Information System (INIS)

Fujine, Sachio; Uchiyama, Gunzou; Sugikawa, Susumu; Maeda, Mitsuru; Tsujino, Takeshi.

1989-10-01

Tritium distribution ratios between the organic and aqueous phases were measured for the system of 30 % tributyl phosphate(TBP)-normal dodecane(nDD)/uranyl nitrate-nitric acid water. It was confirmed that tritium is extracted by TBP into the organic phase in both chemical forms of tritiated water (HTO) and tritiated nitric acid (TNO 3 ). The value of tritium distribution ratio ranged from 0.002 to 0.005 for the conditions of 0-6 mol/L nitric acid, 0.5-800 mCi/L tritium in aqueous phase, and 0-125 g-U/L uranium in organic phase. Isotopic distribution coefficient of tritium between the organic and aqueous phases was observed to be about 0.95. (author)

Glycine phases formed from frozen aqueous solutions: Revisited

Science.gov (United States)

Surovtsev, N. V.; Adichtchev, S. V.; Malinovsky, V. K.; Ogienko, A. G.; Drebushchak, V. A.; Manakov, A. Yu.; Ancharov, A. I.; Yunoshev, A. S.; Boldyreva, E. V.

2012-08-01

Glycine phases formed when aqueous solutions were frozen and subsequently heated under different conditions were studied by Raman scattering, x-ray diffraction, and differential scanning calorimetry (DSC) techniques. Crystallization of ice Ih was observed in all the cases. On cooling at the rates of 0.5 K/min and 5 K/min, glassy glycine was formed as an intermediate phase which lived about 1 min or less only, and then transformed into β-polymorph of glycine. Quench cooling of glycine solutions (15% w/w) in liquid nitrogen resulted in the formation of a mixture of crystalline water ice Ih and a glassy glycine, which could be preserved at cryogenic temperatures (80 K) for an indefinitely long time. This mixture remained also quite stable for some time after heating above the cryogenic temperature. Subsequent heating under various conditions resulted in the transformation of the glycine glass into an unknown crystalline phase (glycine "X-phase") at 209-216 K, which at 218-226 K transformed into β-polymorph of glycine. The "X-phase" was characterized by Raman spectroscopy; it could be obtained in noticeable amounts using a special preparation technique and tentatively characterized by x-ray powder diffraction (P2, a = 6.648 Å, b = 25.867 Å, c = 5.610 Å, β = 113.12°); the formation of "X-phase" from the glycine glassy phase and its transformation into β-polymorph were followed by DSC. Raman scattering technique with its power for unambiguous identification of the crystalline and glassy polymorphs without limitation on the crystallite size helped us to follow the phase transformations during quenching, heating, and annealing. The experimental findings are considered in relation to the problem of control of glycine polymorphism on crystallization.

Secondary organic aerosol (trans)formation through aqueous phase guaiacol photonitration: a kinetic study

Science.gov (United States)

Kroflič, Ana; Grgić, Irena

2014-05-01

It is well known that atmospheric aerosols play a crucial role in the Earth's climate and public health (Pöschl 2005). Despite a great effort invested in the studies of secondary organic aerosol (SOA) budget, composition, and its formation mechanisms, there is still a gap between field observations and atmospheric model predictions (Heald et al. 2005, Hallquist et al. 2009, and Lim et al. 2010). The insisting uncertainties surrounding SOA formation and aging thus gained an increasing interest in atmospheric aqueous phase chemistry; they call for more complex and time consuming studies at the environmentally relevant conditions allowing confident extrapolation to desired ambient conditions. In addition to the adverse health effects of atmospheric particulate matter (PM) as such, toxicity is also attributed to nitro-aromatic and other organic compounds which have already been detected in real aerosol samples (Traversi et al. 2009). Moreover, low-volatility aromatic derivatives are believed to form at least partly in the aerosol aqueous phase and not only in the gas phase from where they partition into water droplets (Ervens et al. 2011). Two nitro derivatives of biomass burning tracer guaiacol have recently been found in winter PM10 samples from the city of Ljubljana, Slovenia, and aqueous photonitration reaction was proposed as their possible production pathway (Kitanovski et al. 2012). In this study the kinetics of guaiacol nitration in aqueous solution was investigated in the presence of H2O2 and NO2¯ upon simulated solar irradiation (Xenon lamp, 300 W). During the experiment the DURAN® flask with the reaction mixture was held in the thermostated bath and thoroughly mixed. The reaction was monitored for 44 hours at different temperatures. Guaiacol and its main nitro-products (4-nitroguaiacol, 4-NG; 6-nitroguaiacol, 6-NG; and 4,6-dinitroguaiacol, 4,6-DNG) were quantified in every aliquot, taken from the reaction mixture, by use of high pressure liquid

Capturing [11C]CO2 for use in aqueous applications

International Nuclear Information System (INIS)

Vandehey, Nicholas T.; O’Neil, James P.

2014-01-01

We present a simple method for trapping [ 11 C]CO 2 gas and releasing it into a buffered solution using an ion-exchange cartridge. Sodium hydroxide cartridges captured >99% of [ 11 C]CO 2 following NaOH activation. A sodium bicarbonate solution eluted >99% of trapped radioactivity. Trapping [ 11 C]CO 2 directly in small volumes of several solutions was less effective than cartridge methods. The recommended methods allow for fast and simple production of highly concentrated carbon-11 containing aqueous solutions for use in filling phantoms, calibrating detectors, or (bio)geochemical experiments. - Highlights: • An ion exchange resin can trap [ 11 C]CO 2 gas and release it with saturated bicarbonate. • Elution from cartridge requires as little as 300 µL volume, with eluant at pH=10. • SPE trap-and-release provided better results than trapping in solution

Possibility of high temperature superconducting phases in PdH

Energy Technology Data Exchange (ETDEWEB)

Tripodi, Paolo; Di Gioacchino, Daniele; Borelli, Rodolfo; Vinko, Jenny Darja

2003-05-15

Possible new superconducting phases with a high critical transition temperature (T{sub c}) have been found in stable palladium-hydrogen (PdH{sub x}) samples for stoichiometric ratio x=H/Pd{>=}1, in addition to the well-known low critical transition temperature (0{<=}T{sub c}{<=}9) when x is in the range (0.75{<=}x{<=}1.00). Possible new measured superconducting phases with critical temperature in the range 51{<=}T{sub c}{<=}295 K occur. This T{sub c} varies considerably with every milli part of x when x exceeds unit. A superconducting critical current density J{sub c}{>=}6.1x10{sup 4} A cm{sup -2} has been measured at 77 K with H{sub DC}=0 T.

Hydrogen production by aqueous phase catalytic reforming of glycerine

International Nuclear Information System (INIS)

Ozguer, Derya Oncel; Uysal, Bekir Zuehtue

2011-01-01

Hydrogen is believed to be the one of the main energy carriers in the near future. In this research glycerine, which is produced in large quantities as a by-product of biodiesel process, was converted to hydrogen aiming to contribute to clean energy initiative. Conversion of glycerol to hydrogen was achieved via aqueous-phase reforming (APR) with Pt/Al 2 O 3 catalyst. The experiments were carried out in an autoclave reactor and a continuous fixed-bed reactor. The effects of reaction temperature (160-280 o C), feed flow rate (0.05-0.5 mL/dak) and feed concentration (5-85 wt-% glycerine) on product distribution were investigated. Optimum temperature for hydrogen production with APR was determined as 230 o C. Maximum gas production rate was found at the feed flow rates around 0.1 mL/min. It was also found that hydrogen concentration in the gas product increased with decreasing glycerol concentration in the feed.

An optical spectrum of a large isolated gas-phase PAH cation: C78H26+

Science.gov (United States)

Zhen, Junfeng; Mulas, Giacomo; Bonnamy, Anthony; Joblin, Christine

2016-01-01

A gas-phase optical spectrum of a large polycyclic aromatic hydrocarbon (PAH) cation - C78H26+- in the 410-610 nm range is presented. This large all-benzenoid PAH should be large enough to be stable with respect to photodissociation in the harsh conditions prevailing in the interstellar medium (ISM). The spectrum is obtained via multi-photon dissociation (MPD) spectroscopy of cationic C78H26 stored in the Fourier Transform Ion Cyclotron Resonance (FT-ICR) cell using the radiation from a mid-band optical parametric oscillator (OPO) laser. The experimental spectrum shows two main absorption peaks at 431 nm and 516 nm, in good agreement with a theoretical spectrum computed via time-dependent density functional theory (TD-DFT). DFT calculations indicate that the equilibrium geometry, with the absolute minimum energy, is of lowered, nonplanar C2 symmetry instead of the more symmetric planar D2h symmetry that is usually the minimum for similar PAHs of smaller size. This kind of slightly broken symmetry could produce some of the fine structure observed in some diffuse interstellar bands (DIBs). It can also favor the folding of C78H26+ fragments and ultimately the formation of fullerenes. This study opens up the possibility to identify the most promising candidates for DIBs amongst large cationic PAHs. PMID:26942230

Recovery of laccase from processed Hericium erinaceus (Bull.:Fr) Pers. fruiting bodies in aqueous two-phase system.

Science.gov (United States)

Rajagopalu, Devamalini; Show, Pau Loke; Tan, Yee Shin; Muniandy, Sekaran; Sabaratnam, Vikineswary; Ling, Tau Chuan

2016-09-01

The feasible use of aqueous two-phase systems (ATPSs) to establish a viable protocol for the recovery of laccase from processed Hericium erinaceus (Bull.:Fr.) Pers. fruiting bodies was evaluated. Cold-stored (4.00±1.00°C) H. erinaceus recorded the highest laccase activities of 2.02±0.04 U/mL among all the processed techniques. The evaluation was carried out in twenty-five ATPSs, which composed of polyethylene glycol (PEG) with various molecular weights and potassium phosphate salt solution to purify the protein from H. erinaceus. Optimum recovery condition was observed in the ATPS which contained 17% (w/w) PEG with a molecular weight of 8000 and 12.2% (w/w) potassium phosphate solution, at a volume ratio (VR) of 1.0. The use of ATPS resulted in one-single primary recovery stage process that produced an overall yield of 99% with a purification factor of 8.03±0.46. The molecular mass of laccases purified from the bottom phase was in the range of 55-66 kDa. The purity of the partitioned laccase was confirmed with sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE). Copyright © 2016 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Non-conventional solvents in liquid phase microextraction and aqueous biphasic systems.

Science.gov (United States)

An, Jiwoo; Trujillo-Rodríguez, María J; Pino, Verónica; Anderson, Jared L

2017-06-02

The development of rapid, convenient, and high throughput sample preparation approaches such as liquid phase microextraction techniques have been continuously developed over the last decade. More recently, significant attention has been given to the replacement of conventional organic solvents used in liquid phase microextraction techniques in order to reduce toxic waste and to improve selectivity and/or extraction efficiency. With these objectives, non-conventional solvents have been explored in liquid phase microextraction and aqueous biphasic systems. The utilized non-conventional solvents include ionic liquids, magnetic ionic liquids, and deep eutectic solvents. They have been widely used as extraction solvents or additives in various liquid phase microextraction modes including dispersive liquid-liquid microextraction, single-drop microextraction, hollow fiber-liquid phase microextraction, as well as in aqueous biphasic systems. This review provides an overview into the use of non-conventional solvents in these microextraction techniques in the past 5 years (2012-2016). Analytical applications of the techniques are also discussed. Copyright © 2017 Elsevier B.V. All rights reserved.

A new aqueous activity model for geothermal brines in the system Na-K-Ca-Mg-H-Cl-SO4-H2O from 25 to 300 degrees C

DEFF Research Database (Denmark)

Hingerl, Ferdinand F.; Wagner, Thomas; Kulik, Dmitrii A.

2014-01-01

A revised formulation (named REUNIQUAC) of the Extended Universal QUAsiChemical (EUNIQUAC) activity model has been developed, which fits excess thermodynamic properties of binary and selected aqueous ternary electrolyte solutions in the system Na-K-Ca-Mg-H-Cl-SO4-H2O over temperatures from 298 to...

Determination of ammonium in aqueous samples using new headspace dynamic in-syringe liquid-phase microextraction with in situ derivitazation coupled with liquid chromatography-fluorescence detection.

Science.gov (United States)

Muniraj, Sarangapani; Yan, Cheing-Tong; Shih, Hou-Kung; Ponnusamy, Vinoth Kumar; Jen, Jen-Fon

2012-11-19

A new simultaneous derivatization and extraction method for the preconcentration of ammonia using new one-step headspace dynamic in-syringe liquid-phase microextraction with in situ derivatization was developed for the trace determination of ammonium in aqueous samples by liquid chromatography with fluorescence detection (LC-FLD). The acceptor phase (as derivatization reagent) containing o-phthaldehyde and sodium sulfite was held within a syringe barrel and immersed in the headspace of sample container. The gaseous ammonia from the alkalized aqueous sample formed a stable isoindole derivative with the acceptor phase inside the syringe barrel through the reciprocated movements of plunger. After derivatization-cum-extraction, the acceptor phase was directly injected into LC-FLD for analysis. Parameters affecting the ammonia evolution and the extraction/derivatization efficiency such as sample matrix, pH, temperature, sampling time, and the composition of derivatization reagent, reaction temperature, and frequency of reciprocated plunger, were studied thoroughly. Results indicated that the maximum extraction efficiency was obtained by using 100μL derivatization reagent in a 1-mL gastight syringe under 8 reciprocated movements of plunger per min to extract ammonia evolved from a 20mL alkalized aqueous solution at 70°C (preheated 4min) with 380rpm stirring for 8min. The detection was linear in the concentration range of 0.625-10μM with the correlation coefficient of 0.9967 and detection limit of 0.33μM (5.6ng mL(-1)) based on SN(-1)=3. The method was applied successfully to determine ammonium in real water samples without any prior cleanup of the samples, and has been proved to be a simple, sensitive, efficient and cost-effective procedure for trace ammonium determination in aqueous samples. Copyright © 2012 Elsevier B.V. All rights reserved.

Solubility behaviour of antimony(III) and antimony(V) solids in basic aqueous solutions at 300oC

International Nuclear Information System (INIS)

Lemire, R.J.; Tosello, N.B.; Halliday, J.D.

1999-12-01

The major contributions of the isotopes 122 Sb and 124 Sb to activity transport in a CANDU reactor primary heat transport system (HTS), have been associated with oxygen ingress during reactor shutdown. As part of a program to minimize the release and redeposition of these isotopes, the solubilities of antimony(III) and (V) oxides and salts have been measured in basic solutions at temperatures from 25 to 300 o C. The results provide information on the charge and the stability as a function of temperature of antimony solution species and, hence, a guide to the trends in the temperature dependence of the solubilities of antimony solids. In solutions in which oxidation of antimony(III) to antimony(V) is minimized, the solubility of Sb 2 O 3 increases by about two orders of magnitude between 25 and 200 o C, and then levels out or decreases slightly. At 250 o C, in oxidizing solutions, Sb 2 O 5 ·xH 2 O and simple sodium antimonate(V) were found to be unstable in sodium hydroxide solutions with respect to the solid, Na 2α [H(H 2 O)] 2-2α Sb 2 O 6 , which has a pyrochlore structure. The solubility of this partially protonated sodium antimonate increases from 25 to 200 o C and decreases at temperatures above 250 o C. These solubility changes for the antimony (V) solids reflect changes in the stability of the anionic antimony solution species (SbO 3 - or Sb(OH) 6 - ), even though the compositions of antimony-containing solids in basic oxidizing solutions are strongly dependent on the cations and their aqueous phase concentrations. All solids used in the present experiments would be expected to generate total solution antimony concentrations ≥ 0.00005 mol·dm -3 in any neutral or basic aqueous solutions (assuming no added sodium salts). Therefore, under HTS conditions, precipitation of any antimony oxides or mixed oxides is unlikely. It cannot be ruled out that hydrated Sb 2 O 5 (especially the pyrochlore form) might be less soluble in near-neutral, low

Application of E{sub h}-pH diagram for room temperature precipitation of zinc stannate microcubes in an aqueous media

Energy Technology Data Exchange (ETDEWEB)

Al-Hinai, Ashraf T., E-mail: ashraf@squ.edu.om [Department of Chemistry, College of Science, Sultan Qaboos University, 123, Alkhoud (Oman); Al-Hinai, Muna H. [Department of Chemistry, College of Science, Sultan Qaboos University, 123, Alkhoud (Oman); Water Research Center, Sultan Qaboos University, 123, Alkhoud (Oman); Dutta, Joydeep, E-mail: dutta@squ.ed.om [Water Research Center, Sultan Qaboos University, 123, Alkhoud (Oman)

2014-01-01

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

Adsorptive removal of phenol from aqueous phase by using a porous acrylic ester polymer

International Nuclear Information System (INIS)

Pan Bingjun; Pan Bingcai; Zhang Weiming; Zhang Qingrui; Zhang Quanxing; Zheng Shourong

2008-01-01

The removal of phenol from aqueous solution was examined by using a porous acrylic ester polymer (Amberlite XAD-7) as an adsorbent. Favorable phenol adsorption was observed at acidic solution pH and further increase of solution pH results in a marked decrease of adsorption capacity, and the coexisting inorganic salt NaCl exerts positive effect on the adsorption process. Adsorption isotherms of phenol were linearly correlated and found to be well represented by either the Langmuir or Freundlich isotherm model. Thermodynamic parameters such as changes in the enthalpy (ΔH), entropy (ΔS) and free energy (ΔG) indicate that phenol adsorption onto XAD-7 is an exothermic and spontaneous process in nature, and lower ambient temperature results in more favorable adsorption. Kinetic experiments at different initial solute concentrations were investigated and the pseudo-second-order kinetic model was successfully represented the kinetic data. Additionally, the column adsorption result showed that a complete removal of phenol from aqueous phase can be achieved by XAD-7 beads and the exhausted adsorbent was amenable to an entire regeneration by using ethanol as the regenerant. More interestingly, relatively more volume of hot water in place of ethanol can also achieve a similar result for repeated use of the adsorbent

A model for radiolysis of water and aqueous solutions of H2, H2O2 and O2

International Nuclear Information System (INIS)

Ershov, B.G.; Gordeev, A.V.

2008-01-01

Kinetic model for the radiolysis of pure water describing the formation of H 2 , H 2 O 2 and O 2 and the radiation chemical transformations of aqueous solutions containing these compounds over a broad range of concentrations, pH, absorbed doses and dose rates is proposed and substantiated. The model includes a set of chemical reactions with optimized rate constants and the radiation chemical yields of radiolysis products. The model applicability to the description of the whole set of data on the radiation chemical transformations of water and aqueous solutions of H 2 , H 2 O 2 and O 2 is demonstrated

On the magnetism of the C14 Nb0.975Fe2.025 Laves phase compound: Determination of the H-T phase diagram

Science.gov (United States)

Bałanda, Maria; Dubiel, Stanisław M.

2018-05-01

A C14 Nb0.975Fe2.025 Laves phase compound was investigated aimed at determining the H-T magnetic phase diagram. Magnetization, M, and AC magnetic susceptibility measurement were performed. Concerning the former field-cooled and zero-field-cooled M-curves were recorded in the temperature range of 2-200 K and in applied magnetic field, H, up to 1000 Oe, isothermal M(H) curves at 2 K, 5 K, 50 K, 80 K and 110 K as well as hysteresis loops at several temperatures over the field range of ±10 kOe were measured. Regarding the AC susceptibility, χ, both real and imaginary components were registered as a function of increasing temperature in the interval of 2 K-150 K at the frequencies of the oscillating field, f, from 3 Hz up to 999 Hz. An influence of the external DC magnetic field on the temperature dependence of χ was investigated, too. The measurements clearly demonstrated that the magnetism of the studied sample is weak, itinerant and has a reentrant character. Based on the obtained results a magnetic phase diagram has been constructed in the H-T coordinates.

Solid-phase extraction element based on epoxy polymer monolith for determination of polar organic compounds in aqueous media.

Science.gov (United States)

Takahashi, Tadashi; Odagiri, Kayo; Watanabe, Atsushi; Watanabe, Chuichi; Kubo, Takuya; Hosoya, Ken

2011-10-01

A solid-phase extraction element based on epoxy polymer monolith was fabricated for sorptive enrichment of polar compounds from liquid and gaseous samples. After ultrasonication of the element in an aqueous solution for a given period of time, the thermal desorption (TD) using a pyrolyzer with gas chromatography/mass spectrometry (GC/MS), in which TD temperature was programmed from 50 to 250 °C for the analytes absorbed in the element, was used to evaluate the element for basic extraction performance using the aqueous standard mixtures consisting of compounds having varied polarities such as hexanol, isoamyl acetate, linalool, furfural and decanoic acid, in concentrations ranging from 10 μg/L to 1 mg/L. Excellent linear relationships were observed for all compounds in the standard mixture, except decanoic acid. In the extraction of beverages such as red wine, the extraction element showed stronger adsorption characteristics for polar compounds such as alcohols and acids than a non-polar polydimethylsiloxane-based element. This feature is derived from the main polymer structure along with hydroxyl and amino groups present in the epoxy-based monolith polymer matrix. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

TEM characterization of a Cr/Ti/TiC graded interlayer for magnetron-sputtered TiC/a-C:H nanocomposite coatings

International Nuclear Information System (INIS)

Galvan, D.; Pei, Y.T.; De Hosson, J.Th.M.

2005-01-01

A TiC/a-C:H nanocomposite coating is deposited on top of a Cr/Ti/TiC graded interlayer. Cross-section transmission electron microscopy is employed to investigate the detailed structure of the interlayer and the coating. Five different phases are formed as a consequence of the compositional gradient within the interlayer: pure Cr, a solid solution of Ti in Cr, a Ti/Cr amorphous/nanocrystalline phase, α-Ti and TiC. Solid state amorphization occurs during the interlayer deposition to give a dispersion of TiCr β-phase nanocrystals in an amorphous matrix. The TiC phase is textured and contains numerous stacking faults as a result of the growth in under-stoichiometric carbon concentration. C-enriched columnar boundaries are present within the coating, originating from the TiC column boundaries of the interlayer. The work indicates that an interlayer of amorphous/nanocrystalline Ti/Cr phase would reduce the presence of growth defects such as columnar boundaries within nanocomposite TiC/a-C:H coatings

Aqueous phase oxidation techniques as an alternative to incineration

International Nuclear Information System (INIS)

Gray, L.W.; Adamson, M.G.; Hickman, R.G.; Farmer, J.C.; Chiba, Z.; Gregg, D.W.; Wang, F.T.

1992-03-01

The Lawrence Livermore National Laboratory (LLNL) has three aqueous phase techniques under development for oxidation of high value or high risk waste steams. One is direct electrochemical oxidation and one is mediated electrochemical oxidation utilizing regenerable, strongly oxidizing cations such as Ag(II), Co (III), Ce(IV), etc. These cations can either attack oxidizable materials directly and/or indirectly via first reacting with water to generate OH radicals which then attack the oxidizable materials. The third system utilizes H 2 O 2 and UV light to generate OH radicals directly which in turn attack the oxidizable materials. All systems have the advantage of a chemical off-switch in that when the power is turned off, the reaction quickly subsides. All systems operate with low concentrations (typically <5 wt %) of oxidizable materials, therefore, the stored energy for possible run-away reactions is very low. 15 figures, 22 references

A simple reversed phase high-performance liquid chromatography (RP-HPLC method for determination of curcumin in aqueous humor of rabbit

Directory of Open Access Journals (Sweden)

Akhilesh Mishra

2014-01-01

Full Text Available This article describes a simple and rapid method for determination of curcumin (diferuloylmethane in aqueous humor of rabbit using high-performance liquid chromatography (HPLC. Analysis was performed using a C-18 column (250 × 4.6 mm, 5 μ luna by isocratic elution with a mobile phase containing 25 mM potassium dihydrogen orthophosphate (pH 3.5: Acetonitrile (40:60 and detection at 424 nm using a photodiode array (PDA detector for curcumin. The regression data for curcumin showed a good linear relationship with r 2 > 0.998 over the concentration range of 0.1-10 μg ml−1 . Relative standard deviations (RSD for the intraday and interday coefficient of variations for the assay were less than 5.0 and 8.5, respectively. The recovery of the method was between 79.8-83.6%. The quantification limit of the method for curcumin was 0.01 μg ml−1 . This method has good accuracy, precision, and quantitation limit. It is also concluded that the method is useful for measuring very low curcumin concentrations in aqueous humor.

Aqueous-Phase Reactions of Isoprene with Sulfoxy Radical Anions as a way of Wet Aerosol Formation in the Atmosphere

Science.gov (United States)

Kuznietsova, I.; Rudzinski, K. J.; Szmigielski, R.; Laboratory of the Environmental Chemistry

2011-12-01

Atmospheric aerosols exhibit an important role in the environment. They have implications on human health and life, and - in the larger scale - on climate, the Earth's radiative balance and the cloud's formation. Organic matter makes up a significant fraction of atmospheric aerosols (~35% to ~90%) and may originate from direct emissions (primary organic aerosol, POA) or result from complex physico-chemical processes of volatile organic compounds (secondary organic aerosol, SOA). Isoprene (2-methyl-buta-1,3-diene) is one of the relevant volatile precursor of ambient SOA in the atmosphere. It is the most abundant non-methane hydrocarbon emitted to the atmosphere as a result of living vegetation. According to the recent data, the isoprene emission rate is estimated to be at the level of 500 TgC per year. While heterogeneous transformations of isoprene have been well documented, aqueous-phase reactions of this hydrocarbon with radical species that lead to the production of new class of wet SOA components such as polyols and their sulfate esters (organosulfates), are still poorly recognized. The chain reactions of isoprene with sulfoxy radical-anions (SRA) are one of the recently researched route leading to the formation of organosulfates in the aqueous phase. The letter radical species originate from the auto-oxidation of sulfur dioxide in the aqueous phase and are behind the phenomenon of atmospheric acid rain formation. This is a complicated chain reaction that is catalyzed by transition metal ions, such as manganese(II), iron(III) and propagated by sulfoxy radical anions . The presented work addresses the chemical interaction of isoprene with sulfoxy radical-anions in the water solution in the presence of nitrite ions and nitrous acid, which are important trace components of the atmosphere. We showed that nitrite ions and nitrous acid significantly altered the kinetics of the auto-oxidation of SO2 in the presence of isoprene at different solution acidity from 2 to 8

Biosorption of C.I. Direct Blue 199 from aqueous solution by nonviable Aspergillus niger

International Nuclear Information System (INIS)

Xiong Xiaojing; Meng Xuejiao; Zheng Tianling

2010-01-01

The capacity and mechanism with which nonviable Aspergillus niger removed the textile dye, C.I. Direct Blue 199, from aqueous solution was investigated using different parameters, such as initial dye concentration, pH and temperature. In batch experiments, the biosorption capacity increased with decrease in pH, and the maximum dye uptake capacity of the biosorbent was 29.96 mg g -1 at 400 mg L -1 dye concentration and 45 deg. C. The Langmuir and Freundlich models were able to describe the biosorption equilibrium of C.I. Direct Blue 199 onto the fungal biomass. Biosorption followed a pseudo-second order kinetic model with high correlation coefficients (r 2 > 0.99). Thermodynamic studies revealed that the biosorption process was successful, spontaneous and endothermic in nature.

Thermochemistry analyses for transformation of C6 glucose compound into C9, C12 and C15 alkanes using density functional theory

Science.gov (United States)

Verma, Anand Mohan; Kishore, Nanda

2017-02-01

The hydrolysis of cellulose fraction of biomass yields C6 glucose which further can be transformed into long-chain hydrocarbons by C-C coupling. In this study, C6 glucose is transformed into three chain alkanes, namely, C9, C12 and C15 using C-C coupling reactions under the gas and aqueous phase milieus. The geometry optimisation and vibrational frequency calculations are carried out at well-known hybrid-GGA functional, B3LYP with the basis set of 6-31+g(d,p) under the density functional theory framework. The single point energetics are calculated at M05-2X/6-311+g(3df,2p) level of theory. All thermochemical properties are calculated over a wide range of temperature between 300 and 900 K at an interval of 100 K. The thermochemistry suggested that the aqueous phase behaviour is suitable for the hydrolysis of sugar into long-chain alkanes compared to gas-phase environment. The hydrodeoxygenation reactions under each reaction pathway are found as most favourable reactions in both phases; however, aqueous phase dominates over gas phase in all discussed thermodynamic parameters.

Extraction of UO22+ by two highly sterically hindered (X1) (X2) PO(OH) extractants from an aqueous chloride phase

International Nuclear Information System (INIS)

Mason, G.W.; Lewey, S.M.; Gilles, D.M.; Peppard, D.F.

1978-01-01

The comparative extraction behaviour of tracer-level UO 2 2+ into benzene solutions of two highly sterically hindered extractants, di(2,6-di-iso-propylphenyl) phosphoric acid, HD(2,6-i-PPHI)P and di-tertiary-butyl phosphinic acid, H[Dt-BP], vs an aqueous 1.0 F (NaCl + HCl) phase was studied. The extraction of UO 2 2+ in both systems is directly second-power dependent upon extractant concentration and inversely second-power dependent upon hydrogen ion concentration, the stoichiometry of extraction being UOsub(2A) 2+ + 2(HY)sub(2O) = UO 2 (HY 2 )sub(2O) + 2Hsub(A) + . The expression for the distribution ratio, K is K = Ksub(s)F 2 /[H + ] 2 the general expression for the extraction of any metallic species being K - Ksub(s)Fsup(a)/[H + ]sup(b) where Ksub(s) is a constant characteristic of the system, F the concentration in formality units of extractant in the organic phase, [H + ] the concentration of hydrogen ion in the aqueous phase, and a and b the respective extractant and hydrogen-ion dependencies. Both extractants have a high degree of steric hindrance. The HD(2,6-i-PPHI)P is the more highly acidic, the pKsub(A) value, in 75% ethanol, being 3.2. The pKsub(A), previously reported, for H[Dt-BP] is 6.26. The Ksub(s) for UO 2 2+ in the system HY in benzene diluent vs an aqueous 1.0 F (NaCl + HCl) phase is 2 x 10 4 for H[Dt-BP] and 3 x 10 -1 for HD(2,6-i-PPHI)P; the ratio of the Ksub(s) values nearly 7 x 10 3 , favours the less acidic extractant. For comparative purposes, the Ksub(s) values for UO 2 2+ and for Am 3+ and Eu 3+ in other (X 1 )(X 2 )PO(OH), in benzene diluent, vs 1.0 F (NaCl + HCl) systems are presented. The variations are discussed in terms of the pKsub(A) of the extractant and the steric hindrance within the extractant. (author)

An experimental study of the solubility of molybdenum in H₂O and KCl-H₂O solutions from 500 ºC to 800 ºC, and 150 to 300 MPa

Energy Technology Data Exchange (ETDEWEB)

Ulrich, Thomas; Mavrogenes, John [Australian National University

2008-04-22

The solubility of molybdenum (Mo) was determined at temperatures from 500 °C to 800 °C and 150 to 300 MPa in KCl-H₂O and pure H₂O solutions in cold-seal experiments. The solutions were trapped as synthetic fluid inclusions in quartz at experimental conditions, and analyzed by laser ablation inductively coupled plasma mass spectrometry (LA ICPMS). Mo solubilities of 1.6 wt% in the case of KCl-bearing aqueous solutions and up to 0.8 wt% in pure H₂O were found. Mo solubility is temperature dependent, but not pressure dependent over the investigated range, and correlates positively with salinity (KCl concentration). Molar ratios of ~1 for Mo/Cl and Mo/K are derived based on our data. In combination with results of synchrotron X-ray absorption spectroscopy of individual fluid inclusions, it is suggested that Mo-oxo-chloride complexes are present at high salinity (>20 wt% KCl) and ion pairs at moderate to low salinity (<11 wt% KCl) in KCl-H₂O aqueous solutions. Similarly, in the pure H₂O experiments molybdic acid is the dominant species in aqueous solution. The results of these hydrothermal Mo experiments fit with earlier studies conducted at lower temperatures and indicate that high Mo concentrations can be transported in aqueous solutions. Therefore, the Mo concentration in aqueous fluids seems not to be the limiting factor for ore formation, whereas precipitation processes and the availability of sulfur appear to be the main controlling factors in the formation of molybdenite (MoS₂).

Ammonium fluoride as a mobile phase additive in aqueous normal phase chromatography.

Science.gov (United States)

Pesek, Joseph J; Matyska, Maria T

2015-07-03

The use of ammonium fluoride as a mobile phase additive in aqueous normal phase chromatography with silica hydride-based stationary phases and mass spectrometry detection is evaluated. Retention times, peak shape, efficiency and peak intensity are compared to the more standard additives formic acid and ammonium formate. The test solutes were NAD, 3-hydroxyglutaric acid, α-ketoglutaric acid, p-aminohippuric acid, AMP, ATP, aconitic acid, threonine, N-acetyl carnitine, and 3-methyladipic acid. The column parameters are assessed in both the positive and negative ion detection modes. Ammonium fluoride is potentially an aggressive mobile phase additive that could have detrimental effects on column lifetime. Column reproducibility is measured and the effects of switching between different additives are also tested. Copyright © 2015 Elsevier B.V. All rights reserved.

Experimental measurements of U60 nanocluster stability in aqueous solution

Science.gov (United States)

Flynn, Shannon L.; Szymanowski, Jennifer E. S.; Gao, Yunyi; Liu, Tianbo; Burns, Peter C.; Fein, Jeremy B.

2015-05-01

In this study, the aqueous behavior of isolated U60 nanoclusters (K16Li25[UO2(O2)OH]60)-19 was studied under several pH conditions and nanocluster concentrations to determine if the nanoclusters exhibit solid phase buffering behavior or if they exhibit behavior more like aqueous complexes. U60 is a cage cluster consisting of 60 (UO2)(O2)2(OH)2 uranyl polyhedral which share OH and O2 groups with their neighboring uranyl polyhedral, resulting in negatively charged cage clusters whose charge is at least partially offset by K+ and Li+ in the aqueous phase. Batch experiments to monitor nanocluster stability were conducted for 16 days at pH 7.5, 8.0 and 8.5 at nanocluster suspension concentrations of 1.4, 2.8 and 6.0 g/L. The aqueous concentrations of U, Li, and K, determined after 10 kDa molecular weight filtration, achieved steady-state with the nanoclusters within 24 h. The steady-state aqueous U, Li, and K concentrations were independent of solution pH, however they increased with increasing nanocluster concentration, indicating that the nanoclusters do not buffer the aqueous activities as a bulk solid phase would, but exhibit behavior that is more characteristic of dissolved aqueous complexes. The ion activity product (I.A.P.) value was calculated using two approaches: (1) treating the nanoclusters as a solid phase with an activity of one, and (2) treating the nanoclusters as aqueous complexes with a non-unit activity equal to their concentration in solution. The I.A.P. values that were calculated with non-unit activity for the nanoclusters exhibited significantly less variation as a function of nanocluster concentration compared to the I.A.P. values calculated with a nanocluster activity of one. The results yield a calculated log dissociation constant for the U60 nanoclusters of 9.2 + 0.2/-0.3 (1σ). Our findings provide a better understanding of the thermodynamic stability and behavior of U60 nanoclusters in aqueous systems, and can be used to estimate the

Headspace liquid-phase microextraction of methamphetamine and amphetamine in urine by an aqueous drop

International Nuclear Information System (INIS)

He Yi; Vargas, Angelica; Kang, Youn-Jung

2007-01-01

This study developed a headspace liquid-phase microextraction (LPME) method by using a single aqueous drop in combination with high performance liquid chromatography (HPLC)-UV detection for the determination of methamphetamine (MAP) and amphetamine (AP) in urine samples. The analytes, volatile and basic, were released from sample matrix into the headspace first, and then protonated and dissolved in an aqueous H 3 PO 4 drop hanging in the headspace by a HPLC syringe. After extraction, this drop was directly injected into HPLC. Parameters affecting extraction efficiency were investigated and optimized. This method showed good linearity in the investigated concentration range of 1.0-1500 μg L -1 , repeatability of the extraction (R.S.D. -1 for both analytes). Enrichment factors of about 400-fold and 220-fold were achieved for MAP and AP, respectively, at optimum conditions. The feasibility of the method was demonstrated by analyzing human urine samples

Production of gaseous and liquid chemicals by aqueous phase reforming of crude glycerol: Influence of operating conditions on the process

International Nuclear Information System (INIS)

Remón, J.; Giménez, J.R.; Valiente, A.; García, L.; Arauzo, J.

2016-01-01

Highlights: • Aqueous phase reforming: a tailor-made process for the valorisation of crude glycerol. • In-depth understanding of the effect of the operating conditions on the process. • Process optimisation for the selective production of valuable gas and liquid products. • Low pressure and high temperature and spatial time favour gas production. • High pressure and medium temperature maximise the production of valuable liquids. - Abstract: The present work studies the influence of the temperature (200–240 °C), pressure (38–50 bar), glycerol concentration (10–50 wt.%) and mass of catalyst/ glycerol mass flow rate ratio (W/m_g_l_y_c_e_r_o_l = 10–40 g catalyst min/g glycerol) during the aqueous phase reforming (APR) of a glycerol solution obtained from the production of biodiesel. The operating conditions exerted a statistically significant influence on the reforming results. Specifically, the global glycerol conversion and the carbon converted into gas and liquid products varied as follows: 4–100%, 1–80% and 16–93%, respectively. The gas phase was made up of H_2 (8–55 vol.%), CO_2 (34–66 vol.%), CO (0–4 vol.%) and CH_4 (6–45 vol.%). The liquid phase consisted of a mixture of alcohols (monohydric: methanol and ethanol; and polyhydric: 1,2-propanediol, 1,2-ethanediol, 2,3-butanediol), aldehydes (acetaldehyde), ketones (C3-ketones: acetone and 2-propanone-1-hydroxy; C4-ketones: 2-butanone-3-hydroxy and 2-butanone-1-hydroxy; and cyclic ketones), carboxylic acids (acetic and propionic acids) and esters (1,2,3-propanetriol-monoacetate), together with unreacted glycerol and water. The relative amount (free of water and un-reacted glycerol) of these compounds in the liquid phase was as follows: monohydric alcohols: 4–47%, polyhydric-alcohols: 14–68%, aldehydes: 0–5%, C3-ketones: 2–33%, C4-ketones: 0–10%, ciclo-ketones: 0–6%, carboxylic acids: 2–43%, and esters: 0–46%. This process turned out to be highly customisable for the

Solubility behaviour of antimony(III) and antimony(V) solids in basic aqueous solutions at 300{sup o}C

Energy Technology Data Exchange (ETDEWEB)

Lemire, R.J.; Tosello, N.B.; Halliday, J.D

1999-12-01

The major contributions of the isotopes {sup 122}Sb and {sup 124}Sb to activity transport in a CANDU reactor primary heat transport system (HTS), have been associated with oxygen ingress during reactor shutdown. As part of a program to minimize the release and redeposition of these isotopes, the solubilities of antimony(III) and (V) oxides and salts have been measured in basic solutions at temperatures from 25 to 300{sup o}C. The results provide information on the charge and the stability as a function of temperature of antimony solution species and, hence, a guide to the trends in the temperature dependence of the solubilities of antimony solids. In solutions in which oxidation of antimony(III) to antimony(V) is minimized, the solubility of Sb{sub 2}O{sub 3} increases by about two orders of magnitude between 25 and 200{sup o}C, and then levels out or decreases slightly. At 250{sup o}C, in oxidizing solutions, Sb{sub 2}O{sub 5}{center_dot}xH{sub 2}O and simple sodium antimonate(V) were found to be unstable in sodium hydroxide solutions with respect to the solid, Na{sub 2{alpha}}[H(H{sub 2}O)]{sub 2-2{alpha}}Sb{sub 2}O{sub 6}, which has a pyrochlore structure. The solubility of this partially protonated sodium antimonate increases from 25 to 200{sup o}C and decreases at temperatures above 250{sup o}C. These solubility changes for the antimony (V) solids reflect changes in the stability of the anionic antimony solution species (SbO{sub 3}{sup -} or Sb(OH){sub 6}{sup -}), even though the compositions of antimony-containing solids in basic oxidizing solutions are strongly dependent on the cations and their aqueous phase concentrations. All solids used in the present experiments would be expected to generate total solution antimony concentrations {>=} 0.00005 mol{center_dot}dm{sup -3} in any neutral or basic aqueous solutions (assuming no added sodium salts). Therefore, under HTS conditions, precipitation of any antimony oxides or mixed oxides is unlikely. It cannot be

Separation of uranium from aqueous solutions using calix[6]arenes in liquid-liquid extraction as well as solid phase extraction

International Nuclear Information System (INIS)

Schmeide, K.; Geipel, G.; Bernhard, G.

2004-11-01

The suitability of different calyx[n] arene types for uranyl extraction from liquid solutions was examined by means of liquid-liquid extraction using aqueous phases and organic solvents of varying compositions. It was found that COOH-derivatised calyx[6] arenes have good extraction properties and can even be used in the acid pH range. The use of calixarene-modified fleeces for the separation of uranyl from aqueous phases was examined in batch experiments with pH and uranyl concentration as variables and in the presence or absence of competing ions. The results showed that calixarene-modified fleeces can be used for uranium separation starting from pH 4. At pH 5, up to a maximum of 7.6 x 10 -7 mol uranium can be bound per 1 g of calixarene-modified fleece. The separation of uranyl from synthetic pit waters was examined as a means of testing the separation capacity of calixarene-modified fleeces in environmentally sensitive waters. Studies on the reversibility of uranium bonding to calixarene-treated polyester fleeces have shown that under environmentally realistic conditions (neutral pH range) the uranium is firmly bound to the calixarene-modified fleeces and cannot be mobilised. By contrast, in acidic environments calixarene-modified fleeces are capable of near-complete regeneration. Such regenerated textile filter materials can then be used for further uranium separation cycles [de

Synergistic extraction of transition metal cations from aqueous media by two separated organic phases

International Nuclear Information System (INIS)

Goldberg, I.

1991-12-01

We have therefore initiated novel approaches to the study of the mechanism of the synergistic extraction of metal ions by means of two separated organic phases, which are brought in contact with the same aqueous phase. The present work is concerned with the extraction of transition metals and actinides ions from nitric acid by chelating agents e.g., HTTA thenoyltrifluoroacetone in a diluent - the first organic phase, and by natural donor, e.g., TBP, tri-butyl phosphate in a diluent the second organic phase. The adduct formation was studied by means of spectrochemical and radiochemical methods. In the first approach the aqueous phase was attacked with both organic phases simultanously (the static or parallel extraction). In this method organic phase are separated one from the other. It was shown that even in the absence of mixing, synergism is observed under this experimental conditions. The results indicate, that adduct formation occurs in both organic phases. Nevertheless the enhanchment of extraction in the TBP phase is by far greater than that in the HTTA containing phase. This approach has one disadvatage, viz., the experiments are very time consuming, a typical experiment requiring over 10 days. In order to overcome this difficulty, the following experiments were carried out: the aqueous phase were first shaken with diluent containing an anionic ligand and the phases were allowed to separate. Then the aqueous solution were shaken with diluent containing a netural donor and the phase again were allowed to separate. The concentration of the metal ions in all the phases were determined. The experiments were repeated with an other diluent replacing the first diluent in one or both organic phases. In this way eight sequences of experiments were carried out for each concentration set chosen. The results thus point out that this experimental approach open new possibilities to investigate the mechanism and the kinetics of synergistic extraction processes. (author) the

Biosurfactant production by Pseudomonas sp. and its role in aqueous phase partitioning and biodegradation of chlorpyrifos.

Science.gov (United States)

Singh, P B; Sharma, S; Saini, H S; Chadha, B S

2009-09-01

To study the effect of biosurfactant on aqueous phase solubility and biodegradation of chlorpyrifos. A Pseudomonas sp. (ChlD), isolated from agricultural soil by enrichment culture technique in the presence of chlorpyrifos, was capable of producing biosurfactant (rhamnolipids) and degrading chlorpyrifos (0.01 g l(-1)). The partially purified rhamnolipid biosurfactant preparation, having a CMC of 0.2 g l(-1), was evaluated for its ability to enhance aqueous phase partitioning and degradation of chlorpyrifos (0.01 g l(-1)) by ChlD strain. The best degradation efficiency was observed at 0.1 g l(-1) supplement of biosurfactant, as validated by GC and HPLC studies. The addition of biosurfactant at 0.1 g l(-1) resulted in more than 98% degradation of chlorpyrifos when compared to 84% in the absence of biosurfactant after 120-h incubation. This first report, to the best of our knowledge, on enhanced degradation of chlorpyrifos in the presence of biosurfactant(s), would help in developing bioremediation protocols to counter accumulation of organophosphates to toxic/carcinogenic levels in environment.

Ca2+ pump and Ca2+/H+ antiporter in plasma membrane vesicles isolated by aqueous two-phase partitioning from corn leaves

International Nuclear Information System (INIS)

Kasai, M.; Muto, S.

1990-01-01

Plasma membrane vesicles, which are mostly right side-out, were isolated from corn leaves by aqueous two-phase partitioning method. Characteristics of Ca2+ transport were investigated after preparing inside-out vesicles by Triton X-100 treatment. 45Ca2+ transport was assayed by membrane filtration technique. Results showed that Ca2+ transport into the plasma membrane vesicles was Mg-ATP dependent. The active Ca2+ transport system had a high affinity for Ca2+(Km(Ca2+) = 0.4 microM) and ATP(Km(ATP) = 3.9 microM), and showed pH optimum at 7.5. ATP-dependent Ca2+ uptake in the plasma membrane vesicles was stimulated in the presence of Cl- or NO3-. Quenching of quinacrine fluorescence showed that these anions also induced H+ transport into the vesicles. The Ca2+ uptake stimulated by Cl- was dependent on the activity of H+ transport into the vesicles. However, carbonylcyanide m-chlorophenylhydrazone (CCCP) and VO4(3-) which is known to inhibit the H+ pump associated with the plasma membrane, canceled almost all of the Cl(-)-stimulated Ca2+ uptake. Furthermore, artificially imposed pH gradient (acid inside) caused Ca2+ uptake into the vesicles. These results suggest that the Cl(-)-stimulated Ca2+ uptake is caused by the efflux of H+ from the vesicles by the operation of Ca2+/H+ antiport system in the plasma membrane. In Cl(-)-free medium, H+ transport into the vesicles scarcely occurred and the addition of CCCP caused only a slight inhibition of the active Ca2+ uptake into the vesicles. These results suggest that two Ca2+ transport systems are operating in the plasma membrane from corn leaves, i.e., one is an ATP-dependent active Ca2+ transport system (Ca2+ pump) and the other is a Ca2+/H+ antiport system. Little difference in characteristics of Ca2+ transport was observed between the plasma membranes isolated from etiolated and green corn leaves

Continuous-flow ultrasound assisted oxidative desulfurization (UAOD) process: An efficient diesel treatment by injection of the aqueous phase.

Science.gov (United States)

Rahimi, Masoud; Shahhosseini, Shahrokh; Movahedirad, Salman

2017-11-01

A new continuous-flow ultrasound assisted oxidative desulfurization (UAOD) process was developed in order to decrease energy and aqueous phase consumption. In this process the aqueous phase is injected below the horn tip leading to enhanced mixing of the phases. Diesel fuel as the oil phase with sulfur content of 1550ppmw and an appropriate mixture of hydrogen peroxide and formic acid as the aqueous phase were used. At the first step, the optimized condition for the sulfur removal has been obtained in the batch mode operation. Hence, the effect of more important oxidation parameters; oxidant-to-sulfur molar ratio, acid-to-sulfur molar ratio and sonication time were investigated. Then the optimized conditions were obtained using Response Surface Methodology (RSM) technique. Afterwards, some experiments corresponding to the best batch condition and also with objective of minimizing the residence time and aqueous phase to fuel volume ratio have been conducted in a newly designed double-compartment reactor with injection of the aqueous phase to evaluate the process in a continuous flow operation. In addition, the effect of nozzle diameter has been examined. Significant improvement on the sulfur removal was observed specially in lower sonication time in the case of dispersion method in comparison with the conventional contact between two phases. Ultimately, the flow pattern induced by ultrasonic device, and also injection of the aqueous phase were analyzed quantitatively and qualitatively by capturing the sequential images. Copyright © 2017 Elsevier B.V. All rights reserved.

Precipitation of aluminum and magnesium secondary minerals from uranium mill raffinate (pH 1.0–10.5) and their controls on aqueous contaminants

International Nuclear Information System (INIS)

Robertson, Jared; Hendry, M. Jim; Essilfie-Dughan, J.; Chen, J.

2016-01-01

Models of geochemical controls on elements of concern (EOCs; e.g., As, Se, Mo, Ni) in U tailings are dominated by ferrihydrite. However, the evolution of aqueous concentrations of Al and Mg through the Key Lake (KL) U mill bulk neutralization process indicates that secondary Al and Mg minerals comprise a large portion of the tailings solids. X-ray diffraction, Al K-edge XAS, and TEM elemental mapping of solid samples collected from a pilot-scale continuous-flow synthetic raffinate neutralization system of the KL mill indicate the secondary Al–Mg minerals present include Mg–Al hydrotalcite, amorphous Al(OH)_3, and an amorphous hydrobasaluminite-type phase. The ferrihydrite present contains Al and may be more accurately described as Al–Fe(OH)_3. In the final combined tailings sample (pH 10.5) collected from the model experiments using raffinate with Al, Mg, and Fe, solid phase EOCs were associated with Al–Fe(OH)_3 and Mg–Al hydrotalcite. In model experiments using raffinate devoid of Fe, aqueous EOC concentrations decreased greatly at pH 4.0 (i.e., where ferrihydrite would precipitate) and largely remained in the solid phase when increased to the terminal pH of 10.5; this suggests Al–Mg minerals can control aqueous concentrations of EOCs in the raffinate in the absence of Fe. Maximum adsorption capacities for individual and mixtures of adsorbates by Mg–Al hydrotalcite were determined. A revised model of the geochemical controls in U mill tailings is presented in which Al and Mg minerals co-exist with Fe minerals to control EOC concentrations. - Highlights: • Simulated a U mill neutralization process to identify Al–Mg secondary mineralogy. • Identified AlOHSO_4, Al–Fe(OH)_3, Al(OH)_3, and Mg–Al hydrotalcite as precipitates. • Aqueous As, Ni, Mo, and Se concentrations controlled by Al–Mg minerals. • Experimental hydrotalcite uptake of As, Mo, and Se was comparable to ferrihydrite. • Updates the current model of aqueous contaminant

Characterization of Laves phase in Crofer 22 H stainless steel.

Science.gov (United States)

Hsiao, Zheng-Wen; Kuhn, Bernd; Chen, Delphic; Singheiser, Lorenz; Kuo, Jui-Chao; Lin, Dong-Yih

2015-07-01

This study investigated the effect of annealing temperature on the precipitation behavior of Crofer(®) 22 H at 600°C, 700°C, and 800°C. The grain size distribution, precipitate phase identification, and microstructure were analyzed using electron backscatter diffraction (EBSD) and energy dispersive X-ray spectroscopy (EDS). The morphology of Laves phase (Fe,Cr,Si)(2)(Nb,W) precipitates having the Cr(2)Nb structure changed from strip-like to needle-shaped as the annealing temperature was increased. The precipitates of the Laves phase also shifted from the grain boundaries to the grain interiors when the temperature was increased. However, the average grain size (150 μm) of the ferritic matrix did not significantly change at 600°C, 700°C, and 800°C for 10 h. Copyright © 2015 Elsevier Ltd. All rights reserved.

Biosorption of C.I. Direct Blue 199 from aqueous solution by nonviable Aspergillus niger

Energy Technology Data Exchange (ETDEWEB)

Xiong Xiaojing, E-mail: xiongxj@xmu.edu.cn [Environmental Science Research Center, State Key Laboratory of Marine Environmental Science, Xiamen University, Xiamen 361005 (China); Meng Xuejiao [Environmental Science Research Center, State Key Laboratory of Marine Environmental Science, Xiamen University, Xiamen 361005 (China); Zheng Tianling [Environmental Science Research Center, State Key Laboratory of Marine Environmental Science, Xiamen University, Xiamen 361005 (China); Key Laboratory of Ministry of Education for Coast and Wetland Ecosystems, School of Life Sciences, Xiamen University, Xiamen 361005 (China)

2010-03-15

The capacity and mechanism with which nonviable Aspergillus niger removed the textile dye, C.I. Direct Blue 199, from aqueous solution was investigated using different parameters, such as initial dye concentration, pH and temperature. In batch experiments, the biosorption capacity increased with decrease in pH, and the maximum dye uptake capacity of the biosorbent was 29.96 mg g{sup -1} at 400 mg L{sup -1} dye concentration and 45 deg. C. The Langmuir and Freundlich models were able to describe the biosorption equilibrium of C.I. Direct Blue 199 onto the fungal biomass. Biosorption followed a pseudo-second order kinetic model with high correlation coefficients (r{sup 2} > 0.99). Thermodynamic studies revealed that the biosorption process was successful, spontaneous and endothermic in nature.

Specific processes and scrambling in the dehydrogenation of ethane and the degenerate hydrogen exchange in the gas-phase ion chemistry of the Ni(C,H3,O)+/C2H6 couple

Czech Academy of Sciences Publication Activity Database

Schlangen, M.; Schwarz, H.; Schröder, Detlef

2007-01-01

Roč. 90, č. 5 (2007), s. 847-853 ISSN 0018-019X Institutional research plan: CEZ:AV0Z40550506 Keywords : alkoxides * C-H activation * gas-phase investigations * mass spectrometry * nicel Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.515, year: 2007

Headspace liquid-phase microextraction of methamphetamine and amphetamine in urine by an aqueous drop

Energy Technology Data Exchange (ETDEWEB)

He Yi [Department of Sciences, John Jay College of Criminal Justice, City University of New York, 445 W 59th Street, New York, NY 10019 (United States)]. E-mail: yhe@jjay.cuny.edu; Vargas, Angelica [Department of Sciences, John Jay College of Criminal Justice, City University of New York, 445 W 59th Street, New York, NY 10019 (United States); Kang, Youn-Jung [Department of Sciences, John Jay College of Criminal Justice, City University of New York, 445 W 59th Street, New York, NY 10019 (United States)

2007-04-25

This study developed a headspace liquid-phase microextraction (LPME) method by using a single aqueous drop in combination with high performance liquid chromatography (HPLC)-UV detection for the determination of methamphetamine (MAP) and amphetamine (AP) in urine samples. The analytes, volatile and basic, were released from sample matrix into the headspace first, and then protonated and dissolved in an aqueous H{sub 3}PO{sub 4} drop hanging in the headspace by a HPLC syringe. After extraction, this drop was directly injected into HPLC. Parameters affecting extraction efficiency were investigated and optimized. This method showed good linearity in the investigated concentration range of 1.0-1500 {mu}g L{sup -1}, repeatability of the extraction (R.S.D. < 5%, n = 6), and low detection limits (0.3 {mu}g L{sup -1} for both analytes). Enrichment factors of about 400-fold and 220-fold were achieved for MAP and AP, respectively, at optimum conditions. The feasibility of the method was demonstrated by analyzing human urine samples.

Synthesis and characterization of conditioned carbon with iron nanoparticles for the arsenic removal in aqueous phase

International Nuclear Information System (INIS)

Flores C, D. O.

2012-01-01

Using pineapple husks conditioned with carboxymethylcellulose, hexamine and ferric nitrate, a carbonaceous material was obtained with nanoparticles of Fe (C Fe), which was characterized and tested for arsenic removal in the aqueous phase. The microscopic study showed spheres 4 microns and filaments 100 nm wide, so as iron particles whose diameter decreases to an average of 38.81 nm, when pyrolysis time was increased to 180 min. their distribution in the carbonaceous matrix is homogeneous. According to energy dispersive X-ray spectroscopy, C Fe contains C (82.29%), O (7.23%), K (0.68%), Ca (3.77%) and Fe (6.25%) and its diffraction pattern shows the characteristic peak of Fe (0), which is not observed in the coal without iron. By neutron activation analysis were quantified Al, Br, Ce, Co, Cr, Cs, Eu, Hf, K, Mg, Mn, Na, Rb, Sb, Sc and Zn, they can be involved in the process of sorption of As (v) forming surface active sites. For C Fe and C B characterized by Fourier transform infrared spectrometry, groups C-H, C=O, C=C, -Nh, NH 2 , isocyanate and isonitrile were found, the last two were formed by the present hexamine. X-ray photoelectron spectroscopy showed energy states of C 1 and O 1 in pineapple shell washed, shell conditioned with iron, C Fe at different times and the pyrolysis coal without iron (C B). The material C Fe 180 presented a specific area of 167 m 2 /g and 7.12 ± 1 sites/nm 2 isoelectric point while pH i = 11.1 C B is 98.80 m 2 /g specific area and 1.5 ± 1 sites/nm 2 and pH i = 10.6, being favorable to the sorption process. The highest removal of As(v) for both materials was at ph = 2, fitting the kinetic data to pseudo-second order model. The isotherms as a function of concentration were adjusted to Freundlich model indicating multilayer chemisorption at specific sites of a heterogeneous medium. Characterization by scanning electron microscopy after the sample sorption Fe nanoparticles remain in the carbonaceous matrix being not affected by the

Development of linear free energy relationships for aqueous phase radical-involved chemical reactions.

Science.gov (United States)

Minakata, Daisuke; Mezyk, Stephen P; Jones, Jace W; Daws, Brittany R; Crittenden, John C

2014-12-02

Aqueous phase advanced oxidation processes (AOPs) produce hydroxyl radicals (HO•) which can completely oxidize electron rich organic compounds. The proper design and operation of AOPs require that we predict the formation and fate of the byproducts and their associated toxicity. Accordingly, there is a need to develop a first-principles kinetic model that can predict the dominant reaction pathways that potentially produce toxic byproducts. We have published some of our efforts on predicting the elementary reaction pathways and the HO• rate constants. Here we develop linear free energy relationships (LFERs) that predict the rate constants for aqueous phase radical reactions. The LFERs relate experimentally obtained kinetic rate constants to quantum mechanically calculated aqueous phase free energies of activation. The LFERs have been applied to 101 reactions, including (1) HO• addition to 15 aromatic compounds; (2) addition of molecular oxygen to 65 carbon-centered aliphatic and cyclohexadienyl radicals; (3) disproportionation of 10 peroxyl radicals, and (4) unimolecular decay of nine peroxyl radicals. The LFERs correlations predict the rate constants within a factor of 2 from the experimental values for HO• reactions and molecular oxygen addition, and a factor of 5 for peroxyl radical reactions. The LFERs and the elementary reaction pathways will enable us to predict the formation and initial fate of the byproducts in AOPs. Furthermore, our methodology can be applied to other environmental processes in which aqueous phase radical-involved reactions occur.

Solid phase extraction of uranium and thorium on octadecyl bonded silica modified with Cyanex 302 from aqueous solutions

International Nuclear Information System (INIS)

Nilchi, A.; Shariati Dehaghan, T.; Rasouli Garmarodi, S.

2013-01-01

A simple and reliable method for rapid extraction and determination of uranium and thorium using octadecyl-bonded silica modified with Cyanex 302 is presented. Extraction efficiency and the influence of various parameters such as aqueous phase pH, flow rate of sample solution and amount of extractant has been investigated. The study showed that the extraction of uranium and thorium increase with increasing pH value and was found to be quantitative at pH 6; and the retention of ions was not affected significantly by the flow rate of sample solution. The extraction percent were found to be 89.55 and 86.27 % for uranium and thorium, respectively. The maximal capacity of the cartridges modified by 30 mg of Cyanex 302 was found to be 20 mg of uranium and thorium. The method was successfully applied to the extraction and determination of uranium and thorium in aqueous solutions. The percentage recovery of uranium and thorium in a number of natural as well as seawater samples of Iran were also investigated and found to be in the range of 85-95%. (author)

Explicit modeling of volatile organic compounds partitioning in the atmospheric aqueous phase

Directory of Open Access Journals (Sweden)

C. Mouchel-Vallon

2013-01-01

Full Text Available The gas phase oxidation of organic species is a multigenerational process involving a large number of secondary compounds. Most secondary organic species are water-soluble multifunctional oxygenated molecules. The fully explicit chemical mechanism GECKO-A (Generator of Explicit Chemistry and Kinetics of Organics in the Atmosphere is used to describe the oxidation of organics in the gas phase and their mass transfer to the aqueous phase. The oxidation of three hydrocarbons of atmospheric interest (isoprene, octane and α-pinene is investigated for various NO_x conditions. The simulated oxidative trajectories are examined in a new two dimensional space defined by the mean oxidation state and the solubility. The amount of dissolved organic matter was found to be very low (yield less than 2% on carbon atom basis under a water content typical of deliquescent aerosols. For cloud water content, 50% (isoprene oxidation to 70% (octane oxidation of the carbon atoms are found in the aqueous phase after the removal of the parent hydrocarbons for low NO_x conditions. For high NO_x conditions, this ratio is only 5% in the isoprene oxidation case, but remains large for α-pinene and octane oxidation cases (40% and 60%, respectively. Although the model does not yet include chemical reactions in the aqueous phase, much of this dissolved organic matter should be processed in cloud drops and modify both oxidation rates and the speciation of organic species.

Solid Phase Extraction of Trace Copper in Aqueous Samples Using C18 Membrane Disks Modified by Benzildithiosemicarbazone Prior to Flame Atomic Absorption Spectrometric (FAAS Determination

Directory of Open Access Journals (Sweden)

M. Mohammadhosseini

2013-08-01

Full Text Available A highly convenient, selective and sensitive procedure for pre-concentration, separation and determination of sub-ppm levels of Cu2+ in aqueous samples based on modification of octadecyl silica bonded phase membrane (OSBPM disks is described using benzildithiosemicarbazone  (BDSC as a powerful modifier. It was revealed that each loaded OSBPM disk with 6.0 mg of BDSC serves as excellent bead for trapping, enrichment and isolation of trace copper. The analyte was trapped during introduction the aqueous solutions through the surface of each modified membrane, quantitatively, while other interfering ions passed through the disk to drain. The adsorbed Cu2+ ions were then stripped by appropriate eluting agents followed by monitoring of the eluates by FAAS. The effects of sample pH, amount of the modifier, stripping agent types and sample flow-rates were also investigated. The described method permitted a pre-concentration factor of about 200. The detection limit of the procedure was predicted to be about 0.013 ng L-1. The method was successfully employed for recovery and quantification of trace copper in different water samples. 

Separation and Enrichment of Lectin from Zihua Snap-Bean (Phaseolus vulgaris Seeds by PEG 600–Ammonium Sulfate Aqueous Two-Phase System

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Bin Jiang

2017-09-01

Full Text Available A fast and efficient method based on a polyethylene glycol (PEG 600/(NH42SO4 aqueous two-phase system for extracting lectin from Zihua snap-bean (Phaseolus vulgaris seeds was established. According to a Box–Behnken design (BBD, involving four factors at three levels each subjected to analysis of variance (ANOVA and response surface analysis, the protein recovery and the purification factor of lectin in the top phase were used as the response values of the variance analysis to acquire the multivariate quadratic regression model. SDS–PAGE electrophoresis and the hemagglutination test were used to detect the distribution of lectin in the aqueous two-phase system (ATPS. The obtained data indicated that lectin was preferentially partitioned into the PEG-rich phase, and the ATPS, composed of 15% (NH42SO4 (w/w, 18% PEG 600 (w/w, 0.4 g/5 g NaCl and 1 mL crude extract, showed good selectivity for lectin when the pH value was 7.5. Under the optimal conditions, most of the lectin was assigned to the top phase in the ATPS, and the hemagglutination activity of the purified lectin in the top phase was 3.08 times that of the crude extract. Consequently, the PEG 600/(NH42SO4 aqueous two-phase system was an effective method for separating and enriching lectin directly from the crude extract of Zihua snap-bean seeds.

Extraction of peptide tagged cutinase in detergent-based aqueous two-phase systems

NARCIS (Netherlands)

Rodenbrock, A.; Selber, K.; Egmond, M.R.; Kula, M.-R.

2010-01-01

Detergent-based aqueous two-phase systems have the advantage to require only one auxiliary chemical to induce phase separation above the cloud point. In a systematic study the efficiency of tryptophan-rich peptide tags was investigated to enhance the partitioning of an enzyme to the detergent-rich

Computational Study of Pincer Iridium Catalytic Systems: C-H, N-H, and C-C Bond Activation and C-C Coupling Reactions

Science.gov (United States)

Zhou, Tian

Computational chemistry has achieved vast progress in the last decades in the field, which was considered to be only experimental before. DFT (density functional theory) calculations have been proven to be able to be applied to large systems, while maintaining high accuracy. One of the most important achievements of DFT calculations is in exploring the mechanism of bond activation reactions catalyzed by organometallic complexes. In this dissertation, we discuss DFT studies of several catalytic systems explored in the lab of Professor Alan S. Goldman. Headlines in the work are: (1) (R4PCP)Ir alkane dehydrogenation catalysts are highly selective and different from ( R4POCOP)Ir catalysts, predicting different rate-/selectivity-determining steps; (2) The study of the mechanism for double C-H addition/cyclometalation of phenanthrene or biphenyl by (tBu4PCP)Ir(I) and ( iPr4PCP)Ir illustrates that neutral Ir(III) C-H addition products can undergo a very facile second C-H addition, particularly in the case of sterically less-crowded Ir(I) complexes; (3) (iPr4PCP)Ir pure solid phase catalyst is highly effective in producing high yields of alpha-olefin products, since the activation enthalpy for dehydrogenation is higher than that for isomerization via an allyl pathway; higher temperatures favor the dehydrogenation/isomerization ratio; (4) (PCP)Ir(H)2(N2H4) complex follows a hydrogen transfer mechanism to undergo both dehydrogenation to form N 2 and H2, as well as hydrogen transfer followed by N-N bond cleavage to form NH3, N2, and H2; (5) The key for the catalytic effect of solvent molecule in CO insertion reaction for RMn(CO)5 is hydrogen bond assisted interaction. The basicity of the solvent determines the strength of the hydrogen bond interaction during the catalytic path and determines the catalytic power of the solvent; and (6) Dehydrogenative coupling of unactivated C-H bonds (intermolecular vinyl-vinyl, intramolecular vinyl-benzyl) is catalyzed by precursors of the

Lactose hydrolysis in aqueous two-phase system by whole-cell {beta}-galactosidase of Kluyveromyces marxianus. Semicontinuous and continuous processes

Energy Technology Data Exchange (ETDEWEB)

Tomaska, M [Slovak Technical Univ., Bratislava (Slovakia). Dept. of Biochemical Technology; Stredansky, M [Slovak Technical Univ., Bratislava (Slovakia). Dept. of Biochemical Technology; Tomaskova, A [Slovak Technical Univ., Bratislava (Slovakia). Dept. of Biochemical Technology; Sturdik, E [Slovak Technical Univ., Bratislava (Slovakia). Dept. of Biochemical Technology

1995-01-01

Semicontinuous and continuous hydrolysis of lactose in aqueous two-phase systems (polyethylene glycol 20000/ dextran 40) with whole-cell {beta}-galactosidase of K. marxianus were studied. Both phase polymers had no effect on {beta}-galactosidase activity confined in cells. Good operational stability of the biocatalyst during 55 cycles of semicontinuous process was observed without appreciable decrease in product concentration. Continuous hydrolysis of lactose was performed in the stirred bioreactor, connected with the phase separator. The satisfactory degree of hydrolysis (between 82-88%) and volumetric productivity (21.6 g/l/h) were reached during 72 hours of continuous hydrolysis of 5% (w/w) lactose. (orig.)

Toward stable nickel catalysts for aqueous phase reforming of biomass-derived feedstock under reducing and alkaline conditions

NARCIS (Netherlands)

Haasterecht, van T.; Ludding, C.C.I.; Jong, de K.P.; Bitter, J.H.

2014-01-01

Nickel nanoparticles supported on carbon nanofibers (CNF) can be stabilized in aqueous phase processes at elevated temperatures and pressures by tuning the reaction conditions to control Ni oxidation and leaching. As a showcase, Ni/CNF was used for the production of hydrogen via aqueous phase

Aqueous enzymatic extraction of Moringa oleifera oil.

Science.gov (United States)

Mat Yusoff, Masni; Gordon, Michael H; Ezeh, Onyinye; Niranjan, Keshavan

2016-11-15

This paper reports on the extraction of Moringa oleifera (MO) oil by using aqueous enzymatic extraction (AEE) method. The effect of different process parameters on the oil recovery was discovered by using statistical optimization, besides the effect of selected parameters on the formation of its oil-in-water cream emulsions. Within the pre-determined ranges, the use of pH 4.5, moisture/kernel ratio of 8:1 (w/w), and 300stroke/min shaking speed at 40°C for 1h incubation time resulted in highest oil recovery of approximately 70% (goil/g solvent-extracted oil). These optimized parameters also result in a very thin emulsion layer, indicating minute amount of emulsion formed. Zero oil recovery with thick emulsion were observed when the used aqueous phase was re-utilized for another AEE process. The findings suggest that the critical selection of AEE parameters is key to high oil recovery with minimum emulsion formation thereby lowering the load on the de-emulsification step. Copyright © 2016 Elsevier Ltd. All rights reserved.

Spheroidization behavior of dendritic b.c.c. phase in Zr-based モ-phase composite

Directory of Open Access Journals (Sweden)

Sun Guoyuan

2013-03-01

Full Text Available The spheroidization behavior of the dendritic b.c.c. phase dispersed in a bulk metallic glass (BMG matrix was investigated through applying semi-solid isothermal processing and a subsequent rapid quenching procedure to a Zr-based モ-phase composite. The Zr-based composite with the composition of Zr56.2Ti13.8Nb5.0Cu6.9Ni5.6Be12.5 was prefabricated by a water-cooled copper mold-casting method and characterized by X-ray diffraction (XRD and scanning electron microscope (SEM. The results show that the composite consists of a glassy matrix and uniformly distributed fine dendrites of the モ-Zr solid solution with the body-centered-cubic (b.c.c. structure. Based on the differential scanning calorimeter (DSC examination results, and in view of the b.c.c. モ-Zr to h.c.p. メ-Zr phase transition temperature, a semi-solid holding temperature of 900 ìC was determined. After reheating the prefabricated composite to the semi-solid temperature, followed by an isothermal holding process at this temperature for 5 min, and then quenching the semi-solid mixture into iced-water; the two-phase microstructure composed of a BMG matrix and uniformly dispersed spherical b.c.c. モ-Zr particles with a high degree of sphericity was achieved. The present spheroidization transition is a thermodynamically autonomic behavior, and essentially a diffusion process controlled by kinetic factors; and the formation of the BMG matrix should be attributed to the rapid quenching of the semi-solid mixture as well as the large glass-forming ability of the remaining melt in the semi-solid mixture.

Hydroxyapatite-based sorbents: elaboration, characterization and application for the removal of catechol from the aqueous phase.

Science.gov (United States)

Sebei, Haroun; Pham Minh, Doan; Lyczko, Nathalie; Sharrock, Patrick; Nzihou, Ange

2017-10-01

Hydroxyapatite (HAP) is highly considered as good sorbent for the removal of metals from the aqueous phase. However, soluble metals co-exist with organic pollutants in wastewaters. But little work has been devoted to investigate the reactivity of HAP for the removal of organic compounds. The main objective of this work is to study the reactivity of HAP-based sorbents for the removal of catechol as a model organic pollutant from an aqueous solution. Thus, HAP sorbents were firstly synthesized using calcium carbonate and potassium dihydrogen phosphate under moderate conditions (25-80°C, atmospheric pressure). A zinc-doped HAP was also used as sorbent, which was obtained from the contact of HAP with an aqueous solution of zinc nitrate. All the sorbents were characterized by different standard physico-chemical techniques. The sorption of catechol was carried out in a batch reactor under stirring at room temperature and pressure. Zinc-doped HAP sorbent was found to be more reactive than non-doped HAP sorbents for the fixation of catechol. The highest sorption capacity was of 15 mg of C per gram of zinc-doped HAP sorbent. The results obtained suggest the reaction scheme of HAP sorbents with metals and organic pollutants when HAP sorbents were used for the treatment of complex wastewaters.

Kinetics, Mechanism, and Secondary Organic Aerosol Yield of Aqueous Phase Photo-oxidation of α-Pinene Oxidation Products.

Science.gov (United States)

Aljawhary, Dana; Zhao, Ran; Lee, Alex K Y; Wang, Chen; Abbatt, Jonathan P D

2016-03-10

Formation of secondary organic aerosol (SOA) involves atmospheric oxidation of volatile organic compounds (VOCs), the majority of which are emitted from biogenic sources. Oxidation can occur not only in the gas-phase but also in atmospheric aqueous phases such as cloudwater and aerosol liquid water. This study explores for the first time the aqueous-phase OH oxidation chemistry of oxidation products of α-pinene, a major biogenic VOC species emitted to the atmosphere. The kinetics, reaction mechanisms, and formation of SOA compounds in the aqueous phase of two model compounds, cis-pinonic acid (PIN) and tricarballylic acid (TCA), were investigated in the laboratory; TCA was used as a surrogate for 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA), a known α-pinene oxidation product. Aerosol time-of-flight chemical ionization mass spectrometry (Aerosol-ToF-CIMS) was used to follow the kinetics and reaction mechanisms at the molecular level. Room-temperature second-order rate constants of PIN and TCA were determined to be 3.3 (± 0.5) × 10(9) and 3.1 (± 0.2) × 10(8) M(-1) s(-1), respectively, from which were estimated their condensed-phase atmospheric lifetimes. Aerosol-ToF-CIMS detected a large number of products leading to detailed reaction mechanisms for PIN and MBTCA. By monitoring the particle size distribution after drying, the amount of SOA material remaining in the particle phase was determined. An aqueous SOA yield of 40 to 60% was determined for PIN OH oxidation. Although recent laboratory studies have focused primarily on aqueous-phase processing of isoprene-related compounds, we demonstrate that aqueous formation of SOA materials also occurs from monoterpene oxidation products, thus representing an additional source of biogenically driven aerosol formation.

Iridium complexes containing mesoionic C donors: selective C(sp3)-H versus C(sp2)-H bond activation, reactivity towards acids and bases, and catalytic oxidation of silanes and water.

Science.gov (United States)

Petronilho, Ana; Woods, James A; Mueller-Bunz, Helge; Bernhard, Stefan; Albrecht, Martin

2014-11-24

Metalation of a C2-methylated pyridylimidazolium salt with [IrCp*Cl2]2 affords either an ylidic complex, resulting from C(sp(3))-H bond activation of the C2-bound CH3 group if the metalation is performed in the presence of a base, such as AgO2 or Na2CO3, or a mesoionic complex via cyclometalation and thermally induced heterocyclic C(sp(2))-H bond activation, if the reaction is performed in the absence of a base. Similar cyclometalation and complex formation via C(sp(2))-H bond activation is observed when the heterocyclic ligand precursor consists of the analogous pyridyltriazolium salt, that is, when the metal bonding at the C2 position is blocked by a nitrogen rather than a methyl substituent. Despite the strongly mesoionic character of both the imidazolylidene and the triazolylidene, the former reacts rapidly with D(+) and undergoes isotope exchange at the heterocyclic C5 position, whereas the triazolylidene ligand is stable and only undergoes H/D exchange under basic conditions, where the imidazolylidene is essentially unreactive. The high stability of the Ir-C bond in aqueous solution over a broad pH range was exploited in catalytic water oxidation and silane oxidation. The catalytic hydrosilylation of ketones proceeds with turnover frequencies as high as 6,000 h(-1) with both the imidazolylidene and the triazolylidene system, whereas water oxidation is enhanced by the stronger donor properties of the imidazol-4-ylidene ligands and is more than three times faster than with the triazolylidene analogue. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A new set of K3Fe3(PO4)4·yH2O (0 ≤ y ≤ 1) layered phases obtained by topotactic reactions

Science.gov (United States)

Trad, Khiem; Wattiaux, Alain; Ben Amara, Mongi; Delmas, Claude; Carlier, Dany

2018-06-01

K3Fe3(PO4)4·H2O powder was synthesized by Na+/K+ exchange reaction from Na3Fe3(PO4)4 in aqueous medium. The replacement of the sodium cations by the potassium larger ones and water molecules causes a structural distortion leading to P2/n monoclinic K3Fe3(PO4)4·H2O. This new layered phase was characterized by XRD, Mössbauer spectroscopy and magnetic measurements. The study of its thermal stability reveals that other new layered K3Fe3(PO4)4·yH2O with (0 ≤ y ≤ 1) phases can be stabilized up to 600 °C and finally at higher temperature a new K3Fe3(PO4)4 polymorph with a different structural type is irreversibility formed.

Saturated phase densities of (CO_2 + H_2O) at temperatures from (293 to 450) K and pressures up to 64 MPa

International Nuclear Information System (INIS)

Efika, Emmanuel C.; Hoballah, Rayane; Li, Xuesong; May, Eric F.; Nania, Manuela; Sanchez-Vicente, Yolanda; Martin Trusler, J.P.

2016-01-01

Highlights: • Saturated phase densities of CO_2 + H_2O were measured with a 1.5 kg · m"−"3 uncertainty. • Aqueous phase densities can be predicted within 3 kg · m"−"3 using empirical models. • The CO_2-rich phase density was within 8 kg · m"−"3 of pure CO_2 at the same (p, T). • The cubic EOS of Spycher and Pruess deviates from the data by up to about 8 kg · m"−"3. - Abstract: An apparatus consisting of an equilibrium cell connected to two vibrating tube densimeters and two syringe pumps was used to measure the saturated phase densities of (CO_2 + H_2O) at temperatures from (293 to 450) K and pressures up to 64 MPa, with estimated average standard uncertainties of 1.5 kg · m"−"3 for the CO_2-rich phase and 1.0 kg · m"−"3 for the aqueous phase. The densimeters were housed in the same thermostat as the equilibrium cell and were calibrated in situ using pure water, CO_2 and helium. Following mixing, samples of each saturated phase were displaced sequentially at constant pressure from the equilibrium cell into the vibrating tube densimeters connected to the top (CO_2-rich phase) and bottom (aqueous phase) of the cell. The aqueous phase densities are predicted to within 3 kg · m"−"3 using empirical models for the phase compositions and partial molar volumes of each component. However, a recently developed multi-parameter equation of state (EOS) for this binary mixture, Gernert and Span [32], was found to under predict the measured aqueous phase density by up to 13 kg · m"−"3. The density of the CO_2-rich phase was always within about 8 kg · m"−"3 of the density for pure CO_2 at the same pressure and temperature; the differences were most positive near the critical density, and became negative at temperatures above about 373 K and pressures below about 10 MPa. For this phase, the multi-parameter EOS of Gernert and Span describes the measured densities to within 5 kg · m"−"3, whereas the computationally-efficient cubic EOS model of

Aqueous preparation of polyethylene glycol/sulfonated graphene phase change composite with enhanced thermal performance

International Nuclear Information System (INIS)

Li, Hairong; Jiang, Ming; Li, Qi; Li, Denian; Chen, Zongyi; Hu, Waping; Huang, Jing; Xu, Xizhe; Dong, Lijie; Xie, Haian; Xiong, Chuanxi

2013-01-01

Highlights: • We report an aqueous preparation technique of PEG/graphene phase change composite. • Hydrophilic sulfonated graphene (SG) nanosheets were synthesized. • Large increase in thermal conductivity is attained at low SG loading. • High latent heat is retained due to the low filler loading. • Affinity between SG and PEG contributes to the enhanced thermal performance. - Abstract: A polyethylene glycol (PEG)/sulfonated graphene (SG) phase change composite with enhanced thermal performance was prepared by solution processing in aqueous medium. It is remarkable that the addition of only 4 wt.% of SG to PEG could lead to a four times higher increase in thermal conductivity and a slight decrease in the phase change enthalpy, which is attributed to the formation of efficient thermal conductive network within the PEG matrix relevant to the excellent thermal property and unique 2-dimensional morphology of graphene as well as strong interface affinity between PEG matrix and SG nanosheets. The aqueous preparation technique is expected to pioneer a new way to prepare environment friendly organic phase change materials, and the production of PEG/SG composites is potentially scalable due to the facile fabricating process

Phase equilibrium of (CO2 + 1-aminopropyl-3-methylimidazolium bromide + water) electrolyte system and effects of aqueous medium on CO2 solubility: Experiment and modeling

International Nuclear Information System (INIS)

Chen, Ying; Guo, Kaihua; Bi, Yin; Zhou, Lan

2017-01-01

Highlights: • Phase and chemical equilibrium data for (CO 2 + [APMIm]Br + H 2 O) electrolyte system. • A modified eNRTL model for CO 2 solubility in the amino-based IL aqueous solution. • Effects of aqueous medium on both chemical and physical dissolution of CO 2 . • The correlative coefficient, R s ∗ , for the Henry’s constant of the solution. • New parameters for the segments interaction and the chemical equilibrium constants. - Abstract: New experimental data for solubility of carbon dioxide (CO 2 ) in the aqueous solution of 1-aminopropyl-3-methylimidazolium bromide ([APMIm]Br) with four different water mass fractions (0.559, 0.645, 0.765 and 0.858) at T = (278.15–348.15) K with an interval of T = 10 K and p = (0.1237–6.9143) MPa were presented. The electrolyte nonrandom two-liquid (eNRTL) model was modified to be applicable for an ionic liquid (IL) aqueous solution system, by introducing an idle factor β to illustrate the association effect of IL molecules. A solution Henry’s constant for CO 2 solubility in the IL aqueous solution was defined by introducing a correlative coefficient R s ∗ . The vapor-liquid phase equilibrium of the [APMIm]Br-H 2 O-CO 2 ternary system was successfully calculated with the modified eNRTL model. The chemical and physical mechanisms for the ionized CO 2 formation and the molecular CO 2 dissolved in the solution were identified. The effects of aqueous medium on both chemical and physical dissolution of CO 2 in the [APMIm]Br aqueous solution were studied, and a considerable enhancement of the solubility of CO 2 with increase of the water content in the solution was observed.

Peptide-tagged proteins in aqueous two-phase systems

OpenAIRE

Nilsson, Anna

2002-01-01

This thesis deals with proteins containing peptide tags for improved partitioning in aqueous two-phase systems. Qualitatively the peptide-tagged protein partitioning could be predicted from peptide data, i.e. partitioning trends found for peptides were also found for the peptide-tagged proteins. However, full effect of the tag as expected from peptide partitioning was not found in the tagged protein. When alkyl-ethylene oxide surfactant was included in a two-polymer system, almost full effect...

Tetracycline degradation by ozonation in the aqueous phase: Proposed degradation intermediates and pathway

International Nuclear Information System (INIS)

Khan, M. Hammad; Bae, Hyokwan; Jung, Jin-Young

2010-01-01

During the ozonation of tetracycline (TC) in aqueous media at pHs 2.2 and 7.0, the effects of pH variations, protonation and dissociation of functional groups and variation in free radical exposure were investigated to elucidate the transformation pathway. Liquid chromatography-triple quadrupole mass spectrometry detected around 15 ozonation products, and uncovered their production and subsequent degradation patterns. During ozonation at pH 2.2, the TC degradation pathway was proposed on the basis of the structure, ozonation chemistry and mass spectrometry data of TC. Ozonation of TC at the C11a-C12 and C2-C3 double bonds, aromatic ring and amino group generated products of m/z 461, 477, 509 and 416, respectively. Further ozonation at the above mentioned sites gave products of m/z 432, 480, 448, 525 and 496. The removal of TOC reached a maximum of ∼40% after 2 h of ozonation, while TC was completely removed within 4-6 min at both pHs. The low TOC removal efficiency might be due to the generation of recalcitrant products and the low ozone supply for high TC concentration. Ozonation decreased the acute toxicity of TC faster at pH 7.0 than pH 2.2, but the maximum decrease was only about 40% at both pHs after 2 h of ozonation. In this study, attempts were made to understand the correlation between the transformation products, pathway, acute toxicity and quantity of residual organics in solution. Overall, ozonation was found to be a promising process for removing TC and the products initially generated.

Drug release from non-aqueous suspensions. II. The release of methylxanthines from paraffin suspensions

NARCIS (Netherlands)

Blaey, C.J. de; Fokkens, J.G.

1984-01-01

The release of 3 methylxanthines, i.e. caffeine, theobromine and theophylline, from suspensions in liquid paraffin to an aqueous phase was determined in an in vitro apparatus. The release rates were determined as a function of the pH of the aqueous phase. It was proved that the release process was

Multiphase flow and transport caused by spontaneous gas phase growth in the presence of dense non-aqueous phase liquid.

Science.gov (United States)

Roy, James W; Smith, James E

2007-01-30

Disconnected bubbles or ganglia of trapped gas may occur below the top of the capillary fringe through a number of mechanisms. In the presence of dense non-aqueous phase liquid (DNAPL), the disconnected gas phase experiences mass transfer of dissolved gases, including volatile components from the DNAPL. The properties of the gas phase interface can also change. This work shows for the first time that when seed gas bubbles exist spontaneous gas phase growth can be expected to occur and can significantly affect water-gas-DNAPL distributions, fluid flow, and mass transfer. Source zone behaviour was observed in three different experiments performed in a 2-dimensional flow cell. In each case, a DNAPL pool was created in a zone of larger glass beads over smaller glass beads, which served as a capillary barrier. In one experiment effluent water samples were analyzed to determine the vertical concentration profile of the plume above the pool. The experiments effectively demonstrated a) a cycle of spontaneous gas phase expansion and vertical advective mobilization of gas bubbles and ganglia above the DNAPL source zone, b) DNAPL redistribution caused by gas phase growth and mobilization, and c) that these processes can significantly affect mass transport from a NAPL source zone.

A thermodynamic model for aqueous solutions of liquid-like density

Energy Technology Data Exchange (ETDEWEB)

Pitzer, K.S.

1987-06-01

The paper describes a model for the prediction of the thermodynamic properties of multicomponent aqueous solutions and discusses its applications. The model was initially developed for solutions near room temperature, but has been found to be applicable to aqueous systems up to 300/sup 0/C or slightly higher. A liquid-like density and relatively small compressibility are assumed. A typical application is the prediction of the equilibrium between an aqueous phase (brine) and one or more solid phases (minerals). (ACR)

Acid-base equilibrium in aqueous solutions of 1,3-dimethylbarbituric acid as studied by 13C NMR spectroscopy

Science.gov (United States)

Gryff-Keller, A.; Kraska-Dziadecka, A.

2011-12-01

13C NMR spectra of 1,3-dimethylbarbituric acid in aqueous solutions of various acidities and for various solute concentrations have been recorded and interpreted. The spectra recorded at pH = 2 and below contain the signals of the neutral solute molecule exclusively, while the ones recorded at pH = 7 and above only the signals of the appropriate anion, which has been confirmed by theoretical GIAO-DFT calculations. The signals in the spectra recorded for solutions of pH pH variation have been observed for the parent barbituric acid.

Flocculation kinetics of kaolinite : role of aqueous phase species

Energy Technology Data Exchange (ETDEWEB)

House, P.; Wang, C.; Dhadli, N. [Shell Canada Ltd., Calgary, AB (Canada)

2010-07-01

Flocculation kinetics were used to study the rate-based processes that lead to aggregate growth and breakage of kaolinite in oil sands tailings. The role of aqueous phase species on aggregate growth, breakage and flocculant de-activation was studied. Collision efficiency and deactivation parameters were presented. The study showed that collisions can be efficient when the adsorption of the polymer is thermodynamically favorable. Up to 94 percent of adsorption takes place at the kaolinite edge. Studies have shown that hydrogen bonding sites on the kaolinite disappear with increases in pH values. The impact of molecular level interactions on flocculation kinetics were assessed in order to determine collision efficiencies and aggregate breakage rates. A focused beam reflectance model was used to monitor flocculation kinetics in situ. The period over which reflectance was observed was coupled with the laser velocity to determine the chord length of the particle. The kinetics of flocculation were observed for a 10 minute period. The effects of pH, calcium additions, and EDTA chelating agent additions were investigated. The study showed that calcium additions accelerate the rate of flocculant growth dramatically, and provide a much higher collision efficiency. Flocculants formed in the presence of calcium were weaker. The presence of salts promoted polymer adsorption by non-specific Van der Waals forces. tabs., figs.

Deformation-induced phase transformation in 4H–SiC nanopillars

International Nuclear Information System (INIS)

Chen, Bin; Wang, Jun; Zhu, Yiwei; Liao, Xiaozhou; Lu, Chunsheng; Mai, Yiu-Wing; Ringer, Simon P.; Ke, Fujiu; Shen, Yaogen

2014-01-01

The deformation behaviour of single-crystal SiC nanopillars was studied by a combination of in situ deformation transmission electron microscopy and molecular dynamics simulations. An unexpected deformation-induced phase transformation from the 4H hexagonal structure to the 3C face-centred cubic structure was observed in these nanopillars at room temperature. Atomistic simulations revealed that the 4H to 3C phase transformation follows a stick–slip process with initiation and end stresses of 12.1–14.0 and 7.9–9.0 GPa, respectively. The experimentally measured stress of 9–10 GPa for the phase transformation falls within the range of these theoretical upper and lower stresses. The reasons for the phase transformation are discussed. The finding sheds light on the understanding of phase transformation in polytypic materials at low temperature

Secondary organic aerosol formation from semi- and intermediate-volatility organic compounds and glyoxal: Relevance of O/C as a tracer for aqueous multiphase chemistry

Science.gov (United States)

Waxman, Eleanor M.; Dzepina, Katja; Ervens, Barbara; Lee-Taylor, Julia; Aumont, Bernard; Jimenez, Jose L.; Madronich, Sasha; Volkamer, Rainer

2013-03-01

The role of aqueous multiphase chemistry in the formation of secondary organic aerosol (SOA) remains difficult to quantify. We investigate it here by testing the rapid formation of moderate oxygen-to-carbon (O/C) SOA during a case study in Mexico City. A novel laboratory-based glyoxal-SOA mechanism is applied to the field data, and explains why less gas-phase glyoxal mass is observed than predicted. Furthermore, we compare an explicit gas-phase chemical mechanism for SOA formation from semi- and intermediate-volatility organic compounds (S/IVOCs) with empirical parameterizations of S/IVOC aging. The mechanism representing our current understanding of chemical kinetics of S/IVOC oxidation combined with traditional SOA sources and mixing of background SOA underestimates the observed O/C by a factor of two at noon. Inclusion of glyoxal-SOA with O/C of 1.5 brings O/C predictions within measurement uncertainty, suggesting that field observations can be reconciled on reasonable time scales using laboratory-based empirical relationships for aqueous chemistry.

NEARSOL, Aqueous Speciation and Solubility of Actinides for Waste Disposal

International Nuclear Information System (INIS)

Leach, S.J.; Pryke, D.C.

1989-01-01

A - Description of program or function: NEARSOL models the aqueous speciation and solubility of actinides under near-field conditions for disposal using a simple thermodynamic approach. B - Method of solution: The program draws information from a thermodynamic data base consisting of solubility products and complex formation constants for all known species, and standard electrode potentials, at 25 C, corrected for ionic strength effects. By minimising the free energy of the system through a series of iterations, a precipitating solid phase is predicted which limits the solubility, and the concentration of the main aqueous species are calculated as a function of pH. Initially the program evaluates only hydroxide and carbonate species, but the effect of sulphate, phosphate and fluoride anions can also be included. The program is simple to use, requiring inputs of: 1. Actinide(s); 2. pH range; 3. Ionic strength; 4. Redox conditions; 5. Ligand concentrations. Functions are included to calculate the distribution of the protonated and un-protonated forms of carbonate and phosphate and the value of Eh as a function of pH under disposal conditions as required. The program can further evaluate the role of free calcium ions. C - Restrictions on the complexity of the problem: None

Dissolved organic carbon enhances the mass transfer of hydrophobic organic compounds from Nonaqueous Phase Liquids (NAPLs) into the aqueous phase

NARCIS (Netherlands)

Smith, K.E.C.; Thullner, M.; Wick, L.Y.; Harms, H.

2011-01-01

The hypothesis that dissolved organic carbon (DOC) enhances the mass transfer of hydrophobic organic compounds from nonaqueous phase liquids (NAPLs) into the aqueous phase above that attributable to dissolved molecular diffusion alone was tested. In controlled experiments, mass transfer rates of

Analysis of continuous fermentation processes in aqueous two-phase systems

Energy Technology Data Exchange (ETDEWEB)

Jarzebski, A B; Malinowski, J J [Polish Academy of Sciences, Gliwice (Poland). Inst. of Chemical Engineering; Goma, G; Soucaille, P [INSA, 31 - Toulouse (France). Dept. de Genie Biochimique et Alimentaire

1992-05-01

Simulations of continuous ethanol or acetonobutylic fermentations in aqueous two-phase systems show that at high substrate feed concentrations it is possible to obtain solvent productivities about 25-40% higher than in conventional systems with cell recycle if the biomass bleed rate is kept about one tenth of the value of D. (orig.).

Cloud-point extraction of green-polymers from Cupriavidus necator lysate using thermoseparating-based aqueous two-phase extraction.

Science.gov (United States)

Leong, Yoong Kit; Lan, John Chi-Wei; Loh, Hwei-San; Ling, Tau Chuan; Ooi, Chien Wei; Show, Pau Loke

2017-03-01

Polyhydroxyalkanoates (PHAs), a class of renewable and biodegradable green polymers, have gained attraction as a potential substitute for the conventional plastics due to the increasing concern towards environmental pollution as well as the rapidly depleting petroleum reserve. Nevertheless, the high cost of downstream processing of PHA has been a bottleneck for the wide adoption of PHAs. Among the options of PHAs recovery techniques, aqueous two-phase extraction (ATPE) outshines the others by having the advantages of providing a mild environment for bioseparation, being green and non-toxic, the capability to handle a large operating volume and easily scaled-up. Utilizing unique properties of thermo-responsive polymer which has decreasing solubility in its aqueous solution as the temperature rises, cloud point extraction (CPE) is an ATPE technique that allows its phase-forming component to be recycled and reused. A thorough literature review has shown that this is the first time isolation and recovery of PHAs from Cupriavidus necator H16 via CPE was reported. The optimum condition for PHAs extraction (recovery yield of 94.8% and purification factor of 1.42 fold) was achieved under the conditions of 20 wt/wt % ethylene oxide-propylene oxide (EOPO) with molecular weight of 3900 g/mol and 10 mM of sodium chloride addition at thermoseparating temperature of 60°C with crude feedstock limit of 37.5 wt/wt %. Recycling and reutilization of EOPO 3900 can be done at least twice with satisfying yield and PF. CPE has been demonstrated as an effective technique for the extraction of PHAs from microbial crude culture. Copyright © 2016 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

A Layered Solution Crystal Growth Technique and the Crystal Structure of (C 6H 5C 2H 4NH 3) 2PbCl 4

Science.gov (United States)

Mitzi, D. B.

1999-07-01

Single crystals of the organic-inorganic perovskite (C6H5C2H4NH3)2PbCl4 have been grown at room temperature using a layered solution approach. The bottom solution layer, contained within a long straight tube, consists of PbCl2 dissolved in concentrated aqueous HCl. A less dense layer of methanol is carefully placed on top of the HCl/PbCl2 solution using a syringe. Finally, a stoichiometric quantity of C6H5C2H4NH2 (relative to the PbCl2) is added to the top of the column. As the layers slowly diffuse together, well-formed crystals of (C6H5C2H4NH3)2PbCl4 appear near the interface between the HCl/PbCl2 and C6H5C2H4NH2 solutions. The thick, plate-like crystals are well suited for X-ray crystallography studies. Room temperature intensity data were refined using a triclinic (Poverline1) cell (a=11.1463(3) Å, b=11.2181(3) Å, c=17.6966(5) Å, α= 99.173(1)°, β=104.634(1)°, γ=89.999(1)°, V=2111.8(1) Å3, Z=4, Rf/Rw=0.031/0.044). The organic-inorganic layered perovskite structure features well-ordered sheets of corner-sharing distorted PbCl6 octahedra separated by bilayers of phenethylammonium cations. Tilting and rotation of the PbCl6 octahedra within the perovskite sheets, coupled with organic cation ordering, leads to the unusual in-sheet 2ap×2ap superstructure, where ap is the lattice constant for the ideal cubic perovskite.

Superhard nanocomposite nc-TiC/a-C:H film fabricated by filtered cathodic vacuum arc technique

International Nuclear Information System (INIS)

Wang Yaohui; Zhang Xu; Wu Xianying; Zhang Huixing; Zhang Xiaoji

2008-01-01

Superhard nanocomposite nc-TiC/a-C:H films, with an excellent combination of high elastic recovery, low friction coefficient and good H/E ratio, were prepared by filtered cathodic vacuum arc technique using the C 2 H 2 gas as the precursor. The effect of C 2 H 2 flow rate on the microstructure, phase composition, mechanical and tribological properties of nanocomposite nc-TiC/a-C:H films have been investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy disperse spectroscopy (EDS), microindentation and tribotester measurements. It was observed that the C 2 H 2 flow rate significantly affected the Ti content and hardness of films. Furthermore, by selecting the proper value for C 2 H 2 flow rate, 20 sccm, one can deposit the nanocomposite film nc-TiC/a-C:H with excellent properties such as superhardness (66.4 GPa), high elastic recovery (83.3%) and high H/E ratio (0.13)

Prediction of pH-dependent aqueous solubility of druglike molecules

DEFF Research Database (Denmark)

Hansen, Niclas Tue; Kouskoumvekaki, Irene; Jørgensen, Flemming Steen

2012-01-01

In the present work, the Henderson-Hasselbalch (HH) equation has been employed for the development of a tool for the prediction of pH-dependent aqueous solubility of drugs and drug candidates. A new prediction method for the intrinsic solubility was developed, based on artificial neural networks...

Platinum-Catalyzed, Terminal-Selective C(sp(3))-H Oxidation of Aliphatic Amines.

Science.gov (United States)

Lee, Melissa; Sanford, Melanie S

2015-10-14

This Communication describes the terminal-selective, Pt-catalyzed C(sp(3))-H oxidation of aliphatic amines without the requirement for directing groups. CuCl2 is employed as a stoichiometric oxidant, and the reactions proceed in high yield at Pt loadings as low as 1 mol%. These transformations are conducted in the presence of sulfuric acid, which reacts with the amine substrates in situ to form ammonium salts. We propose that protonation of the amine serves at least three important roles: (i) it renders the substrates soluble in the aqueous reaction medium; (ii) it limits binding of the amine nitrogen to Pt or Cu; and (iii) it electronically deactivates the C-H bonds proximal to the nitrogen center. We demonstrate that this strategy is effective for the terminal-selective C(sp(3))-H oxidation of a variety of primary, secondary, and tertiary amines.

A spectrophotometric study of aqueous Au(III) halide-hydroxide complexes at 25-80 °C

Science.gov (United States)

Usher, Al; McPhail, D. C.; Brugger, Joël

2009-06-01

The mobility and transport of gold in low-temperature waters and brines is affected by the aqueous speciation of gold, which is sensitive in particular to pH, oxidation and halide concentrations. In this study, we use UV-Vis spectrophotometry to identify and measure the thermodynamic properties of Au(III) aqueous complexes with chloride, bromide and hydroxide. Au(III) forms stable square planar complexes with hydroxide and halide ligands. Based on systematic changes in the absorption spectra of solutions in three binary systems NaCl-NaBr, NaCl-NaOH and NaBr-NaOH at 25 °C, we derived log dissociation constants for the following mixed and end-member halide and hydroxide complexes: [AuCl 3Br] -, [AuCl 2Br 2] -, [AuBr 3Cl] - and [AuBr 4] -; [AuCl 3(OH)] -, [AuCl 2(OH) 2] -, [AuCl(OH) 3] - and [Au(OH) 4] -; and [AuBr 3(OH)] -, [AuBr 2(OH) 2] - and [AuBr(OH) 3] -. These are the first reported results for the mixed chloride-bromide complexes. Increasing temperature to 80 °C resulted in an increase in the stability of the mixed chloride-bromide complexes, relative to the end-member chloride and bromide complexes. For the [AuCl (4-n)(OH) n] - series of complexes ( n = 0-4), there is an excellent agreement between our spectrophotometric results and previous electrochemical results of Chateau et al. [Chateau et al. (1966)]. In other experiments, the iodide ion (I -) was found to be unstable in the presence of Au(III), oxidizing rapidly to I 2(g) and causing Au to precipitate. Predicted Au(III) speciation indicates that Au(III) chloride-bromide complexes can be important in transporting gold in brines with high bromide-chloride ratios (e.g., >0.05), under oxidizing (atmospheric), acidic (pH < 5) conditions. Native gold solubility under atmospheric oxygen conditions is predicted to increase with decreasing pH in acidic conditions, increasing pH in alkaline conditions, increasing chloride, especially at acid pH, and increasing bromide for bromide/chloride ratios greater than 0

Structural, Mechanical, Anisotropic, and Thermal Properties of AlAs in oC12 and hP6 Phases under Pressure

Directory of Open Access Journals (Sweden)

Wei Zhang

2018-05-01

Full Text Available The structural, mechanical, anisotropic, and thermal properties of oC12-AlAs and hP6-AlAs under pressure have been investigated by employing first-principles calculations based on density functional theory. The elastic constants, bulk modulus, shear modulus, Young’s modulus, B/G ratio, and Poisson’s ratio for oC12-AlAs and hP6-AlAs have been systematically investigated. The results show that oC12-AlAs and hP6-AlAs are mechanically stable within the considered pressure. Through the study of lattice constants (a, b, and c with pressure, we find that the incompressibility of oC12-AlAs and hP6-AlAs is the largest along the c-axis. At 0 GPa, the bulk modulus B of oC12-AlAs, hP6-AlAs, and diamond-AlAs are 76 GPa, 75 GPa, and 74 Gpa, respectively, indicating that oC12-AlAs and hP6-AlAs have a better capability of resistance to volume than diamond-AlAs. The pressure of transition from brittleness to ductility for oC12-AlAs and hP6-AlAs are 1.21 GPa and 2.11 GPa, respectively. The anisotropy of Young’s modulus shows that oC12-AlAs and hP6-AlAs have greater isotropy than diamond-AlAs. To obtain the thermodynamic properties of oC12-AlAs and hP6-AlAs, the sound velocities, Debye temperature, and minimum thermal conductivity at considered pressure were investigated systematically. At ambient pressure, oC12-AlAs (463 K and hP6-AlAs (471 K have a higher Debye temperature than diamond-AlAs (433 K. At T = 300 K, hP6-AlAs (0.822 W/cm·K−1 has the best thermal conductivity of the three phases, and oC12-AlAs (0.809 W/cm·K−1 is much close to diamond-AlAs (0.813 W/cm·K−1.

Theoretical Investigation of the Structural Stabilities of Ceria Surfaces and Supported Metal Nanocluster in Vapor and Aqueous Phases

Energy Technology Data Exchange (ETDEWEB)

Ren, Zhibo [State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China; Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Liu, Ning [State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China; Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Chen, Biaohua [State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China; Li, Jianwei [State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China; Mei, Donghai [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, Richland, Washington 99352, United States

2018-01-25

Understanding the structural stability and dynamics at the interface between the solid metal oxide and aqueous phase is significant in a variety of industrial applications including heterogeneous catalysis and environmental remediation. In the present work, the stabilities of three low-index ceria (CeO2) surfaces, i.e., (111), (110) and (100) in vapor and aqueous phases were studied using ab initio molecular dynamics simulations and density functional theory (DFT) calculations. Gibbs surface free energies as a function of temperature, water partial pressure, and water coverages were calculated using DFT based atomistic thermodynamic approach. On the basis of surface free energies, the morphology and exposed surface structures of the CeO2 nanoparticle were predicted using Wulff construction principle. It is found that the partially hydroxylated (111) and (100) are two major surface structures of CeO2 nanoparticles in vapor phase at ambient temperature (300 K). As the temperature increases, the fully dehydrated (111) surface gradually becomes the most dominant surface structure. While in aqueous phase, the exposed surface of the CeO2 nanoparticle is dominated by the hydroxylated (110) structure at 393 K. Finally, the morphology and stability of a cuboctahedron Pt13 nanocluster supported on CeO2 surfaces in both gas and aqueous phases were investigated. In gas phase, the supported Pt13 nanocluster has the tendency to wetting the CeO2 surface due to the strong metal-support interaction. The calculated interaction energies suggest the CeO2(110) surface provides the best stability for the Pt13 nanocluster. The CeO2 supported Pt13 nanoclusters are oxidized. Compared to the gas phase, the morphology of the CeO2 supported Pt13 nanocluster is less distorted due to the solvation effect provided by surrounding water molecules in aqueous phase. More electrons are transferred from the Pt13 nanocluster to the CeO2 support, implying the supported Pt13 nanocluster is further

Sustainable Carbon/Carbon Supercapacitors Operating Down to -40 °C in Aqueous Electrolyte Made with Cholinium Salt.

Science.gov (United States)

Abbas, Qamar; Béguin, François

2018-03-09

Cholinium chloride at a concentration of 5 mol kg -1 in water is proposed as a low-cost and environmentally friendly aqueous electrolyte, enabling extension of the operating range of carbon/carbon supercapacitors (SCs) down to -40 °C. This solution has a pH close to neutrality (pH 6.1) and high conductivity of 88 mS cm -1 at 24 °C. The supercapacitors demonstrate a high capacitance of 126 F g -1 (per mass of one electrode) and long life span at voltages up to 1.5 V. At -40 °C, the carbon/carbon SCs display excellent electrochemical characteristics with only slightly reduced capacitance of 106 F g -1 and negligible ohmic losses. As compared to previous works, where antifreezing additives were introduced in traditional neutral electrolytes, the low solubility of the salt and related poor conductivity of the solution is no longer an issue, which makes cholinium salt aqueous solutions very promising for SCs operating at sub-ambient temperature conditions. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electroviscous dissipation in aqueous electrolyte films with overlapping electric double layers

OpenAIRE

Liu, Fei; Klaassen, Aram Harold; Zhao, Cunlu; Mugele, Friedrich Gunther; van den Ende, Henricus T.M.

2018-01-01

We use dynamic atomic force microscopy (AFM) to investigate the forces involved in squeezing out thin films of aqueous electrolyte between an AFM tip and silica substrates at variable pH and salt concentration. From amplitude and phase of the AFM signal we determine both conservative and dissipative components of the tip sample interaction forces. The measured dissipation is enhanced by up to a factor of 5 at tip–sample separations of ≈ one Debye length compared to the expectations based on c...

Purification of pectinase from mango (Mangifera indica L. cv. Chokanan) waste using an aqueous organic phase system: a potential low cost source of the enzyme.

Science.gov (United States)

Amid, Mehrnoush; Abdul Manap, Mohd Yazid; Mustafa, Shuhaimi

2013-07-15

As a novel method of purification, an aqueous organic phase system (AOPS) was employed to purify pectinase from mango waste. The effect of different parameters, such as the alcohol concentration (ethanol, 1-propanol, and 2-propanol), the salt type and concentration (ammonium sulfate, potassium phosphate and sodium citrate), the feed stock crude load, the aqueous phase pH and NaCl concentration, were investigated in the recovery of pectinase from mango peel. The partition coefficient (K), selectivity (S), purification factor (PF) and yield (Y, %) were investigated in this study as important parameters for the evaluation of enzyme recovery. The desirable partition efficiency for pectinase purification was achieved in an AOPS of 19% (w/w) ethanol and 22% (w/w) potassium phosphate in the presence of 5% (w/w) NaCl at pH 7.0. Based on the system, the purification factor of pectinase was enhanced 11.7, with a high yield of 97.1%. Copyright © 2013 Elsevier B.V. All rights reserved.

A Novel Aqueous Micellar Two-Phase System Composed of Surfactant and Sorbitol for Purification of Pectinase Enzyme from Psidium guajava and Recycling Phase Components

Science.gov (United States)

Murshid, Fara Syazana; Manap, Mohd Yazid; Hussin, Muhaini

2015-01-01

A novel aqueous two-phase system composed of a surfactant and sorbitol was employed for the first time to purify pectinase from Psidium guajava. The influences of different parameters, including the type and concentration of the surfactant and the concentration and composition of the surfactant/sorbitol ratio, on the partitioning behavior and recovery of pectinase were investigated. Moreover, the effects of system pH and the crude load on purification fold and the yield of purified pectinase were studied. The experimental results indicated that the pectinase was partitioned into surfactant-rich top phase, and the impurities were partitioned into the sorbitol-rich bottom phase with the novel method involving an ATPS composed of 26% (w/w) Triton X-100 and 23% (w/w) sorbitol at 54.2% of the TLL crude load of 20% (w/w) at pH 6.0. The enzyme was successfully recovered by this method with a high purification factor of 15.2 and a yield of 98.3%, whereas the phase components were also recovered and recycled at rates above 96%. This study demonstrated that this novel ATPS method can be used as an efficient and economical alternative to the traditional ATPS for the purification and recovery of the valuable enzyme. PMID:25756051

A novel aqueous micellar two-phase system composed of surfactant and sorbitol for purification of pectinase enzyme from Psidium guajava and recycling phase components.

Science.gov (United States)

Amid, Mehrnoush; Murshid, Fara Syazana; Manap, Mohd Yazid; Hussin, Muhaini

2015-01-01

A novel aqueous two-phase system composed of a surfactant and sorbitol was employed for the first time to purify pectinase from Psidium guajava. The influences of different parameters, including the type and concentration of the surfactant and the concentration and composition of the surfactant/sorbitol ratio, on the partitioning behavior and recovery of pectinase were investigated. Moreover, the effects of system pH and the crude load on purification fold and the yield of purified pectinase were studied. The experimental results indicated that the pectinase was partitioned into surfactant-rich top phase, and the impurities were partitioned into the sorbitol-rich bottom phase with the novel method involving an ATPS composed of 26% (w/w) Triton X-100 and 23% (w/w) sorbitol at 54.2% of the TLL crude load of 20% (w/w) at pH 6.0. The enzyme was successfully recovered by this method with a high purification factor of 15.2 and a yield of 98.3%, whereas the phase components were also recovered and recycled at rates above 96%. This study demonstrated that this novel ATPS method can be used as an efficient and economical alternative to the traditional ATPS for the purification and recovery of the valuable enzyme.

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

Neutron quasi-elastic scattering study of translational motions in the smectic H, C and A phases of TBBA

International Nuclear Information System (INIS)

Dianoux, A.J.; Volino, F.; Heidemann, A.; Hervet, H.

1975-01-01

Neutron quasi-elastic scattering experiments in the smectic H, C and A phases of TBBA are presented, using the high resolution backscattering technique. The data are analyzed in terms of translational motion and are characterized by an apparent self diffusion coefficient Dsub(ap). The physical meaning of Dsub(ap) is discussed in terms of the true bulk self diffusion tensor and other kinds of translational motions [fr

Characterization of μc-Si:H/a-Si:H tandem solar cell structures by spectroscopic ellipsometry

International Nuclear Information System (INIS)

Murata, Daisuke; Yuguchi, Tetsuya; Fujiwara, Hiroyuki

2014-01-01

In order to perform the structural characterization of Si thin-film solar cells having submicron-size rough textured surfaces, we have developed an optical model that can be utilized for the spectroscopic ellipsometry (SE) analysis of a multilayer solar cell structure consisting of hydrogenated amorphous silicon (a-Si:H) and microcrystalline silicon (μc-Si:H) layers fabricated on textured SnO 2 :F substrates. To represent the structural non-uniformity in the textured structure, the optical response has been calculated from two regions with different thicknesses of the Si layers. Moreover, in the optical model, the interface layers are modeled by multilayer structures assuming two-phase composites and the volume fractions of the phases in the layers are controlled by the structural curvature factor. The polarized reflection from the μc-Si:H layer that shows extensive surface roughening during the growth has also been modeled. In this study, a state-of-the-art solar cell structure with the textured μc-Si:H (2000 nm)/ZnO (100 nm)/a-Si:H (200 nm)/SnO 2 :F/glass substrate structure has been characterized. The μc-Si:H/a-Si:H textured structure deduced from our SE analysis shows remarkable agreement with that observed by transmission electron microscopy. From the above results, we have demonstrated the high-precision characterization of highly-textured μc-Si:H/a-Si:H solar cell structures. - Highlights: • Characterization of textured μc-Si:H/a-Si:H solar cell structures by ellipsometry • A new optical model using surface area and multilayer models • High precision characterization of submicron-range rough interface structures

pH dependent green synthesis of gold nanoparticles by completely C6-carboxylated curdlan under high temperature and various pH conditions.

Science.gov (United States)

Qiu, Wen-Yi; Wang, Kai; Wang, Yao-Yao; Ding, Zhi-Chao; Wu, Li-Xia; Cai, Wu-Dan; Yan, Jing-Kun

2018-01-01

A C6-carboxylated curdlan (C6-Cc) obtained from 4-acetamido-TEMPO-mediated oxidation of curdlan was used both as a reducing and stabilizing agent for green synthesis of pH-responsive AuNPs, which was carried out by controlling the pH of the C6-Cc solution at a high temperature (100°C). C6-Cc presented a semi-flexible random coil chain in the aqueous medium at pH 5.5 and became more expanded and rigid in alkaline conditions (pH 7.1-12.0), though the primary chemical structure of C6-Cc was virtually unchanged with the pH variation. The AuNPs prepared with C6-Cc at various pHs were characterized by various instrumental measurements. The shapes and sizes of AuNPs were found to be strongly dependent on the pH of the C6-Cc solution. The C6-Cc-decorated AuNPs exhibited a more well-dispersed spherical morphology with smaller particle sizes under alkaline conditions (pH 7.1-12.0). Through this study, a facile, simple, and green method has been demonstrated for preparation of stimuli-sensitive AuNPs using biocompatible polyanionic polysaccharides. Copyright © 2017 Elsevier B.V. All rights reserved.

Indirect phase transition of TiC, ZrC, and HfC crystal structures

Energy Technology Data Exchange (ETDEWEB)

Abavare, Eric K.K.; Dodoo, Samuel N.A. [Department of Physics, Kwame Nkrumah University of Science and Technology, Kumasi (Ghana); Uchida, Kazuyuki; Oshiyama, Atsushi [Department of Applied Physics, The University of Tokyo, Hongo, Tokyo (Japan); Nkurumah-Buandoh, George K.; Yaya, Abu [Department of Physics, University of Ghana, Legon (Ghana)

2016-06-15

We have performed first-principles calculations to analyze the electronic structures, static, and dynamical structural stabilities of the pressure-induced phase transformation of refractory compounds (transition-metal carbides) from NaCl-type (B1) to CsCl-type (B2) via zinc-blende phase using the plane-wave pseudopotential approach in the framework of the generalized gradient approximation (GGA) for the exchange and correlation functional. The ground-state properties, equilibrium lattice constant, bulk moduli, and band structures are determined for the stoichiometry of the compounds and compared with known experimental and theoretical values. We find that the phase-transition pressure for the indirect phase transition from B1→B2 via zinc-blende structure is about 17-fold for TiC, 12-fold for both ZrC and HfC, respectively, when compared with the direct phase transition. Calculated phonon instability exists for the CsCl-B2 phase, which can prevent the structures from forming and contrary to the zinc-blende and the NaCl-B1 phases. The band dispersion and electronic density of states for B1 and B2 crystal phases were explored and found to indicate metallic character in contrast with the zinc-blende phase, which has a pseudogap opening in the bandgap region suggesting a semiconducting property and also a frequency gap in the phonon spectrum. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Cyanide and antimony thermodynamic database for the aqueous species and solids for the EPA-MINTEQ geochemical code

International Nuclear Information System (INIS)

Sehmel, G.A.

1989-05-01

Thermodynamic data for aqueous species and solids that contain cyanide and antimony were tabulated from several commonly accepted, published sources of thermodynamic data and recent journal article. The review does not include gases or organic complexes of either antimony or cyanide, nor does the review include the sulfur compounds of cyanide. The basic thermodynamic data, ΔG/sub f,298//sup o/, ΔH/sub f,298//sup o/, and S/sub f//sup o/ values, were chosen to represent each solid phase and aqueous species for which data were available in the appropriate standard state. From these data the equilibrium constants (log K/sub r,298//sup o/) and enthalpies of reaction (ΔH/sub r,298//sup o/) at 298 K (25/degree/C) were calculated for reactions involving the formation of these aqueous species and solids from the basic components. 34 refs., 14 tabs

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

International Nuclear Information System (INIS)

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

2014-01-01

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

Compositional, structural and mechanical characteristics of nc-TiC/a-C:H nanocomposite films

International Nuclear Information System (INIS)

Wang Yaohui; Zhang Xu; Wu Xianying; Zhang Huixing; Zhang Xiaoji

2008-01-01

Nanocomposite nc-TiC/a-C:H films, with an unusual combination of superhardness, high elastic modulus and high elastic recovery, are prepared by filtered cathodic vacuum arc technique using the C 2 H 2 gas as the precursor. The effects of filter coil current on compositional, structural and mechanical properties of the nc-TiC/a-C:H films have been investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy disperse spectroscopy (EDS), microindentation and tribotester measurements. XPS and Raman analyses show that composition and nanostructure of the nc-TiC/a-C:H films can be changed by varying the filter coil current. By selecting the proper value of filter coil current, 2.5 A, one can remarkably enhance the mechanical properties of films such as superhardness (43.6 GPa). The superhardness can be ascribed to the phase variation and the nanostructure.

Tribological properties of TiC/a-C:H nanocomposite coatings prepared via HiPIMS

Science.gov (United States)

Sánchez-López, J. C.; Dominguez-Meister, S.; Rojas, T. C.; Colasuonno, M.; Bazzan, M.; Patelli, A.

2018-05-01

High power impulse magnetron sputtering (HiPIMS) technology has been employed to prepare TiC/a-C:H nanocomposite coatings from a titanium target in acetylene (C2H2) reactive atmospheres. Gas fluxes were varied from 1.3 to 4.4 sccm to obtain C/Ti ratios from 2 to 15 as measured by electron probe microanalysis (EPMA). X-ray diffraction and transmission electron microscopy demonstrate the presence of TiC nanocrystals embedded in an amorphous carbon-based matrix. The hardness properties decrease from 17 to 10 GPa as the carbon content increases. The tribological properties were measured using a pin-on-disk tribometer in ambient air (RH = 30-40%) at 10 cm/s with 5 N of applied load against 6-mm 100Cr6 balls. The friction coefficient and the film wear rates are gradually improved from 0.3 and 7 × 10-6 mm3/N m to 0.15 and 2 × 10-7 mm3/N m, respectively, by increasing the C2H2 flux. To understand the tribological processes appearing at the interface and to elucidate the wear mechanism, microstructural and chemical investigations of the coatings were performed before and after the friction test. EPMA, X-ray photoelectron and electron energy-loss spectroscopies were employed to obtain an estimation of the fraction of the a-C:H phase, which can be correlated with the tribological behavior. Examination of the friction counterfaces (ball and track) by Raman microanalysis reveals an increased ordering of the amorphous carbon phase concomitant with friction reduction. The tribological results were compared with similar TiC/a-C(:H) composites prepared by the conventional direct current process.

Modeling photodegradation kinetics of three systemic neonicotinoids-dinotefuran, imidacloprid, and thiamethoxam-in aqueous and soil environment.

Science.gov (United States)

Kurwadkar, Sudarshan; Evans, Amanda; DeWinne, Dustan; White, Peter; Mitchell, Forrest

2016-07-01

Environmental presence and retention of commonly used neonicotinoid insecticides such as dinotefuran (DNT), imidacloprid (IMD), and thiamethoxam (THM) are a cause for concern and prevention because of their potential toxicity to nontarget species. In the present study the kinetics of the photodegradation of these insecticides were investigated in water and soil compartments under natural light conditions. The results suggest that these insecticides are fairly unstable in both aqueous and soil environments when exposed to natural sunlight. All 3 insecticides exhibit strong first-order degradation rate kinetics in the aqueous phase, with rate constants kDNT , kIMD , and kTHM of 0.20 h(-1) , 0.30 h(-1) , and 0.18 h(-1) , respectively. However, in the soil phase, the modeled photodegradation kinetics appear to be biphasic, with optimal rate constants k1DNT and k2DNT of 0.0198 h(-1) and 0.0022 h(-1) and k1THM and k2THM of 0.0053 h(-1) and 0.0014 h(-1) , respectively. Differentially, in the soil phase, imidacloprid appears to follow the first-order rate kinetics with a kIMD of 0.0013 h(-1) . These results indicate that all 3 neonicotinoids are photodegradable, with higher degradation rates in aqueous environments relative to soil environments. In addition, soil-encapsulated imidacloprid appears to degrade slowly compared with dinotefuran and thiamethoxam and does not emulate the faster degradation rates observed in the aqueous phase. Environ Toxicol Chem 2016;35:1718-1726. © 2015 SETAC. © 2015 SETAC.

Study of surface activity of piroxicam at the interface of palm oil esters and various aqueous phases.

Science.gov (United States)

Abdulkarim, Muthanna Fawzy; Abdullah, Ghassan Zuhair; Chitneni, Mallikarjun; Yam, Mun Fei; Mahdi, Elrashid Saleh; Salman, Ibrahim Muhammad; Ameer, Omar Ziad; Sattar, Munavvar Abdul; Basri, Mahiran; Noor, Azmin Mohd

2012-04-01

The surface activity of some non-steroidal anti-inflammatory agents like ibuprofen was investigated extensively. This fact has attracted the researchers to extend this behavior to other agents like piroxicam. Piroxicam molecules are expected to orient at the interface of oil and aqueous phase. The aim of this study was, firstly, to assess the surface and interfacial tension behaviour of newly synthesised palm oil esters and various pH phosphate buffers. Furthermore, the surface and interfacial tension activity of piroxicam was studied. All the measurements of surface and interfacial tension were made using the tensiometer. The study revealed that piroxicam has no effect on surface tension values of all pH phosphate buffers and palm oil esters. Similarly, various concentrations of piroxicam did not affect the interfacial tensions between the oil phase and the buffer phases. Accordingly, the interfacial tension values of all mixtures of oil and phosphate buffers were considerably high which indicates the immiscibility. It could be concluded that piroxicam has no surface activity. Additionally, there is no surface pressure activity of piroxicam at the interface of plam oil esters and phosphate buffers in the presence of Tweens and Spans.

Ionic liquid and aqueous two-phase extraction based on salting-out coupled with high-performance liquid chromatography for the determination of seven rare ginsenosides in Xue-Sai-Tong injection.

Science.gov (United States)

Li, Lan-Jie; Jin, Yong-Ri; Wang, Xiao-Zhong; Liu, Ying; Wu, Qian; Shi, Xiao-Lei; Li, Xu-Wen

2015-09-01

A method of ionic liquid salt aqueous two-phase extraction coupled with high-performance liquid chromatography has been developed for the analysis of seven rare ginsenosides including Rg6 , F4 , 20(S)-Rg3 , 20(R)-Rg3 , Rk3 , Rk1 , and Rg5 in Xue-Sai-Tong injection. The injection was mixed with ionic liquid 1-butyl-3-methylimidazolium bromide aqueous solution, and a mixture was obtained. With the addition of sodium dodecyl sulfate and dipotassium phosphate into the mixture, the aqueous two-phase mixture was formed after ultrasonic treatment and centrifuged. Rare ginsenosides were extracted into the upper phase. To obtain a high extraction factors, various influences were considered systematically, such as the volume of ionic liquid, the category and amount of salts, the amount of sodium dodecyl sulfate, the pH value of system, and the time of ultrasonic treatment. Under the optimal condition, rare ginsenosides in Xue-Sai-Tong injection were enriched and detected, the recoveries of seven rare ginsenosides ranged from 90.05 to 112.55%, while relative standard deviations were lower than 2.50%. The developed method was reliable, rapid and sensitive for the determination of seven rare ginsenosides in the injections. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of H/D isotope substitution on physicochemical properties of aqueous solutions of urea and thiourea

International Nuclear Information System (INIS)

Jelinska-Kazimierczuk, M.; Szydlowski, J.

2001-01-01

The influence of the H/D isotope substitution on excess volumes, partial molar volumes, viscosity and ultrasound speed in aqueous solutions of urea and thiourea are studied at 20 o C. The excess volume of the solutions studied is relatively small - however, it is negative in urea and positive in thiourea solutions. On the other hand, the deuteration affects the excess volume in both solutions in the same way: deuterated systems show smaller deviation from additivity than regular ones. The speed of sound in the systems studied increases monotonously with concentration , but its isotope effect decreases as the concentration increases. The curves of viscosity are monotonous too, but isotope effect of kinematic viscosity is practically the same in the whole concentration range studied. The present results for urea and thiourea aqueous solutions are compared with those previously obtained for amide- water systems. (author)

One-pot aqueous phase catalytic conversion of sorbitol to gasoline over nickel catalyst

International Nuclear Information System (INIS)

Weng, Yujing; Qiu, Songbai; Xu, Ying; Ding, Mingyue; Chen, Lungang; Zhang, Qi; Ma, Longlong; Wang, Tiejun

2015-01-01

Highlights: • Directly production gasoline (C5–C12 alkanes) from biomass-derived sugar alcohol sorbitol. • Temperature of STG (553–593 K) was lower than that of traditional methanol to gasoline (MTG) (623–773 K). • Gasoline yield of 46.9% and C7–C12 hydrocarbons reached up to 45.5% in the gasoline products. - Abstract: The carbon chain extension and hydrodeoxygenation steps play critical roles in the high-energy-density hydrocarbons production. In this paper, a systematic study had been carried out to investigate one-pot aqueous phase catalytic conversion of sorbitol to gasoline (STG) over bifunctional Ni-based catalysts. Characterization technologies of N 2 physisorption, X-ray diffraction (XRD), Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and NH 3 temperature-programmed desorption (NH 3 -TPD) were used to study the textural properties, phase compositions, acid behavior and morphologies of the catalysts. The catalytic performances were tested in a fixed bed reactor. It was found that the physically mixed Ni/HZSM-5 and Ni/silica-gel (mesoporous SG) catalyst realized the carbon chain extension and exhibited excellent performances on hydrodeoxygenation (HDO) reaction (46.9% of gasoline (C5–C12) yield and 45.5% of C7–C12 hydrocarbons in the gasoline products). Especially, the temperature of STG (553–593 K) was lower obviously than that of the traditional methanol to gasoline (MTG) process (623–773 K). It provided a novel transformation of sorbitol to long-chain alkanes by one-pot process over the bifunctional catalyst (Ni@HZSM-5/SG), wherein hydrodeoxygenation, ketonization and aldol condensation steps were integrated

Extraction and high-performance liquid chromatographic analysis of C60, C70, and [6,6]-phenyl C61-butyric acid methyl ester in synthetic and natural waters.

Science.gov (United States)

Bouchard, Dermont; Ma, Xin

2008-09-05

Studies have shown that C(60) fullerene can form stable colloidal suspensions in water that result in C(60) aqueous concentrations many orders of magnitude above C(60)'s aqueous solubility; however, quantitative methods for the analysis of C(60) and other fullerenes in environmental media are scarce. Using a 80/20v/v toluene-acetonitrile mobile phase and a 4.6 mm x 150 mm Cosmosil 5micron PYE column, C(60), C(70), and PCBM ([6,6]-phenyl C(61)-butyric acid methyl ester) were fully resolved. Selectivity factors (alpha) for C(60) relative to PCBM and C(70) relative to C(60) were 3.18 and 2.19, respectively. The best analytical wavelengths for the fullerenes were determined to be 330, 333, and 333 nm with log molar absorption coefficients (log epsilon) of 4.63, 4.82, and 4.60 for PCBM, C(60), C(70), respectively. Extraction and quantitation of all three fullerenes in aqueous suspensions over a range of pH (4-10) and ionic strengths were very good. Whole-method quantification limits for ground and surface suspensions were 2.87, 2.48, and 6.54 microg/L for PCBM, C(60), and C(70), respectively.

Direct conversion of h-BN into c-BN and formation of epitaxial c-BN/diamond heterostructures

International Nuclear Information System (INIS)

Narayan, Jagdish; Bhaumik, Anagh; Xu, Weizong

2016-01-01

We have created a new state of BN (named Q-BN) through rapid melting and super undercooling and quenching by using nanosecond laser pulses. Phase pure c-BN is formed either by direct quenching of super undercooled liquid or by nucleation and growth from Q-BN. Thus, a direct conversion of hexagonal boron nitride (h-BN) into phase-pure cubic boron nitride (c-BN) is achieved by nanosecond pulsed laser melting at ambient temperatures and atmospheric pressure in air. According to the P-T phase diagram, the transformation from h-BN into c-BN under equilibrium processing can occur only at high temperatures and pressures, as the hBN-cBN-Liquid triple point is at 3500 K/9.5 GPa or 3700 K/7.0 GPa with a recent theoretical refinement. Using nonequilibrium nanosecond laser melting, we have created super undercooled state and shifted this triple point to as low as 2800 K and atmospheric pressure. The rapid quenching from super undercooled state leads to the formation of a new phase, named as Q-BN. We present detailed characterization of Q-BN and c-BN layers by using Raman spectroscopy, high-resolution scanning electron microscopy, electron-back-scatter diffraction, high-resolution TEM, and electron energy loss spectroscopy, and discuss the mechanism of formation of nanodots, nanoneedles, microneedles, and single-crystal c-BN on sapphire substrate. We have also deposited diamond by pulsed laser deposition of carbon on c-BN and created c-BN/diamond heterostructures, where c-BN acts as a template for epitaxial diamond growth. We discuss the mechanism of epitaxial c-BN and diamond growth on lattice matching c-BN template under pulsed laser evaporation of amorphous carbon, and the impact of this discovery on a variety of applications.

Removal of 2,4-Dichlorophenolyxacetic acid (2,4-D) herbicide in the aqueous phase using modified granular activated carbon

OpenAIRE

Dehghani, Mansooreh; Nasseri, Simin; Karamimanesh, Mojtaba

2014-01-01

Background Low cost 2,4-Dichlorophenolyxacetic acid (2,4-D) widely used in controlling broad-leafed weeds is frequently detected in water resources. The main objectives of this research were focused on evaluating the feasibility of using granular activated carbon modified with acid to remove 2,4-D from aqueous phase, determining its removal efficiency and assessing the adsorption kinetics. Results The present study was conducted at bench-scale method. The influence of different pH (3–9), the ...

Gas-Phase Oxidation of Aqueous Ethanol by Nanoparticle Vanadia/Anatase Catalysts

DEFF Research Database (Denmark)

Jørgensen, Betina; Kristensen, Steffen Buus; Kunov-Kruse, Andreas Jonas

2009-01-01

The gas-phase oxidation of aqueous ethanol with dioxygen has been examined with a new nanoparticle V2O5/TiO2 catalyst. Product selectivity could to a large extent be controlled by small alterations of reaction parameters, allowing production of acetaldehyde at a selectivity higher than 90%, near...

Investigation into the effects of temperature and stirring rate on the solid-phase extraction of diuron from water using a C18 extraction disk.

Science.gov (United States)

Green, C E; Abraham, M H

2000-07-14

A novel experimental method for determining the equilibrium constant, Keq, and the uptake rate constant, kup, for the solid-phase extraction (SPE) of diuron from water using a C18 Empore extraction disk is reported. Log Keq and log kup are determined at 7.0, 11.0, 18.0 and 23.0 degrees C and for stirring rates of 100, 200 and 400 rpm. From a Van 't Hoff plot of log Keq versus T-1 the enthalpy of sorption, delta H0, is shown to be negative which indicates that the thermodynamic process of uptake is exothermic. The rate of stirring has no effect on log Keq over the temperature range 7.0-23.0 degrees C. The enthalpy of activation, delta H0, calculated from Arrhenius plots of log kup versus T-1 at 100, 200 and 400 rpm show that the kinetic process of uptake is endothermic. At 100 rpm the rate of uptake is limited by the aqueous diffusion of diuron. At 200 rpm or greater the aqueous diffusion layer around the disk is sufficiently small to prevent diffusion from being a limiting factor. The method described in this paper is limited to the analysis of analytes that contain a significant UV chromophore and are relatively soluble in water, but it can also be used to investigate pH and salinity effects on the SPE of diuron from water.

Decomposition reaction rate of BCl3-C3H6(propene)-H2 in the gas phase.

Science.gov (United States)

Xiao, Jun; Su, Kehe; Liu, Yan; Ren, Hongjiang; Zeng, Qingfeng; Cheng, Laifei; Zhang, Litong

2012-07-05

The decomposition reaction rate in the BCl(3)-C(3)H(6)-H(2) gas phase reaction system in preparing boron carbides was investigated based on the most favorable reaction pathways proposed by Jiang et al. [Theor. Chem. Accs. 2010, 127, 519] and Yang et al. [J. Theor. Comput. Chem. 2012, 11, 53]. The rate constants of all the elementary reactions were evaluated with the variational transition state theory. The vibrational frequencies for the stationary points as well as the selected points along the minimum energy paths (MEPs) were calculated with density functional theory at the B3PW91/6-311G(d,p) level and the energies were refined with the accurate model chemistry method G3(MP2). For the elementary reaction associated with a transition state, the MEP was obtained with the intrinsic reaction coordinates, while for the elementary reaction without transition state, the relaxed potential energy surface scan was employed to obtain the MEP. The rate constants were calculated for temperatures within 200-2000 K and fitted into three-parameter Arrhenius expressions. The reaction rates were investigated by using the COMSOL software to solve numerically the coupled differential rate equations. The results show that the reactions are, consistent with the experiments, appropriate at 1100-1500 K with the reaction time of 30 s for 1100 K, 1.5 s for 1200 K, 0.12 s for 1300 K, 0.011 s for 1400 K, or 0.001 s for 1500 K, for propene being almost completely consumed. The completely dissociated species, boron carbides C(3)B, C(2)B, and CB, have very low concentrations, and C(3)B is the main product at higher temperatures, while C(2)B is the main product at lower temperatures. For the reaction time 1 s, all these concentrations approach into a nearly constant. The maximum value (in mol/m(3)) is for the highest temperature 1500 K with the orders of -13, -17, and -23 for C(3)B, C(2)B, and CB, respectively. It was also found that the logarithm of the overall reaction rate and reciprocal

Structure and molecular motion in three modifications of a binary C23H48-C24H50 paraffin

International Nuclear Information System (INIS)

Craievich, A.F.; Denicolo, I.; Doucet, J.

1983-01-01

The temperature dependence of the intensities of the (00l) X-ray reflections from a binary paraffin (C 23 H 48 -25% C 24 H 50 ) was determined, in order to obtain structure parameters related to the molecular motion and intramolecular defects. The long lattice spacing was also determined as a function of the temperature. All of these results are compared with the temperature dependence of the ratio of the two short lattice parameters. The clear correlation of all of these experimental results provides a close characterization of the molecular structures and their changes at the several solid state phase transitions. (Author) [pt

In situ x-ray observations of the diamond formation process in the C-H sub 2 O-MgO system

CERN Document Server

Okada, T; Shimomura, O

2002-01-01

The diamond formation process in aqueous fluid catalyst under high-pressure and high-temperature conditions has been observed for the first time. Quench experiments and in situ x-ray diffraction experiments using synchrotron radiation have been performed upon a mixture of brucite (Mg(OH) sub 2) and graphite as the starting material. It was confirmed that brucite decomposed into periclase and H sub 2 O at 3.6 GPa and 1050 deg. C while its complete melting occurred at 6.2 GPa and 1150 deg. C, indicating that the solubility of MgO in H sub 2 O greatly increases with increasing pressure. The conversion of carbon from its graphite to its diamond form in aqueous fluid was observed at 7.7 GPa and 1835 deg. C.

Photochemical processing of aldrin and dieldrin in frozen aqueous solutions under arctic field conditions

Energy Technology Data Exchange (ETDEWEB)

Rowland, Glenn A.; Bausch, Alexandra R. [Department of Chemistry, Villanova University, Villanova, PA 19085 (United States); Grannas, Amanda M., E-mail: amanda.grannas@villanova.edu [Department of Chemistry, Villanova University, Villanova, PA 19085 (United States)

2011-05-15

Organochlorine (OC) contaminants are transported to the Polar Regions, where they have the potential to bioaccumulate, presenting a threat to the health of wildlife and indigenous communities. They deposit onto snowpack during winter, and accumulate until spring, when they experience prolonged solar irradiation until snowmelt occurs. Photochemical degradation rates for aldrin and dieldrin, in frozen aqueous solution made from MilliQ water, 500 {mu}M hydrogen peroxide solution or locally-collected melted snow were measured in a field campaign near Barrow, AK, during spring-summer 2008. Significant photoprocessing of both pesticides occurs; the reactions depend on temperature, depth within the snowpack and whether the predominant phase is ice or liquid water. The effect of species present in natural snowpack is comparable to 500 {mu}M hydrogen peroxide, pointing to the potential significance of snowpack-mediated reactions. Aldrin samples frozen at near 0 deg. C were more reactive than comparable liquid samples, implying that the microenvironments experienced on frozen ice surfaces are an important consideration. - Highlights: > Photodegradation rates for aldrin and dieldrin in frozen aqueous solutions made from MilliQ water, H{sub 2}O{sub 2} or melted snow are reported. > Photoprocessing depends on temperature, depth beneath the snowpack surface and dominant phase. > Species present in natural snowpack have a photosensitizing effect comparable to 500 {mu}M H{sub 2}O{sub 2}. > Aldrin samples frozen at near 0 deg. C were more reactive than comparable liquid samples. > Collectively we find that frozen aqueous surfaces play a unique role in aldrin and dieldrin photochemistry. - A field study finds that frozen aqueous solutions of aldrin and dieldrin undergo photochemical degradation under arctic snowpack conditions. The reactions are enhanced in frozen systems and by natural snowpack constituents.

Interconversion of η3-H2SiRR' σ-complexes and 16-electron silylene complexes via reversible H-H or C-H elimination.

Science.gov (United States)

Lipke, Mark C; Neumeyer, Felix; Tilley, T Don

2014-04-23

Solid samples of η(3)-silane complexes [PhBP(Ph)3]RuH(η(3)-H2SiRR') (R,R' = Et2, 1a; PhMe, 1b; Ph2, 1c, MeMes, 1d) decompose when exposed to dynamic vacuum. Gas-phase H2/D2 exchange between isolated, solid samples of 1c-d3 and 1c indicate that a reversible elimination of H2 is the first step in the irreversible decomposition. An efficient solution-phase trap for hydrogen, the 16-electron ruthenium benzyl complex [PhBP(Ph)3]Ru[η(3)-CH2(3,5-Me2C6H3)] (3) reacts quantitatively with H2 in benzene via elimination of mesitylene to form the η(5)-cyclohexadienyl complex [PhBP(Ph)3]Ru(η(5)-C6H7) (4). This H2 trapping reaction was utilized to drive forward and quantify the elimination of H2 from 1b,d in solution, which resulted in the decomposition of 1b,d to form 4 and several organosilicon products that could not be identified. Reaction of {[PhBP(Ph)3]Ru(μ-Cl)}2 (2) with (THF)2Li(SiHMes2) forms a new η(3)-H2Si species [PhBP(Ph)3]Ru[CH2(2-(η(3)-H2SiMes)-3,5-Me2C6H2)] (5) which reacts with H2 to form the η(3)-H2SiMes2 complex [PhBP(Ph)3]RuH(η(3)-H2SiMes2) (1e). Complex 1e was identified by NMR spectroscopy prior to its decomposition by elimination of Mes2SiH2 to form 4. DFT calculations indicate that an isomer of 5, the 16-electron silylene complex [PhBP(Ph)3]Ru(μ-H)(═SiMes2), is only 2 kcal/mol higher in energy than 5. Treatment of 5 with XylNC (Xyl = 2,6-dimethylphenyl) resulted in trapping of [PhBP(Ph)3]Ru(μ-H)(═SiMes2) to form the 18-electron silylene complex [PhBP(Ph)3]Ru(CNXyl)(μ-H)(═SiMes2) (6). A closely related germylene complex [PhBP(Ph)3]Ru[CN(2,6-diphenyl-4-MeC6H2)](H)(═GeH(t)Bu) (8) was prepared from reaction of (t)BuGeH3 with the benzyl complex [PhBP(Ph)3]Ru[CN(2,6-diphenyl-4-MeC6H2)][η(1)-CH2(3,5-Me2C6H3)] (7). Single crystal XRD analysis indicated that unlike for 6, the hydride ligand in 8 is a terminal hydride that does not engage in 3c-2e Ru-H → Ge bonding. Complex 1b is an effective precatalyst for the catalytic Ge-H dehydrocoupling

Characterization of bovine serum albumin partitioning behaviors in polymer-salt aqueous two-phase systems.

Science.gov (United States)

Chow, Yin Hui; Yap, Yee Jiun; Tan, Chin Ping; Anuar, Mohd Shamsul; Tejo, Bimo Ario; Show, Pau Loke; Ariff, Arbakariya Bin; Ng, Eng-Poh; Ling, Tau Chuan

2015-07-01

In this paper, a linear relationship is proposed relating the natural logarithm of partition coefficient, ln K for protein partitioning in poly (ethylene glycol) (PEG)-phosphate aqueous two-phase system (ATPS) to the square of tie-line length (TLL(2)). This relationship provides good fits (r(2) > 0.98) to the partition of bovine serum albumin (BSA) in PEG (1450 g/mol, 2000 g/mol, 3350 g/mol, and 4000 g/mol)-phosphate ATPS with TLL of 25.0-50.0% (w/w) at pH 7.0. Results also showed that the plot of ln K against pH for BSA partitioning in the ATPS containing 33.0% (w/w) PEG1450 and 8.0% (w/w) phosphate with varied working pH between 6.0 and 9.0 exhibited a linear relationship which is in good agreement (r(2) = 0.94) with the proposed relationship, ln K = α' pH + β'. These results suggested that both the relationships proposed could be applied to correlate and elucidate the partition behavior of biomolecules in the polymer-salt ATPS. The influence of other system parameters on the partition behavior of BSA was also investigated. An optimum BSA yield of 90.80% in the top phase and K of 2.40 was achieved in an ATPS constituted with 33.0% (w/w) PEG 1450 and 8.0% (w/w) phosphate in the presence of 8.5% (w/w) sodium chloride (NaCl) at pH 9.0 for 0.3% (w/w) BSA load. Copyright © 2014 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Defect-induced polytype transformations in LPE grown SiC epilayers on (1 1 1) 3C-SiC seeds grown by VLS on 6H-SiC

International Nuclear Information System (INIS)

Marinova, Maya; Zoulis, Georgios; Robert, Teddy; Mercier, Frederic; Mantzari, Alkioni; Galben, Irina; Kim-Hak, Olivier; Lorenzzi, Jean; Juillaguet, Sandrine; Chaussende, Didier; Ferro, Gabriel; Camassel, Jean; Polychroniadis, Efstathios K.

2009-01-01

The results of transmission electron microscopy (TEM) with low-temperature photoluminescence (LTPL) and Raman studies of liquid phase grown epilayers on top of a vapor liquid solid (VLS) grown 3C-SiC buffer layer are compared. While the 6H-SiC substrate was completely covered by the 3C-SiC seed after the first VLS process, degradation occurred during the early stage of the liquid phase epitaxy process. This resulted in polytype instabilities, such that several rhombohedral forms stabilized one after the other. These (21R-SiC, 57R-SiC) eventually led after few microns to a final transition back to 6H-SiC. This interplay of polytypes resulted in a complex optical signature, with specific LTPL and Raman features.

Cr6+-containing phases in the system CaO-Al2O3-CrO42--H2O at 23 °C

Science.gov (United States)

Pöllmann, Herbert; Auer, Stephan

2012-01-01

Synthesis and investigation of lamellar calcium aluminium hydroxy salts was performed to study the incorporation of chromate ions in the interlayer of lamellar calcium aluminium hydroxy salts. Different AFm-phases (calcium aluminate hydrate with alumina, ferric oxide, mono-anion phase) containing chromate were synthesized. These AFm-phases belong to the group of layered double hydroxides (LDHs). 3CaO·Al2O3·CaCrO4·nH2O and C3A·1/2Ca(OH)2·1/2CaCrO4·12H2O were obtained as pure phases and their different distinct interlayer water contents and properties determined. Solid solution of chromate-containing phases and tetracalcium-aluminate-hydrate (TCAH) were studied. The uptake of chromate into TCAH from solutions was proven. Chromate contents in solution decrease to <0.2 mg/l.

Vapor-Liquid Equilibrium in the Mixture 1,1-Difluoroethane C2H4F2 + C4H8 2-Methylpropene (EVLM1131, LB5730_E)

Science.gov (United States)

Cibulka, I.; Fontaine, J.-C.; Sosnkowska-Kehiaian, K.; Kehiaian, H. V.

This document is part of Subvolume A 'Binary Liquid Systems of Nonelectrolytes I' of Volume 26 'Heats of Mixing, Vapor-Liquid Equilibrium, and Volumetric Properties of Mixtures and Solutions' of Landolt-Börnstein Group IV 'Physical Chemistry'. It contains the Chapter 'Vapor-Liquid Equilibrium in the Mixture 1,1-Difluoroethane C2H4F2 + C4H8 2-Methylpropene (EVLM1131, LB5730_E)' providing data from direct measurement of pressure and mole fraction in vapor phase at variable mole fraction in liquid phase and constant temperature.

Hydrogen insertion in titanium carbide based thin films (nc-TiC{sub x}/a-C:H) - comparison with bulk TiC{sub x}

Energy Technology Data Exchange (ETDEWEB)

Nguyen, Julien; Jaoul, Cédric, E-mail: jaoul@ensil.unilim.fr; Glandut, Nicolas; Lefort, Pierre

2016-08-01

Nanocomposites composed of titanium carbide nanosized grains embedded in an amorphous hydrogenated carbon matrix (nc-TiC{sub x}/a-C:H) are prepared by hybrid Magnetron Sputtering - PECVD process using a titanium metal target and gaseous C{sub 6}H{sub 6}. By controlling the benzene flow rate, thin films with different carbon content are obtained. The structures of nc-TiC{sub x}/a-C:H materials are analyzed by X-ray diffraction, X-ray photoelectron and Raman spectroscopic methods. The electrochemical hydrogen insertion, as studied by cyclic voltammetry, strongly depends on the carbon content in the thin films. The correlation between the hydrogen insertion ability and the structure of materials are discussed. Furthermore, we show that the hydrogen insertion in these thin films reaches values much more significant than in bulk substoichiometric titanium carbide obtained by reactive sintering. - Highlights: • nc-TiC{sub x}/a-C:H thin films are prepared hybrid Magnetron Sputtering - PECVD process. • Different carbon contents are obtained by changing the hydrocarbon flowrate. • Expanded lattice parameter of the TiC{sub x} phase and a-C:H phase are observed. • Electrochemical hydrogen insertion strongly depends on the carbon content. • The maximum insertion is 22 times more important than bulk TiC{sub x}.

Apparent and partial molar volumes of long-chain alkyldimethylbenzylammonium chlorides and bromides in aqueous solutions at T=15 deg. C and T=25 deg. C

International Nuclear Information System (INIS)

Gonzalez-Perez, A.; Ruso, J.M.; Nimo, J.; Rodriguez, J.R.

2003-01-01

Density measurements of dodecyl- (C 12 DBACl), tetradecyl- (C 14 DBACl), hexadecyldimethylbenzylammonium chloride (C 16 DBACl) and of decyl- (C 10 DBABr) and dodecyldimethylbenzylammonium bromide (C 12 DBABr) in aqueous solutions at T=15 deg. C and T=25 deg. C have been carried out. From these results, apparent and partial molar volumes were calculated. Positive deviations from the Debye-Hueckel limiting law provide evidence for limited association at concentrations below the critical micelle concentration. The change of the apparent molar volume upon micellization was calculated. The relevant parameters have been presented in function of the alkyl chain length. Apparent molar volumes of the present compounds in the micellar phase, V phi m , and the change upon micellization, ΔV phi m , have been discussed in terms of temperature and type of counterion

γ-radiolysis of aqueous and aqueous-ethanol solutions of cobalt(3) cyanide complexes

International Nuclear Information System (INIS)

Kutsaev, V.G.; Potapov, I.A.; Rozenkevich, M.B.; Sakharovskij, Yu.A.; Bulgakova, G.P.; Zagorets, P.A.

1984-01-01

The method of stationary γ-radiolysis has been used to investigate Na 3 [Co 3 (CN) 6 ] and K 2 [Co 3 (CN) 5 H 2 O] reduction in aqueous solutions in the presence of NaCN, KCN, KCl and C 2 H 5 OH additions. [Co 2 (CN) 5 ] 3- ion is shown to be the product of reduction. Radiation-chemical yield increases in the presence of alkali metal cyanides and large quantities (10-20 vol.%) of C 2 H 5 OH. Energy consumption for radiation-chemical reduction of Co 3 cyanide complexes is 50 times lower than for photochemical one

Extractive separation of Al(III) and Ni(II) by Di-2-Ethylhexyl phosphoric acid-kerosene system from aqueous fluoride medium

International Nuclear Information System (INIS)

Islam, M.F.; Begum, D.A.; Rahman, M.; Rahman, M.S.

2009-01-01

In the study of the extractive separation of Al(III) and Ni(II) by di-2-ethylhexyl phosphoric acid D2EHPA-kerosene from aqueous fluoride medium, about 94% Al(III) and 2% Ni(II) were extracted with 0.3 M D2EHPA (pH 2.1 and temperature 30+-1 degree C). Extraction of Ni(II) decreased with increasing extractant concentration. D2EHPA-kerosene-fluoride system showed better extraction of Al(III) with higher extractant concentration and aqueous pH and vice versa for the extraction of Ni(II). The maximum separation factor (beta 1380) was obtained for Al(III) at 20 degree C and decreased to (beta 732) at 60 degree C. The separation of Al(III) from Ni(II) was favoured at normal temperature. Extraction followed the order Al(III), Ni(II). About 99% stripping of Al(III) was attained from the loaded 0.20 M D2EHPA. Much faster extraction of Al(III) compared to Ni(II) and preferential loading were shown by D2EHPA-kerosene in the presence of fluoride ion in the aqueous phase. Separation of Al(III) was the most outstanding from Ni-Al-F-complex solution. (author)

Violent flows in aqueous foams III: physical multi-phase model comparison with aqueous foam shock tube experiments

Science.gov (United States)

Redford, J. A.; Ghidaglia, J.-M.; Faure, S.

2018-06-01

Mitigation of blast waves in aqueous foams is a problem that has a strong dependence on multi-phase effects. Here, a simplified model is developed from the previous articles treating violent flows (D'Alesio et al. in Eur J Mech B Fluids 54:105-124, 2015; Faure and Ghidaglia in Eur J Mech B Fluids 30:341-359, 2011) to capture the essential phenomena. The key is to have two fluids with separate velocities to represent the liquid and gas phases. This allows for the interaction between the two phases, which may include terms for drag, heat transfer, mass transfer due to phase change, added mass effects, to be included explicitly in the model. A good test for the proposed model is provided by two experimental data sets that use a specially designed shock tube. The first experiment has a test section filled with spray droplets, and the second has a range of aqueous foams in the test section. A substantial attenuation of the shock wave is seen in both cases, but a large difference is observed in the sound speeds. The droplets cause no observable change from the air sound speed, while the foams have a reduced sound speed of approximately 50-75 m/s . In the model given here, an added mass term is introduced in the governing equations to capture the low sound speed. The match between simulation and experiment is found to be satisfactory for both droplets and the foam. This is especially good when considering the complexity of the physics and the effects that are unaccounted for, such as three-dimensionality and droplet atomisation. The resulting statistics illuminate the processes occurring in such flows.

Textural and mechanical characterization of C-S-H gels from hydration of synthetic T1-C3S, β-C2S and their blends

International Nuclear Information System (INIS)

Goni, S.; Guerrero, A.; Puertas, F.; Hernandez, M. S.; Palacios, M.; Dolado, J. S.; Zhu, W.; Howind, T.

2011-01-01

The textural and mechanical characterization of C-S-H gels formed from the hydration of pure T1-C 3 S, β-C 2 S and their blends are studied by Nitrogen sorption and nano indentation experiments. The surface area and nano porosity of C-S-H gels formed from the hydration of β-C 2 S and the 30-70 (T1-C 3 S and β-C 2 S mixture) are higher than those from hydration of T1-C 3 S, and 70-30, with the difference decreasing with hydration age. Such changes are well supported by findings of nano indentation study, which shows the greater relative volume of C-S-H phases with lower densities in the β-C 2 S and the 30-70 pastes. With the increase in hydration age, the relative volume of C-S-H phases with higher densities increased at the expenses of those with lower density. Important quantitative correlations were found among these textural characteristics and the mean chain length, determined from 2 9Si magic-angle-spinning (MAS) NMR, of the C-S-H gels. (Author) 36 refs.

Effects of pH on the stability of cyanidin and cyanidin 3-O-β-glucopyranoside in aqueous solution

Directory of Open Access Journals (Sweden)

Rakić Violeta P.

2015-01-01

Full Text Available The colour variation, colour intensity and stability at various pH values (2.0, 4.0, 7.0 and 9.0 of cyanidin 3-O-β-glucopyranoside (Cy3Glc and its aglycone cyanidin was investigated during a period of 8 hours storage at 25ºC. Our data showed that pH of aqueous solution had impact on spectroscopic profile of cyanidin and Cy3Glc. Beginning with the most acidic solutions, increasing the pH induce bathochromic shifts of absorbance maximum in the visible range for all examined pH values (with the exception pH 4.0 for cyanidin, while the presence of the 3-glucosidic substitution induce hypsochromic shift. Compared to cyanidin, Cy3Glc has higher colour intensity and higher stability in the whole pH range, except at pH 7.0. The 3-glucosidic substitution influences on the colour intensity of Cy3Glc in the alkaline region. After 8-hour incubation of Cy3Glc and cyanidin at pH 2.0 and 25 ºC, 99% of Cy3Glc and only 27% of cyanidin remained unchanged.

Evolution of 3C-SiC islands nucleated from a liquid phase on Si face α-SiC substrates

International Nuclear Information System (INIS)

Kim-Hak, Olivier; Ferro, Gabriel; Lorenzzi, Jean; Carole, Davy; Dazord, Jacques; Chaudouet, Patrick; Chaussende, Didier; Miele, Philippe

2010-01-01

The contact between α-SiC crystals and Si-Ge based melts provokes the nucleation of 3C-SiC islands on the crystal surface. Evolution of these islands as a function of various parameters was studied. On both 4H and 6H substrates, it was found that, after nucleation, 3C-SiC islands first enlarge and may form a complete 3C layer under certain conditions. The 3C deposit can then be dissolved by the liquid phase at high temperature or for prolonged contact at relatively moderate temperature. The graphite crucible is proposed to play a central role in these enlargement and dissolution mechanisms by providing extra carbon atoms on the seed surface (enlargement) or provoking thermal induced carbon transport toward the sidewall (dissolution). Several differences between the use of 4H and 6H substrates were also observed.

A review of catalytic aqueous-phase reforming of oxygenated hydrocarbons derived from biorefinery water fractions

NARCIS (Netherlands)

Coronado, I.; Stekrova, M.; Reinikainen, M.; Simell, P.; Lefferts, Leonardus; Lehtonen, J.

2016-01-01

Aqueous-phase reforming (APR) of oxygenated hydrocarbons is a process for the production of hydrogen and light alkanes. The reactants of APR remain in liquid phase during the reaction avoiding an energetically demanding vaporization-step compared to processes such as steam reforming (SR).

A new molybdenum trioxide hydrate MoO3.1/3H2O and a new monoclinic form of MoO3

International Nuclear Information System (INIS)

Harb, F.; Gerand, B.; Nowogrocki, G.; Figlarz, M.

1986-01-01

A new hydrate of molybdenum trioxide MoO 3 .1/3H 2 O has been obtained by hydrothermal treatment at 110 0 C of either aqueous suspensions of MoO 3 .2H 2 O or aqueous molybdic acid solutions. The hydrate crystallizes in the orthorhombic system, lattice parameters are given; a structural model is proposed by comparison with the isostructural WO 3 .1/3H 2 O phase. The dehydration of MoO 3 .1/3H 2 O leads to a new anhydrous molybdenum trioxide, monoclinic, the structure of which is of ReO 3 type [fr

The removal of toxic metals from liquid effluents by ion exchange resins. Part V: Nickel(II/H+/Dowex C400

Directory of Open Access Journals (Sweden)

Francisco José Alguacil

2017-11-01

Full Text Available The cationic exchange resin Dowex C400 was used to remove nickel(II from aqueous solutions of different pH values and under various experimental conditions: stirring speed of the aqueous solution/resin system, temperature, resin dosage and aqueous ionic strength. The selectivity of the resin was investigated against the presence of various metals in the aqueous solution, and the removal of nickel(II from aqueous solutions was also compared with results obtained using multiwalled carbon nanotubes or functionalized (carboxylic groups multiwalled carbon nanotubes as adsorbents. According to batch experimental data, best fit of the results is obtained with the Freundlich model, whereas the ion exchange process is best explained by the pseudo-first order model. Experimental data fit well to the moving boundary controlled model. Elution of the nickel(II loaded onto Dowex C400 resin is fully possible using acidic solutions.

Aqueous two-phase systems for extractive enzymatic hydrolysis of biomass

DEFF Research Database (Denmark)

Bussamra, Bianca Consorti; Azzoni, Sindelia Freitas; Mussatto, Solange I.

and enzymes, phase diagrams and volumetric ratios. The results of this project will make possible to design a process that enables high sugar concentration during the hydrolysis reaction, overcoming one of the biggest drawbacks regarding the production of second-generation ethanol: the enzymatic inhibition...... optimal aqueous two-phase systems for the separation of sugars and enzymes, which allow the development of an improved second-generation ethanol process.......Sugars derived from lignocellulosic materials are the main carbon sources in bio-based processes aiming to produce renewable fuels and chemicals. One of the major drawbacks during enzymatic hydrolysis of lignocellulosic materials to obtainsugars is the inhibition of enzymes by reaction products...

1,4-Iron Migration for Expedient Allene Annulations through Iron-Catalyzed C-H/N-H/C-O/C-H Functionalizations.

Science.gov (United States)

Mo, Jiayu; Müller, Thomas; Oliveira, João C A; Ackermann, Lutz

2018-06-25

C-H activation bears great potential for enabling sustainable molecular syntheses in a step- and atom-economical manner, with major advances having been realized with precious 4d and 5d transition metals. In contrast, we employed earth abundant, nontoxic iron catalysts for versatile allene annulations through a unique C-H/N-H/C-O/C-H functionalization sequence. The powerful iron catalysis occurred under external-oxidant-free conditions even at room temperature, while detailed mechanistic studies revealed an unprecedented 1,4-iron migration regime for facile C-H activations. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of fructose on the diffusion of potassium hydrogen phosphate in aqueous solutions at 25 °C

International Nuclear Information System (INIS)

Verissimo, Luis M.P.; Teigão, Joana M.M.; Ramos, M. Luísa; Burrows, Hugh D.; Esteso, Miguel A.; Ribeiro, Ana C.F.

2016-01-01

Highlights: • Diffusion coefficients of aqueous systems of fructose and potassium hydrogen phosphate measured with Lobo’s cell. • Influence of the fructose on the diffusion of potassium hydrogen phosphate. • Interactions between of hydrogen phosphate anion and fructose. - Abstract: Diffusion coefficients have been measured at 25 °C for potassium hydrogen phosphate (K_2HPO_4, 0.101 mol kg"−"1) in aqueous solutions containing various concentrations of fructose from (0.001 to 0.101) mol kg"−"1, using a conductimetric cell (the Lobo cell) coupled to an automatic data acquisition system. Significant effects of fructose were observed on the diffusion of K_2HPO_4 in these mixtures, which are attributed to the interaction between HPO_4"2"− anion (or other protonated forms) and fructose. Support for this comes from "1H and "1"3C NMR spectroscopy, which are compatible with binding between the anomeric forms of D-fructose and the HPO_4"2"− anion.

Phase Diagrams of the Aqueous Two-Phase Systems of Poly(ethylene glycol/Sodium Polyacrylate/Salts

Directory of Open Access Journals (Sweden)

Adalberto Pessoa Junior

2011-03-01

Full Text Available Aqueous two-phase systems consisting of polyethylene glycol (PEG, sodium polyacrylate (NaPAA, and a salt have been studied. The effects of the polymer size, salt type (NaCl, Na2SO4, sodium adipate and sodium azelate and salt concentrations on the position of the binodal curve were investigated. The investigated PEG molecules had a molar mass of 2,000 to 8,000 g/mol, while that of NaPAA was 8,000 g/mol. Experimental phase diagrams, and tie lines and calculated phase diagrams, based on Flory-Huggins theory of polymer solutions are presented. Due to strong enthalpic and entropic balancing forces, the hydrophobicity of the added salt has a strong influence on the position of the binodal, which could be reproduced by model calculations.

Solid phase microextraction speciation analysis of triclosan in aqueous mediacontaining sorbing nanoparticles

NARCIS (Netherlands)

Zielinska, K.

2014-01-01

Solid phase microextraction (SPME) is applied in the speciation analysis of the hydrophobic compound triclosan in an aqueous medium containing sorbing SiO2 nanoparticles (NPs). It is found that these NPs, as well as their complexes with triclosan, partition between the bulk medium and the solid

Aqueous polyethylene oxide solutions

International Nuclear Information System (INIS)

Breen, J.

1987-01-01

A number of aspects concerning the reorientation of polymer, water and ion hydration complexes have been studied in aqueous solution of polyethylene oxide (PEO). The polymer dynamics are investigated by 1 H-PEO and 13 C-PEO nuclear relaxation experiments. 162 refs.; 30 figs.; 19 tabs

Double labeling autoradiography. Cell kinetic studies with 3H- and 14C-thymidine

International Nuclear Information System (INIS)

Schultze, B.

1981-01-01

Examples of the multiple applicability of the double labeling method with 3 H- and 14 C-TdR are demonstrated. Double labeling with 3 H- and 14 C-TdR makes it possible to determine the cycle and its phases with high precision by modifying the usual percent labeled mitoses method with a single injection of 3 H-TdR. In addition, data is provided on the variances of the transit times through the cycle phases. For example, in the case of the jejunal crypt cells of the mouse, the transit times through successive cycle phases are uncorrelated. In the case of glial cells the double labeling method provides cell kinetic parameters despite the paucity of proliferating glial cells. In the adult untreated animal, glial cell mitoses are so rare that the percent labeled mitoses method can not be utilized. However, the S-phase duration can be measured by double labeling and the cycle time can be determined by the so-called method of labeled S phases. With the latter method the passage through the S phase of the 3 H-TdR-labeled S phase cells can be registered by injecting 14 C-TdR at different time intervals following 3 H-TdR application. In this way an S-phase duration of about 10 hr and a cycle time of about 20 hr was found for glial cells in the adult untreated mouse. An exchange of glial cells between the growth fraction and the nongrowth fraction has also been shown by double labeling. A quite different application of the double labeling method with 3H- and 14 C-TdR is the in vivo study of the cell cycle phase-specific effect of drugs used in chemotherapy of tumors. The effect of vincristine on these cells has been studied. Vincristine affects cells in S and G2 in such a manner that they are arrested during the next metaphase and subsequently become necrotic. It has no effect on G1 cells

Hydrogen production through aqueous-phase reforming of ethylene glycol in a washcoated microchannel

NARCIS (Netherlands)

Neira d'Angelo, M.F.; Ordomskiy, V.; Paunovic, V.; Schaaf, van der J.; Schouten, J.C.; Nijhuis, T.A.

2013-01-01

Aqueous-phase reforming (APR) of biocarbohydrates is conducted in a catalytically stable washcoated microreactor where multiphase hydrogen removal enhances hydrogen efficiency. Single microchannel experiments are conducted following a simplified model based on the microreactor concept. A coating

Recovery of Picloram and 2,4-Dichlorophenoxyacetic Acid from Aqueous Samples by Reversed-Phase Solid-Phase Extraction

Science.gov (United States)

Martha J.M. Wells; Jerry L. Michael

1987-01-01

Extensive preparation of samples before chromatographic analysis is usually the most time-consuming process in the determination of many organic compounds in environmental matrices. In the past, removal of some organic from aqueous solution was commonly done by liquid/liquid extraction. However, the introduction of stable, covalently bonded reversed-phase sorbents now...

Precipitation of Nd-Ca carbonate solid solution at 25 degrees C

International Nuclear Information System (INIS)

Carroll, S.A.

1993-01-01

The formation of a Nd-Ca carbonate solid solution was studied by monitoring the reactions of calcite with aqueous Nd, orthorhombic NdOHCO 3 (s) with aqueous Ca, and calcite with hexagonal Nd-carbonate solid phase as a function of time at 25 degrees C and controlled pCO 2 (g). All experiments reached steady state after 200 h of reaction. The dominant mechanism controlling the formation of the solid solution was precipitation of a Nd-Ca carbonate phase from the bulk solution as individual crystals or at the orthorhombic NdOHCO 3 (s)-solution interface. The lack of Nd adsorption or solid solution at the calcite-solution interface suggests that the solid solution was orthorhombic and may be modeled as a mixture of orthorhombic NdOHCO 3 (s) and aragonite. Orthorhombic NdOHCO 3 (s) was determined to be the stable Nd-carbonate phase in the Nd-CO 2 -H 2 O system at pCO 2 (g) 0.1 atmospheres at 25 degrees C. The equilibrium constant corrected to zero ionic strength for orthorhombic NdOHCO 3 (s) solubility is 10 10.41(±0.29) for the following: NdOHCO 3 (s) + 3H + = Nd 3+ + CO 2 (g) + H 2 O. Results are discussed in relation to radioactive waste disposal by burial, and specifically in relation to americium chemistry

Synthesis of C60(OH)18-20 in aqueous alkaline solution under O2-atmosphere

International Nuclear Information System (INIS)

Alves, Gustavo Catao; Ladeira, Luiz Orlando; Righi, Ariete; Krambrock, Klaus; Pinheiro, Mauricio Veloso B.; Calado, Hallen Daniel; Gil, Rossimiriam Pereira de Freitas

2006-01-01

In this work we report on an alternative synthesis of water-soluble fullerenes known as fullerols, aiming for biomedical applications. The synthesis is based on a process in which polyethylene glycol (PEG400) is used as phase-transfer catalyst between fullerene/benzene and aqueous NaOH solutions. The polyhydroxylation of the fullerenes occurs in the NaOH solution under a continuous flow of O 2 to enhance the reaction yield. The resulting compound was characterized with infrared spectroscopy, nuclear magnetic resonance, thermo-gravimetric analysis and optical absorption. The formation of C 60 (OH) 18-20 in high yields was confirmed. (author)

Textural and mechanical characterization of C-S-H gels from hydration of synthetic T1-C{sub 3}S, {beta}-C{sub 2}S and their blends; Caracterizacion textural y mecanica de geles C-S-H formados en la hidratacion de muestras sinteticas T1-C{sub 3}S, {beta}-C{sub 2}S y sus mezclas

Energy Technology Data Exchange (ETDEWEB)

Goni, S.; Guerrero, A.; Puertas, F.; Hernandez, M. S.; Palacios, M.; Dolado, J. S.; Zhu, W.; Howind, T.

2011-07-01

The textural and mechanical characterization of C-S-H gels formed from the hydration of pure T1-C{sub 3}S, {beta}-C{sub 2}S and their blends are studied by Nitrogen sorption and nano indentation experiments. The surface area and nano porosity of C-S-H gels formed from the hydration of {beta}-C{sub 2}S and the 30-70 (T1-C{sub 3}S and {beta}-C{sub 2}S mixture) are higher than those from hydration of T1-C{sub 3}S, and 70-30, with the difference decreasing with hydration age. Such changes are well supported by findings of nano indentation study, which shows the greater relative volume of C-S-H phases with lower densities in the {beta}-C{sub 2}S and the 30-70 pastes. With the increase in hydration age, the relative volume of C-S-H phases with higher densities increased at the expenses of those with lower density. Important quantitative correlations were found among these textural characteristics and the mean chain length, determined from {sup 2}9Si magic-angle-spinning (MAS) NMR, of the C-S-H gels. (Author) 36 refs.

Hydrogen production by steam reforming of bio-oil aqueous fraction over Co-Fe/ZSM-5

Science.gov (United States)

Chen, Mingqiang; Wang, Yishuang; Liang, Tian; Yang, Zhonglian

2018-02-01

A series of Co-Fe/ZSM-5 catalysts were prepared by impregnation method and their catalytic performance under steam reforming bio-oil aqueous fraction (SRBAF). The as-prepared catalysts were characterized by XRD, BET, and SEM. The characterization results revealed the Co-Fe alloy phase was formed in Co0.5Fe0.5/ZSM-5 catalyst, and this catalyst exhibited unique pore volume (0.28 cm3/g) and pore size (8.4 nm). The results of experiment demonstrated the addition of Fe species could significantly increase C conversion and H2 yield, and the formation of Co-Fe alloy effectively inhibited methanation reaction and improved water-gas shift (WGS) reaction. The highest H2 yield (81%) and C conversion (85%) was obtained at the following reaction conditions: 2.5 g of C0.5F0.5/Z catalyst, T = 700 °C, S/C = 10-14,.feed flow rate was 10.0 gbio-oil/h, N2 flow rate was 0.16 L/min.

Photodegradation of emamectin benzoate in aqueous solutions

International Nuclear Information System (INIS)

Mushtaq, M.; Chukwudebe, A.C.; Wrzesinski, C.; Allen, L.R.S.; Luffer-Atlas, D.; Arison, B.H.

1998-01-01

The half-life of [ 14 C]4'-deoxy-4'-(epi-methylamino)avermectin B1a (MAB1a) benzoate (1 ppm) photodegradation in buffer (pH 7), natural pond water, and sensitized buffer (1% acetone in pH 7 buffer) determined at Three Bridges, NJ (latitude approximately 40 degrees N) during the fall season under natural sunlight was 22, 7, and 1 days, respectively. The half-life of [ 14 C]MAB1a benzoate (10-12 ppm) photodegradation in buffer (pH 7) containing 1% (v/v) acetonitrile, ethanol, or acetone as cosolvent under continuous exposure with a xenon lamp was 64.5, 8.5, or 0.5 days, respectively. The photoisomer 8,9-Z-MAB1a, 8a-hydroxy-MAB1a, and unknown polar residues were found in light-exposed samples of MAB1a in buffer and natural pond water. In light-exposed sensitized buffer samples, 8a-oxo-MAB1a and MAB1a-10,11-14,15-diepoxide were additional products. Very polar residues found in the organic and aqueous phases after extraction increased with time, and their formation followed the order sensitized buffer natural pond water buffer. (author)

Iron oxide functionalized graphene nano-composite for dispersive solid phase extraction of chemical warfare agents from aqueous samples.

Science.gov (United States)

Chinthakindi, Sridhar; Purohit, Ajay; Singh, Varoon; Tak, Vijay; Goud, D Raghavender; Dubey, D K; Pardasani, Deepak

2015-05-15

Present study deals with the preparation and evaluation of graphene based magnetic nano-composite for dispersive solid phase extraction of Chemical Weapons Convention (CWC) relevant chemicals from aqueous samples. Nano-composite, Fe3O4@SiO2-G was synthesized by covalently bonding silica coated Fe3O4 onto the graphene sheets. Nerve agents (NA), Sulfur mustard (SM) and their non-toxic environmental markers were the target analytes. Extraction parameters like amount of sorbent, extraction time and desorption conditions were optimized. Dispersion of 20 milligram of sorbent in 200mL of water sample for 20min. followed by methanol/chloroform extraction produced average to good recoveries (27-94%) of targeted analytes. Recoveries of real agents exhibited great dependency upon sample pH and ionic strength. Sarin produced maximum recovery under mild acidic conditions (56% at pH 5) while VX demanded alkaline media (83% at pH 9). Salts presence in the aqueous samples was found to be advantageous, raising the recoveries to as high as 94% for SM. Excellent limits of detection (LOD) for sulphur mustard and VX (0.11ngmL(-1) and 0.19ngmL(-1) respectively) proved the utility of the developed method for the off-site analysis of CWC relevant chemicals. Copyright © 2015 Elsevier B.V. All rights reserved.

Characterization of aqueous two phase systems by combining lab-on-a-chip technology with robotic liquid handling stations.

Science.gov (United States)

Amrhein, Sven; Schwab, Marie-Luise; Hoffmann, Marc; Hubbuch, Jürgen

2014-11-07

Over the last decade, the use of design of experiment approaches in combination with fully automated high throughput (HTP) compatible screenings supported by robotic liquid handling stations (LHS), adequate fast analytics and data processing has been developed in the biopharmaceutical industry into a strategy of high throughput process development (HTPD) resulting in lower experimental effort, sample reduction and an overall higher degree of process optimization. Apart from HTP technologies, lab-on-a-chip technology has experienced an enormous growth in the last years and allows further reduction of sample consumption. A combination of LHS and lab-on-a-chip technology is highly desirable and realized in the present work to characterize aqueous two phase systems with respect to tie lines. In particular, a new high throughput compatible approach for the characterization of aqueous two phase systems regarding tie lines by exploiting differences in phase densities is presented. Densities were measured by a standalone micro fluidic liquid density sensor, which was integrated into a liquid handling station by means of a developed generic Tip2World interface. This combination of liquid handling stations and lab-on-a-chip technology enables fast, fully automated, and highly accurate density measurements. The presented approach was used to determine the phase diagram of ATPSs composed of potassium phosphate (pH 7) and polyethylene glycol (PEG) with a molecular weight of 300, 400, 600 and 1000 Da respectively in the presence and in the absence of 3% (w/w) sodium chloride. Considering the whole ATPS characterization process, two complete ATPSs could be characterized within 24h, including four runs per ATPS for binodal curve determination (less than 45 min/run), and tie line determination (less than 45 min/run for ATPS preparation and 8h for density determination), which can be performed fully automated over night without requiring man power. The presented methodology provides

Biphase Cobalt-Manganese Oxide with High Capacity and Rate Performance for Aqueous Sodium-Ion Electrochemical Energy Storage

Energy Technology Data Exchange (ETDEWEB)

Shan, Xiaoqiang [Univ. of New Hampshire, Durham, NH (United States). Dept. of Chemical Engineering; Charles, Daniel S. [Univ. of New Hampshire, Durham, NH (United States). Dept. of Chemical Engineering; Xu, Wenqian [Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS). X-ray Science Division; Feygenson, Mikhail [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division and Spallation Neutron Source (SNS) outstation Juelich Centre for Neutron Science (JCNS), Forschungszentrum Juelich GmbH; Su, Dong [Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN); Teng, Xiaowei [Univ. of New Hampshire, Durham, NH (United States). Dept. of Chemical Engineering

2017-11-22

Manganese-based metal oxide electrode materials are of great importance in electrochemical energy storage for their favorable redox behavior, low cost and environmental-friendliness. However, their storage capacity and cycle life in aqueous Na-ion electrolytes is not satisfactory. In this paper, we report the development of a bi-phase cobalt-manganese oxide (Co-Mn-O) nanostructured electrode material, comprised of a layered MnO₂.H₂O birnessite phase and a (Co_0.83Mn_0.13Va_0.04)tetra(Co_0.38Mn_1.62)_octaO_3.72 (Va: vacancy; tetra: tetrahedral sites; octa: octahedral sites) spinel phase, verified by neutron total scattering and pair distribution function analyses. The bi-phase Co-Mn-O material demonstrates an excellent storage capacity towards Na-ions in an aqueous electrolyte (121 mA h g^-1 at a scan rate of 1 mV s^-1 in the half-cell and 81 mA h g^-1 at a current density of 2 A g^-1 after 5000 cycles in full-cells), as well as high rate performance (57 mA h g^-1 a rate of 360 C). Electro-kinetic analysis and in situ X-ray diffraction measurements further confirm that the synergistic interaction between the spinel and layered phases, as well as the vacancy of the tetrahedral sites of spinel phase, contribute to the improved capacity and rate performance of the Co-Mn-O material by facilitating both diffusion-limited redox and capacitive charge storage processes.

Effect of N,C-ITO on Composite N,C-Ti/N,C-ITO/ITO Electrode Used for Photoelectrochemical Degradation of Aqueous Pollutant with Simultaneous Hydrogen Production

Directory of Open Access Journals (Sweden)

Kee-Rong Wu

2012-01-01

Full Text Available This study reports the effect of N,C-ITO (indium tin oxide layer on composite N,C-TiO2/N,C-ITO/ITO (Ti/TO electrode used for efficient photoelectrocatalytic (PEC degradation of aqueous pollutant with simultaneous hydrogen production. The structural properties of the composite Ti/TO electrode that determined by X-ray diffraction and Raman scattering, show primarily the crystallized anatase TiO2 phase and distinct diffraction patterns of polycrystalline In2O3 phase. Under solar light illumination, the composite Ti/TO electrode yields simultaneously a hydrogen production rate of 12.0 μmol cm−2 h−1 and degradation rate constant of  cm−2 h−1 in organic pollutant. It implies that the overlaid N,C-TiO2 layer enhances not only the photocurrent response of the composite Ti/TO electrode at entire applied potentials, but also the flat band potential; a shift of about 0.1 V toward cathode, which is desperately beneficial in the PEC process. In light of the X-ray photoelectron spectroscopy findings, these results are attributable partly to the synergetic effect of N,C-codoping into the TiO2 and ITO lattices on their band gap narrowing and photosensitizing as well. Thus, the Ti/TO electrode can potentially serve an efficient PEC electrode for simultaneous pollutant degradation and hydrogen production.

Ru decorated carbon nanotubes - a promising catalyst for reforming bio-based acetic acid in the aqueous phase

NARCIS (Netherlands)

de Vlieger, Dennis; Lefferts, Leonardus; Seshan, Kulathuiyer

2014-01-01

Catalytic reforming of biomass derived waste streams in the aqueous phase is a promising process for the production of sustainable hydrogen. Acetic acid will be a major component (up to 20 wt%) in many anticipated gasification feed streams (e.g. the aqueous fraction of pyrolysis oil). Conventional

Study of the unimolecular decompositions of the (C3H6)+2 and (c-C3H6)+2 complexes

International Nuclear Information System (INIS)

Tzeng, W.; Ono, Y.; Linn, S.H.; Ng, C.Y.

1985-01-01

The major product channels identified in the unimolecular decompositions ofC 3 H + 6 xC 3 H 6 and c-C 3 H + 6 xc-C 3 H 6 in the total energy [neutral (C 3 H 6 ) 2 or (c-C 3 H 6 ) 2 heat of formation plus excitation energy] range of approx.230--450 kcal/mol are C 3 H + 7 +C 3 H 5 , C 4 H + 7 +C 2 H 5 , C 4 H + 8 +C 2 H 4 , and C 5 H + 9 +CH 3 . The measured appearance energy for C 4 H + 7 (9.54 +- 0.04 eV) from (C 3 H 6 ) 2 is equal to the thermochemical threshold for the formation of C 4 H + 7 +C 2 H 5 from (C 3 H 6 ) 2 , indicating that the exit potential energy barrier for the ion--molecule reaction C 3 H + 6 +C 3 H 6 →C 4 H + 7 +C 2 H 5 is negligible. There is evidence that the formations of C 4 H + 7 +C 2 H 4 +H from (C 3 H 6 ) + 2 and (c-C 3 H 6 ) + 2 also proceed with high probabilities when they are energetically allowed. The variations of the relative abundances for C 4 H + 7 ,C 4 H + 8 , and C 5 H + 9 from (C 3 H 6 ) + 2 and (c-C 3 H 6 ) + 2 as a function of ionizing photon energy are in qualitative agreement, suggesting that (C 3 H 6 ) + 2 and (c-C 3 H 6 ) + 2 rearrange to similar C 6 H + 12 isomers prior to fragmentation. The fact that C 6 H + 11 is found to be a primary ion from the unimolecular decomposition of (c-C 3 H 6 ) + 2 but not (C 3 H 6 ) + 2 supports the conclusion that the distribution of C 6 H + 12 collision complexes involved in the C 3 H + 6 +C 3 H 6 reactions is different from that in the cyclopropane ion--molecule reactions

Adsorption of As(III), As(V) and Cu(II) on zirconium oxide immobilized alginate beads in aqueous phase.

Science.gov (United States)

Kwon, Oh-Hun; Kim, Jong-Oh; Cho, Dong-Wan; Kumar, Rahul; Baek, Seung Han; Kurade, Mayur B; Jeon, Byong-Hun

2016-10-01

A composite adsorbent to remove arsenite [As(III)], arsenate [As(V)], and copper [Cu(II)] from aqueous phase was synthesized by immobilizing zirconium oxide on alginate beads (ZOAB). The composition (wt%) of ZOAB (Zr-34.0; O-32.7; C-21.3; Ca-1.0) was confirmed by energy dispersive X-ray (EDX) analysis. Sorption studies were conducted on single and binary sorbate systems, and the effects of contact time, initial adsorbate concentration, and pH on the adsorption performance of ZOAB (pHPZC = 4.3) were monitored. The sorption process for As(III)/As(V) and Cu(II) reached an equilibrium state within 240 h and 24 h, respectively, with maximum sorption capacities of 32.3, 28.5, and 69.9 mg g(-1), respectively. The addition of Cu(II) was favorable for As(V) sorption in contrast to As(III). In the presence of 48.6 mg L(-1) Cu(II), the sorption capacity of As(V) increased from 1.5 to 3.8 mg g(-1) after 240 h. The sorption data for As(III)/As(V) and Cu(II) conformed the Freundlich and Langmuir isotherm models, respectively. The adsorption of As(III), As(V), and Cu(II) followed pseudo second order kinetics. The effect of arsenic species on Cu(II) sorption was insignificant. The results of present study demonstrated that the synthesized sorbent could be useful for the simultaneous removal of both anionic and cationic contaminants from wastewaters. Copyright © 2016 Elsevier Ltd. All rights reserved.

Extraction and purification of capsaicin from capsicum oleoresin using an aqueous two-phase system combined with chromatography.

Science.gov (United States)

Fan, Yong; Lu, Yan-Min; Yu, Bin; Tan, Cong-Ping; Cui, Bo

2017-09-15

Capsaicin was extracted from capsicum oleoresin using an aqueous two-phase system (ATPS) composed of an ethylene oxide-propylene oxide (EOPO) copolymer, salt and ethanol. Capsaicin was concentrated in the top polymer-rich phase. To determine the optimal conditions, the partitioning of capsaicin in the ATPS was investigated, considering a single-factor experiment including the salt concentration, polymer concentration, buffer pH, ethanol concentration, sample loading and extraction duration. Response surface methodology was applied to investigate the effects of the polymer concentration, buffer pH and sample loading on capsaicin partitioning. A capsaicin yield of 95.5% was obtained using the optimal extraction system, which consisted of 16.3% UCON 50-HB-5100/10% K 2 HPO 4 /1% ethanol, a buffer pH of 4.35 and 0.24g of capsicum oleoresin. Capsaicin was purified from the capsaicinoid extract using a two-step macroporous adsorption resin (MAR) method. After purification using non-polar MAR ADS-17, the recovery and purity of capsaicin were 83.7% and 50.3%, respectively. After purification using weakly polar MAR AB-8, the recovery and purity of capsaicin were 88.0% and 85.1%, respectively. Copyright © 2017. Published by Elsevier B.V.

Aqueous alteration of Japanese simulated waste glass P0798: Effects of alteration-phase formation on alteration rate and cesium retention

International Nuclear Information System (INIS)

Inagaki, Y.; Shinkai, A.; Idemistu, K.; Arima, T.; Yoshikawa, H.; Yui, M.

2006-01-01

Aqueous alteration tests were performed with a Japanese simulated waste glass P0798 in alkaline solutions as a function of pH or species/concentration of alkaline metals in the solution in order to evaluate the alteration conditions determining whether smectite (2:1 clay mineral) or analcime (zeolite) forms as the major alteration-phase. XRD analysis of the alteration-phases showed that smectite forms at any pH between 9.5 and 12, and analcime forms at pH above 11, though the formation also depends on species and concentrations of alkaline metals in the solution. These results cannot agree with the thermodynamically predicted phase stability, e.g., smectite is more stable than the thermodynamic prediction shows. On the basis of the results of alteration conditions, the alteration tests were performed under smectite forming conditions, where only smectite forms or no crystalline phases form, in order to evaluate the alteration rate and the mechanism of cesium release/retention. The results showed that the glass alteration proceeds slowly in proportion to square root of time under smectite forming conditions, which indicates that the alteration rate can be controlled by a diffusion process. It was suggested that the alteration rate under smectite forming conditions is independent of the pH, alkaline metal species/concentration in the solution and whether smectite actually forms or not. The results also indicated that most of cesium dissolved from the glass can be retained in the alteration-phases by reversible sorption onto smectite or irreversible incorporation into analcime, pollucite or solid solutions of them

Determination of stability constants for thallium(III) cyanide complexes in aqueous solution by means of 13C and 205Ti NMR

International Nuclear Information System (INIS)

Blixt, J.; Gyori, B.; Glaser, J.

1989-01-01

In contrast to what is usually assumed, we have found and proved that thallium(III) forms very strong cyanide complexes in aqueous solution. The authors have investigated this system using 205 Tl, 13 C, and 14 N NMR and potentiometry and established the existence of four thallium(III)-cyanide complexes of the composition Tl(CN) n 3-n , n = 1-4. We have measured their chemical shifts and spin-spin coupling constants and determined their formation constants at 25 degree C in dilute (0.05 M) aqueous solution in the ionic medium ([Na + ] = 1 M, [Li + ] + [H + ] = 3 M, [ClO 4 - ] = 4 M). We have also determined the stability constant for HCN in the same ionic medium, log K a = 10.11 (5)

Allelopathic effects of Clinopodium menthifolium and Salvia sclarea aqueous extracts

Directory of Open Access Journals (Sweden)

Šućur Jovana T.

2016-01-01

Full Text Available Secondary plant biomolecules are the main agents in biochemical inter­actions between plants and the environment. It is possible to distinguish the role of secondary biomolecules in allelopathic (plant-plant activity, plant-insect, plant-microbe, plant-herbivore and others. These interactions can significantly affect the productivity of agricultural crops. Application of allelochemicals into agricultural practice may reduce the use of herbicides. Effect of Salvia sclarea L. and Clinopodium menthifolium (Host aqueous extracts on lipid peroxidation process, as well as the activity of antioxidant enzymes in leaves and roots of Jimson weed (Datura stramonium L. and soybean (Glycine max L. seedlings were examined 24 h, 72 h and 120 h after the treatment. The third aim was to evaluate effectiveness of aqueous extract as contact toxicant against Rhyzopertha dominica. Our results showed that S. sclarea aqueous extract induced lipid peroxidation in roots of Jimson weed seedlings 24 h after the treatment. Furthermore, both tested concentrations of C. menthifolium aqueous extract induced lipid peroxidation in Jimson weed roots 72 h and 120 h after the treatment. It was observed that S. sclarea aqueous extract showed toxic effect against R. dominica, with high mortality rate (above 95%.

Degradation of Acid Blue 25 in aqueous media using 1700kHz ultrasonic irradiation: ultrasound/Fe(II) and ultrasound/H(2)O(2) combinations.

Science.gov (United States)

Ghodbane, Houria; Hamdaoui, Oualid

2009-06-01

In this work, the sonolytic degradation of an anthraquinonic dye, C.I. Acid Blue 25 (AB25), in aqueous phase using high frequency ultrasound waves (1700kHz) for an acoustic power of 14W was investigated. The sonochemical efficiency of the reactor was evaluated by potassium iodide dosimeter, Fricke reaction and hydrogen peroxide production yield. The three investigated methods clearly show the production of oxidizing species during sonication and well reflect the sonochemical effects of high frequency ultrasonic irradiation. The effect of operational conditions such as the initial AB25 concentration, solution temperature and pH on the degradation of AB25 was studied. Additionally, the influence of addition of salts on the degradation of dye was examined. The rate of AB25 degradation was dependent on initial dye concentration, pH and temperature. Addition of salts increased the degradation of dye. Experiments conducted using distilled and natural waters demonstrated that the degradation was more efficient in the natural water compared to distilled water. To increase the efficiency of AB25 degradation, experiments combining ultrasound with Fe(II) or H(2)O(2) were conducted. Fe(II) induced the dissociation of ultrasonically produced hydrogen peroxide, leading to additional OH radicals which enhance the degradation of dye. The combination of ultrasound with hydrogen peroxide looks to be a promising option to increase the generation of free radicals. The concentration of hydrogen peroxide plays a crucial role in deciding the extent of enhancement obtained for the combined process. The results of the present work indicate that ultrasound/H(2)O(2) and ultrasound/Fe(II) processes are efficient for the degradation of AB25 in aqueous solutions by high frequency ultrasonic irradiation.

Cat-CVD-prepared oxygen-rich μc-Si:H for wide-bandgap material

International Nuclear Information System (INIS)

Matsumoto, Yasuhiro; Ortega, Mauricio; Peza, Juan-Manuel; Reyes, Mario-Alfredo; Escobosa, Arturo

2005-01-01

Microcrystalline phase-involved oxygen-rich a-Si:H (hydrogenated amorphous silicon) films have been obtained using catalytic chemical vapor deposition (Cat-CVD) process. Pure SiH 4 (silane), H 2 (hydrogen), and O 2 (oxygen) gases were introduced in the chamber by maintaining a pressure of 0.1 Torr. A tungsten catalyzer was fixed at temperatures of 1750 and 1950 deg. C for film deposition on glass and crystalline silicon substrates at 200 deg. C. As revealed from X-ray diffraction spectra, the microcrystalline phase appears for oxygen-rich a-Si:H samples deposited at a catalyzer temperature of 1950 deg. C. However, this microcrystalline phase tends to disappear for further oxygen incorporation. The oxygen content in the deposited films was corroborated by FTIR analysis revealing Si-O-Si bonds and typical Si-H bonding structures. The optical bandgap of the sample increases from 2.0 to 2.7 eV with oxygen gas flow and oxygen incorporation to the deposited films. In the present thin film deposition conditions, no strong tungsten filament degradation was observed after a number of sample preparations

“Towards building better linkages between aqueous phase chemistry and microphysics in CMAQ”

Science.gov (United States)

Currently, CMAQ’s aqueous phase chemistry routine (AQCHEM-base) assumes Henry’s Law equilibrium and employs a forward Euler method to solve a small set of oxidation equations, considering the additional processes of aitken scavenging and wet deposition in series and e...

Microalgae growth on the aqueous phase from Hydrothermal Liquefaction of the same microalgae

NARCIS (Netherlands)

Garcia Alba, Laura; Torri, Cristian; Fabbri, Daniele; Kersten, Sascha R.A.; Brilman, Derk Willem Frederik

2013-01-01

Cultivation of Desmodesmus sp. microalgae in the recycled aqueous phase (AP) recovered after Hydrothermal Liquefaction (HTL) of the same microalgae was studied to evaluate the potential of nutrients recycling. AP dilution ratio was systematically varied, using either water or water enriched with

Basicity determination for neutral phosphorus organic extragents by NMR 31P-method in two-phase systems, and quantitative interrelations of acido-basic extractive properties

International Nuclear Information System (INIS)

Laskorin, B.N.; Yakshin, V.V.; Meshcheryakov, N.M.; Yagodin, V.G.

1988-01-01

Consideration is given to the method for determination of basicity of neutral organophosphorus compounds of XGZP=0 type (X, G, Z=C 4 H 9 , C 8 H 17 , C 6 H 5 ). The method is based on change of chemical shift of phosphorus-31 nuclei in two-phase extraction system depending on acidity function H O , H A , H PO . It is shown that the method can be used for evaluation and forecasting of phosphine oxide ability in the processes of UO 2 SO 4 solvent extraction from aqueous solutions of sulfuric acid

A chromatographic determination of water in non-aqueous phases of solvent extraction systems

International Nuclear Information System (INIS)

Lyle, S.J.; Smith, D.B.

1975-01-01

The disadvantages of the Karl Fischer method for the determination of water in the non-aqueous phases of solvent extraction systems are pointed out, and a gas chromatographic method is described which is claimed to be potentially capable of overcoming these disadvantages. The method, as described, was developed to satisfy conditions relevant to measurement of the transfer rate of water from an aqueous phase into tri-n-butylphosphate in toluene, but it can be used for water determination in other solvent extraction systems. The apparatus used is described in detail. The concentration of water in water-saturated TBP was found to be 3.56 mol/litre, compared with a value of 3.55 obtained by Karl Fischer titration and previous literature values of 3.59 and 3.57. Measurements of water content in benzene solutions of long chain alkylamines were also sucessfully carried out. (U.K.)

Study of complex formation of cobalt (II) and cobalt (III) in acrylamide aqueous solutions and in the phase of acrylamide hydrogel

International Nuclear Information System (INIS)

Ismailova, M.M.; Egorova, L.A.; Khamidov, B.O.

1993-01-01

Present article is devoted to study of complex formation of cobalt (II) and cobalt (III) in acrylamide aqueous solutions and in the phase of acrylamide hydrogel. The condition of cobalt in various rate of oxidation in acrylamide aqueous solutions was studied. The concentration conditions of stability of system Co(II)-Co(III) were defined. The composition of coordination compounds of cobalt (II) and cobalt (III) in acrylamide aqueous solutions and in the phase of acrylamide hydrogel was determined.

Study of L-ascorbic acid (vitamin C)/H 2O mixture across glass transition

Science.gov (United States)

Migliardo, F.; Branca, C.; Faraone, A.; Magazù, S.; Migliardo, P.

2001-07-01

In this paper, we report quasi elastic neutron scattering (QENS) spectra of vitamin C aqueous solutions, obtained using MIBEMOL spectrometer (LLB). The main purpose of this work is to characterize the relaxational and vibrational properties of the Vitamin C/H 2O system below and above the glass transition temperature by analysing the low-frequency neutron scattering spectra. The determination of the relative weight of vibrational over relaxational contributions allows to get information on the fragility degree of this peculiar hydrogen-bond system.

Solvent extraction of Zn(II) from aqueous sulphate media by di(2-ethylhexyl) phosphoric acid in kerosene

International Nuclear Information System (INIS)

Begum, D.A.; Alauddin, M.; Rahman, M.S.

2009-01-01

The extraction equilibrium studies of Zn(II) from sulphate medium by di(2-ethylhexyl) phosphoric acid (D2EHPA, H/sub 2/A/sub 2/) in kerosene revealed that the distribution ratio (D) decreased with the increase of initial (Zn(A(II) in the aqueous phase and increased with the increase of equilibrium pH and extractant concentration. The equilibration is reached within 2 min. The species extracted into the organic phase is thought to be ZnA2, HA. The pH and extractant dependencies were about 2 and 1.67, respectively. The distribution ratio decreased with the increase in sulphate ion concentration in the aqueous phase. The extraction equilibrium reaction is suggested as Zn/sup 2+/ /sub aq/ +1.5 (H/sub 2/A/sub 2/)org - (ZnA/sub 2/, HA)org +2H/sup +/ /sub aq/. The extraction equilibrium constant (kex) for the above reaction was calculated to be 10-2.26. The extraction process was endothermic in nature having positive DH value of 16.27 kJ/mol. The loading of D2EHPA by Zn(II) is about 4.50 g of Zn(II) by 0.10 M D2EHPA. Possible reaction mechanism has been suggested based on distribution data, extractant concentration and equilibrium pH of the aqueous phase. (author)

Thermodynamic modelling of phase equilibrium for water + poly(Ethylene glycol + salt aqueous two-phase systems

Directory of Open Access Journals (Sweden)

R.A.G. Sé

2002-04-01

Full Text Available The NRTL (nonrandom, two-liquid model, expressed in mass fraction instead of mole fraction, was used to correlate liquid-liquid equilibria for aqueous two-phase polymer-salt solutions. New interaction energy parameters for this model were determined using reported data on the water + poly(ethylene glycol + salt systems, with different molecular masses for PEG and the salts potassium phosphate, sodium sulfate, sodium carbonate and magnesium sulfate. The correlation of liquid-liquid equilibrium is quite satisfactory.

Refinement of Modeled Aqueous-Phase Sulfate Production via the Fe- and Mn-Catalyzed Oxidation Pathway

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Syuichi Itahashi

2018-04-01

Full Text Available We refined the aqueous-phase sulfate (SO42− production in the state-of-the-art Community Multiscale Air Quality (CMAQ model during the Japanese model inter-comparison project, known as Japan’s Study for Reference Air Quality Modeling (J-STREAM. In Japan, SO42− is the major component of PM2.5, and CMAQ reproduces the observed seasonal variation of SO42− with the summer maxima and winter minima. However, CMAQ underestimates the concentration during winter over Japan. Based on a review of the current modeling system, we identified a possible reason as being the inadequate aqueous-phase SO42− production by Fe- and Mn-catalyzed O2 oxidation. This is because these trace metals are not properly included in the Asian emission inventories. Fe and Mn observations over Japan showed that the model concentrations based on the latest Japanese emission inventory were substantially underestimated. Thus, we conducted sensitivity simulations where the modeled Fe and Mn concentrations were adjusted to the observed levels, the Fe and Mn solubilities were increased, and the oxidation rate constant was revised. Adjusting the concentration increased the SO42− concentration during winter, as did increasing the solubilities and revising the rate constant to consider pH dependencies. Statistical analysis showed that these sensitivity simulations improved model performance. The approach adopted in this study can partly improve model performance in terms of the underestimation of SO42− concentration during winter. From our findings, we demonstrated the importance of developing and evaluating trace metal emission inventories in Asia.

Partition of proteins in aqueous two-phase systems based on Cashew-nut tree gum and poly(ethylene glycol

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Leonie Asfora Sarubbo

2004-09-01

Full Text Available The partitioning of two proteins, bovine serum albumin (BSA and trypsin was studied in an aqueous poly(ethylene glycol(PEG- Cashew-nut tree gum system. The phase diagram was provided for Cashew-nut tree gum and PEG molecular weight of 1500 at two different temperatures. The influence of several parameters including concentrations of polymers, pH, salt addition and temperature on the partitioning of these proteins were investigated.. The results of this research demonstrated the importance of the protein characteristics for partitioning in aqueous biphasic system.A partição de duas proteínas, albumina de soro bovino (BSA e tripsina foi estudada no sistema bifásico aquoso Polietileno glicol(PEG - Goma do cajueiro. O diagrama de fases foi estabelecido para a Goma do Cajueiro e para PEG de peso molecular 1500 em duas diferentes temperaturas. A influência de vários parâmetros na partição destas proteínas, incluindo concentração dos polímeros, pH, adição de sal e temperatura foi investigada. Os resultados desta pesquisa demonstraram a importância das características da proteína na partição em sistemas bifásicos aquosos.

The Effect of SiC Polytypes on the Heat Distribution Efficiency of a Phase Change Memory.

Science.gov (United States)

Aziz, M. S.; Mohammed, Z.; Alip, R. I.

2018-03-01

The amorphous to crystalline transition of germanium-antimony-tellurium (GST) using three types of silicon carbide’s structure as a heating element was investigated. Simulation was done using COMSOL Multiphysic 5.0 software with separate heater structure. Silicon carbide (SiC) has three types of structure; 3C-SiC, 4H-SiC and 6H-SiC. These structures have a different thermal conductivity. The temperature of GST and phase transition of GST can be obtained from the simulation. The temperature of GST when using 3C-SiC, 4H-SiC and 6H-SiC are 467K, 466K and 460K, respectively. The phase transition of GST from amorphous to crystalline state for three type of SiC’s structure can be determined in this simulation. Based on the result, the thermal conductivity of SiC can affecting the temperature of GST and changed of phase change memory (PCM).

Hexacoordinate Ru-based olefin metathesis catalysts with pH-responsive N-heterocyclic carbene (NHC and N-donor ligands for ROMP reactions in non-aqueous, aqueous and emulsion conditions

Directory of Open Access Journals (Sweden)

Shawna L. Balof

2015-10-01

Full Text Available Three new ruthenium alkylidene complexes (PCy3Cl2(H2ITapRu=CHSPh (9, (DMAP2Cl2(H2ITapRu=CHPh (11 and (DMAP2Cl2(H2ITapRu=CHSPh (12 have been synthesized bearing the pH-responsive H2ITap ligand (H2ITap = 1,3-bis(2’,6’-dimethyl-4’-dimethylaminophenyl-4,5-dihydroimidazol-2-ylidene. Catalysts 11 and 12 are additionally ligated by two pH-responsive DMAP ligands. The crystal structure was solved for complex 12 by X-ray diffraction. In organic, neutral solution, the catalysts are capable of performing standard ring-opening metathesis polymerization (ROMP and ring closing metathesis (RCM reactions with standard substrates. The ROMP with complex 11 is accelerated in the presence of two equiv of H3PO4, but is reduced as soon as the acid amount increased. The metathesis of phenylthiomethylidene catalysts 9 and 12 is sluggish at room temperature, but their ROMP can be dramatically accelerated at 60 °C. Complexes 11 and 12 are soluble in aqueous acid. They display the ability to perform RCM of diallylmalonic acid (DAMA, however, their conversions are very low amounting only to few turnovers before decomposition. However, both catalysts exhibit outstanding performance in the ROMP of dicyclopentadiene (DCPD and mixtures of DCPD with cyclooctene (COE in acidic aqueous microemulsion. With loadings as low as 180 ppm, the catalysts afforded mostly quantitative conversions of these monomers while maintaining the size and shape of the droplets throughout the polymerization process. Furthermore, the coagulate content for all experiments stayed <2%. This represents an unprecedented efficiency in emulsion ROMP based on hydrophilic ruthenium alkylidene complexes.

Photochemical reactivity of aqueous fullerene clusters: C{sub 60} versus C{sub 70}

Energy Technology Data Exchange (ETDEWEB)

Hou, Wen-Che, E-mail: whou@mail.ncku.edu.tw; Huang, Shih-Hong

2017-01-15

Highlights: • Aqueous C{sub 60} and C{sub 70} clusters (nC{sub 60} and nC{sub 70}) formed through direct mixing with water adopted a face-centered cubic crystal structure. • The AQYs of nC{sub 60} were greater than those of nC{sub 70}. • Both nC{sub 60} and nC{sub 70} lost considerable organic carbon contents (>80%) after ∼8 months of outdoor sunlight irradiation. • The intermediate photoproducts of nC{sub 60} and nC{sub 70} exhibited an increased content of oxygen-containing functionalities. - Abstract: Over the past few years, there has been a strong interest in exploring the potential impact of fullerenes in the environment. Despite that both C{sub 60} and C{sub 70} have been detected in environmental matrices, the research on the impact of higher fullerenes, such as C{sub 70,} has been largely missing. This study evaluated and compared the phototransformation of aqueous C{sub 60} and C{sub 70} clusters (nC{sub 60} and nC{sub 70}) and their {sup 1}O{sub 2} production under sunlight and lamp light irradiation (315 nm, 360 nm and 420 nm). The nC{sub 60} and nC{sub 70} samples formed by direct mixing with water adopted a face-centered cubic (FCC) crystal structure. The apparent quantum yields (AQYs) of fullerene phototransformed were relatively constant over the examined wavelengths, while {sup 1}O{sub 2} production AQYs decreased with increased wavelengths. The long-term fate studies with outdoor sunlight indicated that both nC{sub 60} and nC{sub 70} lost considerable organic carbon contents (>80%) in water after ∼8 months of irradiation and that the intermediate photoproducts of nC{sub 60} and nC{sub 70} exhibited a progressively increased level of oxygen-containing functionalities. Overall, the study indicates that nC{sub 70} can be photochemically removed under sunlight conditions and that the photoreactivity of nC{sub 60} based on AQYs is greater than that of nC{sub 70}.

Bioremediation of zirconium from aqueous solution by coriolus versicolor: process optimization

International Nuclear Information System (INIS)

Amin, M.; Bhatti, H. N.; Sadaf, S.

2013-01-01

In the present study the potential of live mycelia of Coriolus versicolor was explored for the removal of zirconium from simulated aqueous solution. Optimum experimental parameters for the bioremediation of zirconium using C. versicolor biomass have been investigated by studying the effect of mycelia dose, concentration of zirconium, contact time and temperature. The isothermal studies indicated that the ongoing bioremediation process was exothermic in nature and obeyed Langmuir adsorption isotherm model. The Gibbs free energy (ΔG), entropy (ΔS) and enthalpy (ΔH) of bioremediation were also determined. The result showed that bioremediation of zirconium by live C. versicolor was feasible and spontaneous at room temperature. The equilibrium data verified the involvement of chemisorption during the bioremediation. The kinetic data indicated the operation of pseudo-second order process during the biosorption of zirconium from aqueous solution. Maximum bioremediation capacity (110.75 mg/g) of C. versicolor was observed under optimum operational conditions: pH 4.5, biomass dose 0.05 mg/100 mL, contact time 6 h and temperature 30 degree C. The results showed that C. versicolor could be used for bioremediation of heavy metal ions from aqueous systems. (author)

New metal-organic frameworks of [M(C6H5O7)(C6H6O7)(C6H7O7)(H2O)] . H2O (M=La, Ce) and [Ce2(C2O4)(C6H6O7)2] . 4H2O

International Nuclear Information System (INIS)

Weng Shengfeng; Wang, Yun-Hsin; Lee, Chi-Shen

2012-01-01

Two novel materials, [M(C 6 H 5 O 7 )(C 6 H 6 O 7 )(C 6 H 7 O 7 )(H 2 O)] . H 2 O (M=La(1a), Ce(1b)) and [Ce 2 (C 2 O 4 )(C 6 H 6 O 7 ) 2 ] . 4H 2 O (2), with a metal-organic framework (MOF) were prepared with hydrothermal reactions and characterized with photoluminescence, magnetic susceptibility, thermogravimetric analysis and X-ray powder diffraction in situ. The crystal structures were determined by single-crystal X-ray diffraction. Compound 1 crystallized in triclinic space group P1-bar (No. 2); compound 2 crystallized in monoclinic space group P2 1 /c (No. 14). The structure of 1 is built from a 1D MOF, composed of deprotonated citric ligands of three kinds. Compound 2 contains a 2D MOF structure consisting of citrate and oxalate ligands; the oxalate ligand arose from the decomposition in situ of citric acid in the presence of Cu II ions. Photoluminescence spectra of compounds 1b and 2 revealed transitions between the 5d 1 excited state and two levels of the 4f 1 ground state ( 2 F 5/2 and 2 F 7/2 ). Compounds 1b and 2 containing Ce III ion exhibit a paramagnetic property with weak antiferromagnetic interactions between the two adjacent magnetic centers. - Graphical Abstract: [M(C 6 H 5 O 7 )(C 6 H 6 O 7 )(C 6 H 7 O 7 )(H 2 O)] . H 2 O (M=La(1a), Ce(1b)) and [Ce 2 (C 2 O 4 )(C 6 H 6 O 7 ) 2 ] . 4H 2 O (2)—with 1D and 2D structures were synthesized and characterized. Highlights: ► Two MOF – [M(C 6 H 5 O 7 )(C 6 H 6 O 7 )(C 6 H 7 O 7 )(H 2 O)] . H 2 O (M=La(1a), Ce(1b)) and [Ce 2 (C 2 O 4 )(C 6 H 6 O 7 ) 2 ] . 4H 2 O (2) – with 1D and 2D structures. ► The adjacent chains of the 1D framework were correlated with each other through an oxalate ligand to form a 2D layer structure. ► The source of the oxalate ligand was the decomposition in situ of citric acid oxidized in the presence of Cu II ions.

Oxidation of magnetite in aerated aqueous media

International Nuclear Information System (INIS)

Taylor, P.; Owen, D.G.

1993-04-01

Metastable equilibria involving phases less stable than hematite can be significantly more oxidizing than the calculated equilibrium between well-crystallized hematite and magnetite. In this report, generalized solubility and stability relationships between magnetite and Fe 2 O 3 .xH 2 O phases are derived to describe the metastable equilibria. Experiments with synthetic magnetite powders in aerated aqueous solutions show that crystalline hematite is formed within days at temperatures above 100 C in pure water or solutions containing anions (e.g., Cl - , SO 4 2 - , HCO 3 - ) that do not form very strong surface complexes with iron oxides. In the presence of dissolved phosphate or silica, however, the dissolution-precipitation route to hematite is strongly inhibited, and maghemite is a persistent metastable product. Thus, phosphate or silica are expected to delay the approach to magnetite-hematite equilibrium in aerated groundwaters conditioned by magnetite. These findings are presented in the context of nuclear fuel waste disposal. (author). 63 refs., 1 tab., 11 figs

Volume dependence of T/sub c/ of Ternary A-15 Phases

International Nuclear Information System (INIS)

Shamrai, V.

1984-01-01

Results are presented of measurements of the superconducting transition temperature T/sub c/, lattice constant a, magnetic susceptibility /sub chi/, and critical field H/sub c/ 2 for many Nb 3 Al and V 3 Si-based ternary phases and Nb 3 SnH/sub x/. For V 3 Si-based ternary systems and Nb 3 SnH/sub x/ the density of states at the Fermi level N(epsilon/sub F/) sharply decreases with the concentration of the alloying element. The variation of N(epsilon/sub F/) in these ternary systems cannot be explained by the variation of a. In ternary phases Nb 3 (Al/sub 1-x/dY/sub x/), where Y can be Ge, Ga, Sb, or Se, a quite clear correlation is revealed between T/sub c/ and a. The dependence of T/sub c/ on V in these systems is due to the variation of the matrix element of the electron-phonon interaction 2 >

Platinum–Rhenium synergy on reducible oxide supports in aqueous-phase glycerol reforming

NARCIS (Netherlands)

Ciftci, A.; Eren, S.; Ligthart, D.A.J.M.; Hensen, E.J.M.

2014-01-01

A significant support effect was observed for the aqueous-phase reforming (APR) of glycerol over a series of Pt- and PtRe-loaded ceria-, ceria–zirconia-, zirconia-, and titania-supported catalysts. Glycerol conversion rates decreased in the order Pt/TiO2>Pt/ZrO2>Pt/CeZrO2>Pt/CeO2. Upon addition of

Renewable Formate from C-H Bond Formation with CO2: Using Iron Carbonyl Clusters as Electrocatalysts.

Science.gov (United States)

Loewen, Natalia D; Neelakantan, Taruna V; Berben, Louise A

2017-09-19

As a society, we are heavily dependent on nonrenewable petroleum-derived fuels and chemical feedstocks. Rapid depletion of these resources and the increasingly evident negative effects of excess atmospheric CO 2 drive our efforts to discover ways of converting excess CO 2 into energy dense chemical fuels through selective C-H bond formation and using renewable energy sources to supply electrons. In this way, a carbon-neutral fuel economy might be realized. To develop a molecular or heterogeneous catalyst for C-H bond formation with CO 2 requires a fundamental understanding of how to generate metal hydrides that selectively donate H - to CO 2 , rather than recombining with H + to liberate H 2 . Our work with a unique series of water-soluble and -stable, low-valent iron electrocatalysts offers mechanistic and thermochemical insights into formate production from CO 2 . Of particular interest are the nitride- and carbide-containing clusters: [Fe 4 N(CO) 12 ] - and its derivatives and [Fe 4 C(CO) 12 ] 2- . In both aqueous and mixed solvent conditions, [Fe 4 N(CO) 12 ] - forms a reduced hydride intermediate, [H-Fe 4 N(CO) 12 ] - , through stepwise electron and proton transfers. This hydride selectively reacts with CO 2 and generates formate with >95% efficiency. The mechanism for this transformation is supported by crystallographic, cyclic voltammetry, and spectroelectrochemical (SEC) evidence. Furthermore, installation of a proton shuttle onto [Fe 4 N(CO) 12 ] - facilitates proton transfer to the active site, successfully intercepting the hydride intermediate before it reacts with CO 2 ; only H 2 is observed in this case. In contrast, isoelectronic [Fe 4 C(CO) 12 ] 2- features a concerted proton-electron transfer mechanism to form [H-Fe 4 C(CO) 12 ] 2- , which is selective for H 2 production even in the presence of CO 2 , in both aqueous and mixed solvent systems. Higher nuclearity clusters were also studied, and all are proton reduction electrocatalysts, but none

Solubility of NaNd(CO3)2.6H2O(c) in concentrated Na2CO3 and NaHCO3 solutions

International Nuclear Information System (INIS)

Rao, L.; Rai, D.; Felmy, A.R.; Fulton, R.W.; Novak, C.F.

1996-01-01

NaNd(CO 3 ) 2 x 6 H 2 O(c) was identified to be the final equilibrium solid phase in suspensions containing concentrated sodium carbonate (0.1 to 2.0 M) and sodium bicarbonate (0.1 to 1.0 M), with either NaNd(CO 3 ) 2 x 6 H 2 O(c) or Nd 2 (CO 3 ) 3 x xH 2 O(s) as initial solids. A thermodynamic model, based on Pitzer's specific into-interaction approach, was developed to interpret the solubility of NaNd(CO 3 ) 2 x 6 H 2 O(c) as functions of sodium carbonate and sodium bicarbonate concentrations. In this model, the solubility data of NaNd(CO 3 ) 2 x 6 H 2 O(c) were explained by assuming the formation of NdCO 3 + , Nd(CO 3 ) 2 - and Nd(CO 3 ) 3 3- species and invoking the specific ion interactions between Na + and Nd(CO 3 ) 3 3- . Ion interaction parameters for Na + -Nd(CO 3 ) 3 3- were developed to fit the solubility data. Based on the model calculations, Nd(CO 3 ) 3 3- was the predominant aqueous neodymium species in 0.1 to 2 M sodium carbonate and 0.1 to 1 M sodium bicarbonate solutions. The logarithm of the NaNd(CO 3 ) 2 x 6 H 2 O solubility product (NaNd(CO 3 ) 2 x 6 H 2 O(c)=Na + +Nd 3+ +2 CO 3 2- +6 H 2 O) was calculated to be -21.39. This model also provided satisfactory interpretation of the solubility data of the analogous Am(III) system in less concentrated carbonate and bicarbonate solutions. (orig.)

Preparative Separation of Six Rhynchophylla Alkaloids from Uncaria macrophylla Wall by pH-Zone Refining Counter-Current Chromatography

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Qinghai Zhang

2013-12-01

Full Text Available pH-Zone refining counter-current chromatography was successfully applied to the preparative isolation and purification of six alkaloids from the ethanol extracts of Uncaria macrophylla Wall. Because of the low content of alkaloids (about 0.2%, w/w in U. macrophylla Wall, the target compounds were enriched by pH-zone refining counter-current chromatography using a two-phase solvent system composed of petroleum ether–ethyl acetate–isopropanol–water (2:6:3:9, v/v, adding 10 mM triethylamine in organic stationary phase and 5 mM hydrochloric acid in aqueous mobile phase. Then pH-zone refining counter-current chromatography using the other two-phase solvent system was used for final purification. Six target compounds were finally isolated and purified by following two-phase solvent system composed of methyl tert-butyl ether (MTBE–acetonitrile–water (4:0.5:5, v/v, adding triethylamine (TEA (10 mM to the organic phase and HCl (5 mM to aqueous mobile phase. The separation of 2.8 g enriched total alkaloids yielded 36 mg hirsutine, 48 mg hirsuteine, 82 mg uncarine C, 73 mg uncarine E, 163 mg rhynchophylline, and 149 mg corynoxeine, all with purities above 96% as verified by HPLC Their structures were identified by electrospray ionization-mass spectrometry (ESI-MS and 1H-NMR spectroscopy.

Preparative separation of six rhynchophylla alkaloids from Uncaria macrophylla wall by pH-zone refining counter-current chromatography.

Science.gov (United States)

Zhang, Qinghai; Lin, Changhu; Duan, Wenjuan; Wang, Xiao; Luo, Aiqin

2013-12-12

pH-Zone refining counter-current chromatography was successfully applied to the preparative isolation and purification of six alkaloids from the ethanol extracts of Uncaria macrophylla Wall. Because of the low content of alkaloids (about 0.2%, w/w) in U. macrophylla Wall, the target compounds were enriched by pH-zone refining counter-current chromatography using a two-phase solvent system composed of petroleum ether-ethyl acetate-isopropanol-water (2:6:3:9, v/v), adding 10 mM triethylamine in organic stationary phase and 5 mM hydrochloric acid in aqueous mobile phase. Then pH-zone refining counter-current chromatography using the other two-phase solvent system was used for final purification. Six target compounds were finally isolated and purified by following two-phase solvent system composed of methyl tert-butyl ether (MTBE)-acetonitrile-water (4:0.5:5, v/v), adding triethylamine (TEA) (10 mM) to the organic phase and HCl (5 mM) to aqueous mobile phase. The separation of 2.8 g enriched total alkaloids yielded 36 mg hirsutine, 48 mg hirsuteine, 82 mg uncarine C, 73 mg uncarine E, 163 mg rhynchophylline, and 149 mg corynoxeine, all with purities above 96% as verified by HPLC Their structures were identified by electrospray ionization-mass spectrometry (ESI-MS) and 1H-NMR spectroscopy.

An efficient and sensitive fluorescent pH sensor based on amino functional metal-organic frameworks in aqueous environment.

Science.gov (United States)

Xu, Xiao-Yu; Yan, Bing

2016-04-28

A pH sensor is fabricated via a reaction between an Al(III) salt and 2-aminoterephthalic acid in DMF which leads to a MOF (Al-MIL-101-NH2) with free amino groups. The Al-MIL-101-NH2 samples show good luminescence and an intact structure in aqueous solutions with pH ranging from 4.0 to 7.7. Given its exceptional stability and pH-dependent fluorescence intensity, Al-MIL-101-NH2 has been applied to fluorescent pH sensing. Significantly, in the whole experimental pH range (4.0-7.7), the fluorescence intensity almost increases with increasing pH (R(2) = 0.99688) which can be rationalized using a linear equation: I = 2.33 pH + 26.04. In addition, error analysis and cycling experiments have demonstrated the accuracy and utilizability of the sensor. In practical applications (PBS and lake water), Al-MIL-101-NH2 also manifests its analytical efficiency in pH sensing. And the samples can be easily isolated from an aqueous solution by incorporating Fe3O4 nanoparticles. Moreover, the possible sensing mechanism based on amino protonation is discussed in detail. This work is on of the few cases for integrated pH sensing systems in aqueous solution based on luminescent MOFs.

Sequential disinfection of E. coli O157:H7 on shredded lettuce leaves by aqueous chlorine dioxide, ozonated water, and thyme essential oil

Science.gov (United States)

Singh, Nepal; Singh, Rakesh K.; Bhunia, Arun K.; Stroshine, Richard L.; Simon, James E.

2001-03-01

There have been numerous studies on effectiveness of different sanitizers for microbial inactivation. However, results obtained from different studies indicate that microorganism cannot be easily removed from fresh cut vegetables because of puncture and cut surfaces with varying surface topographies. In this study, three step disinfection approach was evaluated for inactivation of E. coli O157:H7 on shredded lettuce leaves. Sequential application of thyme oil, ozonated water, and aqueous chlorine dioxide was evaluated in which thyme oil was applied first followed by ozonated water and aqueous chlorine dioxide. Shredded lettuce leaves inoculated with cocktail culture of E. coli O157:H7 (C7927, EDL 933 and 204 P), were washed with ozonated water (15 mg/l for 10min), aqueous chlorine dioxide (10 mg/l,for 10min) and thyme oil suspension (0.1%, v/v for 5min). Washing of lettuce leaves with ozonated water, chlorine dioxide and thyme oil suspension resulted in 0.44, 1.20, and 1.46 log reduction (log10 cfu/g), respectively. However, the sequential treatment achieved approximately 3.13 log reductions (log10 cfu/g). These results demonstrate the efficacy of sequential treatments in decontaminating shredded lettuce leaves containing E. coli O157:H7.

Electrolytic nature of aqueous sulfuric acid. 2. Acidity.

Science.gov (United States)

Fraenkel, Dan

2012-09-27

In part 1 of this study, I reported that the Debye-Hückel limiting law and the smaller-ion shell (SiS) model of strong electrolyte solutions fit nicely with the experimental mean ionic activity coefficient (γ(±)) of aqueous sulfuric acid as a function of concentration and of temperature when the acid is assumed to be a strong 1-3 electrolyte. Here, I report that the SiS-derived activity coefficient of H(+), γ(H(+)), of the 1-3 acid is comparable to that of aqueous HCl. This agrees with titration curves showing, as well-known, that sulfuric acid in water is parallel in strength to aqueous HCl. The calculated pH is in good accord with the Hammett acidity function, H(0), of aqueous sulfuric acid at low concentration, and differences between the two functions at high concentration are discussed and explained. This pH-H(0) relation is consistent with the literature showing that the H(0) of sulfuric acid (in the 1-9 M range) is similar to those of HCl and the other strong mineral monoprotic acids. The titration of aqueous sulfuric acid with NaOH does not agree with the known second dissociation constant of 0.010 23; rather, the constant is found to be ~0.32 and the acid behaves upon neutralization as a strong diprotic acid practically dissociating in one step. A plausible reaction pathway is offered to explain how the acid may transform, upon base neutralization, from a dissociated H(4)SO(5) (as 3H(+) and HSO(5)(3-)) to a dissociated H(2)SO(4) even though the equilibrium constant of the reaction H(+) + HSO(5)(3-) ↔ SO(4)(2-) + H(2)O, at 25 °C, is 10(-37) (part 1).

Platinum-Catalyzed Terminal-Selective C(sp3)–H Oxidation of Aliphatic Amines

Science.gov (United States)

Lee, Melissa; Sanford, Melanie S.

2016-01-01

This paper describes the terminal-selective Pt-catalyzed C(sp3)–H oxidation of aliphatic amines without the requirement for directing groups. CuCl2 is employed as a stoichiometric oxidant, and the reactions proceed in high yield at Pt loadings as low as 1 mol %. These transformations are conducted in the presence of sulfuric acid, which reacts with the amine substrates in situ to form ammonium salts. We propose that protonation of the amine serves at least three important roles: (i) it renders the substrates soluble in the aqueous reaction medium; (ii) it limits binding of the amine nitrogen to Pt or Cu; and (ii) it electronically deactivates the C–H bonds proximal to the nitrogen center. We demonstrate that this strategy is effective for the terminal-selective C(sp3)–H oxidation of a variety of primary, secondary and tertiary amines. PMID:26439251

Aqueous Two-Phase Systems: A New Approach for the Determination of Brilliant Blue FCF in Water and Food Samples

Directory of Open Access Journals (Sweden)

Sabah Shiri

2013-01-01

Full Text Available A novel, simple, and more sensitive spectrophotometric procedure has been developed for the determination of brilliant blue FCF in water and food samples by an aqueous two-phase system (ATPS. In this method, adequate amount of polyethylene glycol/ sodium carbonate (PEG-4000/Na2CO3 was added to aqueous solution for formation of a homogeneous solution. To the mixture solution, suitable amount of Na2CO3 was added, the mixture solution was shaken until the salt was dissolved, and then it was separated into two clear phases easily and rapidly. The target analyte in the water sample was extracted into the polyethylene glycol phase. After extraction, measuring the absorbance at 634 nm was done. The effects of different parameters such as polyethylene glycol (type and concentration, pH, salt (type and amount, centrifuge time, and temperature on the ATPS of dye was investigated and optimum conditions were established. Linear calibration curves were obtained in the range of 0.25–750 ng/mL for brilliant blue FCF under optimum conditions. Detection limit based on three times the standard deviation of the blank (3Sb was 0.12 ng/mL. The relative standard deviation (RSD for 400 ng/mL was 3.14%. The method was successfully applied to the determination of brilliant blue FCF in spiked samples with satisfactory results. The relative recovery was between 96.0 and 102.2%.

Structure and phase transitions of the 6,6-cyclopropane isomer of C61H2

International Nuclear Information System (INIS)

Stetzer, M.R.; Heiney, P.A.; Stephens, P.W.; Dinnebier, R.E.; Zhu, Q.; McGhie, A.R.; Strongin, R.M.; Brandt, B.M.; Smith, A.B. III

2000-01-01

We have used x-ray powder diffraction and differential scanning calorimetry to study the crystalline structures and thermal behavior of the 6,6-cyclopropane isomer of C 61 H 2 . At room temperature, the C 61 H 2 cyclopropane molecules, like those of the 6,5-annulene isomer and C 60 O epoxide, are orientationally disordered and crystallize on a face-centered-cubic lattice such that their methylene groups are statistically disordered among the octahedral voids. Unlike 6,5-C 61 H 2 and C 60 O, the low-temperature structure is not Pa3-bar, but rather a low-symmetry orthorhombic lattice in which a≅b< c. The orientational melting takes place via a two-step transition centered around 198-213 K

Electrochemical degradation of linuron in aqueous solution using Pb/PbO2 and C/PbO2 electrodes

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Nasser Abu Ghalwa

2016-09-01

Full Text Available Two modified electrodes (Pb/PbO2 and C/PbO2 were prepared by electrodeposition and used as anodes for electrochemical degradation of linuron (phenylurea pesticide in aqueous solution. Different operating conditions and factors affecting the treatment process including current density, temperature, initial concentration of linuron, pH, conductive electrolyte and time of electrolysis were studied and optimized. The best degradation occurred in the presence of NaCl (1 gL−1 as conductive electrolyte. After 30 min, nearly complete degradation of linuron was achieved (92% and 84% using C/PbO2 and Pb/PO2 electrodes at pH 7 and 1.5, respectively. Higher degradation efficiency was obtained at low temperature (5–10 °C. The optimum current density for the degradation of linuron on both electrodes was (150 mAcm−2.

Kinetics of the reactions H+C2H4->C2H5, H+C2H5->2CH3 and CH3+C2H5->products studies by pulse radiolysis combined with infrared diode laser spectroscopy

DEFF Research Database (Denmark)

Sillesen, A.; Ratajczak, E.; Pagsberg, P.

1993-01-01

Formation of methyl radicals via the consecutive reactions H+C2H4+M-->C2H5+M (1) and H+C2H5-->CH3+CH3 (2a) was initiated by pulse radiolysis of 10-100 mbar H-2 in the presence of ethylene. The kinetics of CH3 Were studied by monitoring the transient infrared absorption at the Q(3, 3) line of the ...

Evidence and detailed study of a second-order phase transition in the (C6H11NH3)2[PbI4] organic-inorganic hybrid material

International Nuclear Information System (INIS)

Yangui, A.; Pillet, S.; Garrot, D.; Boukheddaden, K.; Triki, S.; Abid, Y.

2015-01-01

The thermal properties of the organic-inorganic hybrid material (C 6 H 11 NH 3 ) 2 [PbI 4 ] are investigated using diffuse reflectivity, spectroscopic ellipsometry, differential scanning calorimetry, Raman spectroscopy, and X-ray diffraction. The diffuse reflectivity, performed in heating mode, clearly evidences the presence of a singularity at 336 K. This is confirmed by the temperature dependence of the spectroscopic ellipsometry spectra, which points out a second-order phase transition at 336 K with a critical exponent ∼0.5. Differential scanning calorimetry measurements on a polycrystalline powder of (C 6 H 11 NH 3 ) 2 [PbI 4 ] show a reversible phase transition detected at T C  = 336 K without hysteresis. Raman spectroscopy data suggest that this transition arises from a change in the interactions between inorganic sheets (([PbI 4 ] 2− ) ∞ ) and organic protonated molecules ([C 6 H 11 NH 3 ] + ). The structural analysis from power X-ray diffraction reveals an incomplete order-disorder transition of the cyclohexylammonium cation, causing a subtle contraction of the inter-plane distance. The transition results from repulsive close contacts between the organic molecules in the interlayer spacing

Phase diagram and equation of state of TiH2 at high pressures and high temperatures

International Nuclear Information System (INIS)

Endo, Naruki; Saitoh, Hiroyuki; Machida, Akihiko; Katayama, Yoshinori; Aoki, Katsutoshi

2013-01-01

Highlights: ► We determined the phase diagram of TiH 2 at high pressures and high temperatures. ► Compression induced stain inhibited the phase transition from the bct to fcc phase. ► The phase boundary was appropriately determined using a sample with heat treatment. ► The high temperature Birch–Murnaghan equation of state of fcc TiH 2 was firstly determined. - Abstract: We determined the phase diagram and the equation of state (EoS) of TiH 2 at high pressures up to 8.7 GPa and high temperatures up to 600 °C by in situ synchrotron radiation X-ray diffraction measurements. Compression induced strain inhibited the phase transition from the low-temperature bct phase to the high-temperature fcc phase, making the phase diagram difficult to determine. However, heating around 600 °C relieved the strain, and the phase boundary between the bct and fcc phases was elucidated. The phase transition temperature at ambient pressure increased from around room temperature to 200 °C at 8.7 GPa. The high temperature Birch–Murnaghan EoS was determined for the fcc phase. With the pressure derivative of the bulk modulus K′ 0 = 4.0, the following parameters were obtained: ambient bulk modulus K 0 = 97.7 ± 0.2 GPa, ambient unit cell of the fcc phase V 0 = 88.57 ± 0.02 Å 3 , temperature derivative of the bulk modulus at constant pressure (∂K/∂T) P = −0.01 ± 0.02, and volumetric thermal expansivity α = a + bT with a = 2.62 ± 1.4 × 10 −5 and b = 5.5 ± 4.5 × 10 −8 . K 0 of fcc TiH 2 was close to those for pure Ti and bct TiH 2 reported in previous studies.

Study of the H+, F- and C2O42- ions effect on the Columbo-Tantalites dissolution

International Nuclear Information System (INIS)

Rodriguez, Mario; Ruiz, Maria del Carmen

2003-01-01

The dissolution reaction of Nb, Ta, Fe and Mn in aqueous solutions of HF, HF-H 2 C 2 O 4 , HF-Na 2 C 2 O 4 and H 2 C 2 O 4 -NaF mixtures, using columbo-tantalites of the San Luis Province, has been studied using a Parr autoclave.The temperature range investigated in this work is between 340 and 396 K.At the moment, the experimental data show that the presence of H + and F - ions in the leaching solution is necessary to produce an appreciable dissolution of columbo-tantalite.Also, the presence of C 2 O 4 2- ions favors the mineral dissolution.On the other hand, both the rise of the H + , F - and C 2 O 4 2- ions concentrations and the increase temperature lead to higher Nb and Ta extractions.Moreover, the presence of the Na + of ion in the leaching media induce the formation of Nb and/or Ta insoluble complexes that settle on the residue

Cosolutes effects on aqueous two-phase systems equilibrium formation studied by physical approaches.

Science.gov (United States)

Bertoluzzo, M Guadalupe; Rigatuso, Rubén; Farruggia, Beatriz; Nerli, Bibiana; Picó, Guillermo

2007-10-01

The effect of urea and sodium salts of monovalent halides on the aqueous polyethyleneglycol solution and binodal diagrams of polyethyleneglycol-potassium phosphate (polyethyleneglycol of molecular mass 1500, 4000, 6000 and 8000) were studied using different physical approaches. The effect of these solutes on the binodal diagram for polyethyleneglycol-potassium phosphate was also investigated. The cosolutes affected in a significant manner the water structured around the ethylene chain of polyethyleneglycol inducing a lost of this. The equilibrium curves for the aqueous two-phase systems were fitting very well by a sigmoidal function with two parameters, which are closely related with the cosolute structure making or breaking capacity on the water ordered.

Basalt Reactivity Variability with Reservoir Depth in Supercritical CO2 and Aqueous Phases

Energy Technology Data Exchange (ETDEWEB)

Schaef, Herbert T.; McGrail, B. Peter; Owen, Antionette T.

2011-04-01

Long term storage of CO{sub 2} in geologic formations is currently considered the most attractive option to reduce greenhouse gas emissions while continuing to utilize fossil fuels for energy production. Injected CO{sub 2} is expected to reside as a buoyant water-saturated supercritical fluid in contact with reservoir rock, the caprock system, and related formation waters. As was reported for the first time at the GHGT-9 conference, experiments with basalts demonstrated surprisingly rapid carbonate mineral formation occurring with samples suspended in the scCO{sub 2} phase. Those experiments were limited to a few temperatures and CO{sub 2} pressures representing relatively shallow (1 km) reservoir depths. Because continental flood basalts can extend to depths of 5 km or more, in this paper we extend the earlier results across a pressure-temperature range representative of these greater depths. Different basalt samples, including well cuttings from the borehole used in a pilot-scale basalt sequestration project (Eastern Washington, U.S.) and core samples from the Central Atlantic Magmatic Province (CAMP), were exposed to aqueous solutions in equilibrium with scCO{sub 2} and water-rich scCO{sub 2} at six different pressures and temperatures for select periods of time (30 to 180 days). Conditions corresponding to a shallow injection of CO{sub 2} (7.4 MPa, 34 C) indicate limited reactivity with basalt; surface carbonate precipitates were not easily identified on post-reacted basalt grains. Basalts exposed under identical times appeared increasingly more reacted with simulated depths. Tests, conducted at higher pressures (12.0 MPa) and temperatures (55 C), reveal a wide variety of surface precipitates forming in both fluid phases. Under shallow conditions tiny clusters of aragonite needles began forming in the wet scCO{sub 2} fluid, whereas in the CO{sub 2} saturated water, cation substituted calcite developed thin radiating coatings. Although these types of coatings

Experimental study of arsenic speciation in vapor phase to 500°C: Implications for As transport and fractionation in low-density crustal fluids and volcanic gases.

OpenAIRE

Pokrovski , Gleb S.; Zakirov , Ildar V.; Roux , Jacques; Testemale , Denis; Hazemann , Jean-Louis; Y. U. Bychkov , Andrew; V. Golikova , Galina

2002-01-01

The stoichiometry and stability of arsenic gaseous complexes were determined in the system As-H2O ± NaCl ± HCl ± H2S at temperatures up to 500°C and pressures up to 600 bar, from both measurements of As(III) and As(V) vapor-liquid and vapor-solid partitioning, and X-ray absorption fine structure (XAFS) spectroscopic study of As(III)-bearing aqueous fluids. Vapor-aqueous solution partitioning for As(III) was measured from 250 to 450°C at the saturated vapor pressure of the system (Psat) with a...

Topically applied standardized aqueous extract of Curcuma longa Linn. suppresses endotoxin-induced uveal inflammation in rats.

Science.gov (United States)

Agarwal, Renu; Gupta, S K; Agarwal, Puneet; Srivastava, Sushma

2013-10-01

Aqueous extract of C. longa when administered 4 h after induction of E. coli lipopolysaccharide-induced uveitis in rats showed significantly suppressed inflammation with a significantly lower mean clinical grade, histopathological grade and aqueous humor (AH) protein level compared to vehicle treated group. Although, prednisolone group showed significantly lower clinical grade, histopathological grades and AH protein levels compared to C. longa group, TNF-alpha levels did not differ significantly. Moreover, when the aqueous extract was administered starting from 3 days before induction of uveitis, the mean clinical and histopathological grade as well as AH protein and TNF-alpha levels were comparable to C. longa group when treatment was administered 4 h after induction of uveitis. It is concluded that topically applied standardized aqueous extract of C. longa suppresses endotoxin-induced uveitis in rats by reducing TNF-alpha activity.

Systems Li2B4O7 (Na2B4O7, K2B4O7)-N2H3H4OH-H2O at 25 deg C

International Nuclear Information System (INIS)

Skvortsov, V.G.; Sadetdinov, Sh.V.; Akimov, V.M.; Mitrasov, Yu.N.; Petrova, O.V.; Klopov, Yu.N.

1994-01-01

Phase equilibriums in the Li 2 B 4 O 7 (Na 2 B 4 O 7 , K 2 B 4 O 7 )-N 2 H 3 H 4 OH-H 2 O systems were investigated by methods of isothermal solubility, refractometry and PH-metry at 25 deg C for the first time. Lithium and sodium tetraborates was established to form phases of changed composition mM 2 B 4 O 7 ·nN 2 H 3 C 2 H 4 OH·XH 2 O, where M=Li, Na with hydrazine ethanol. K 2 B 4 O 7 ·4H 2 O precipitates in solid phase in the case of potassium salt. Formation of isomorphous mixtures was supported by X-ray diffraction and IR spectroscopy methods