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Sample records for electrochemical chlorine evolution

  1. Electrochemical chlorine evolution at rutile oxide (110) surfaces

    Hansen, Heine Anton; Man, Isabela Costinela; Studt, Felix

    2010-01-01

    -sites are established for MO2 (M being Ir, Ru, Pt, Ti). The linear relations form the basis for constructing a generalized surface phase diagram where two parameters, the potential and the binding energy of oxygen, are needed to determine the surface composition. We calculate the catalytic activity as function...... the lowest overpotential at which all elementary reaction steps in the chlorine evolution reaction are downhill in free energy. This condition is then used as a measure for catalytic activity. Linear scaling relations between the binding energies of the intermediates and the oxygen binding energies at cus...... of the oxygen binding energy, giving rise to a Sabatier volcano. By combining the surface phase diagram and the volcano describing the catalytic activity, we find that the reaction mechanism differs depending on catalyst material. The flexibility in reaction path means that the chlorine evolution activity...

  2. Electrochemical Hydrogen Evolution

    Laursen, A.B.; Varela Gasque, Ana Sofia; Dionigi, F.

    2012-01-01

    The electrochemical hydrogen evolution reaction (HER) is growing in significance as society begins to rely more on renewable energy sources such as wind and solar power. Thus, research on designing new, inexpensive, and abundant HER catalysts is important. Here, we describe how a simple experiment...... catalysts based on this. Suited for upper-level high school and first-year university students, this exercise involves using a basic two-cell electrochemical setup to test multiple electrode materials as catalysts at one applied potential, and then constructing a volcano curve with the resulting currents...

  3. Ti atoms in Ru0.3Ti0.7O2 mixed oxides form active and selective sites for electrochemical chlorine evolution

    Karlsson, Rasmus K. B.; Hansen, Heine Anton; Bligaard, Thomas

    2014-01-01

    affected by the presence of small amounts of Ru dopant, whereas oxygen adsorption is relatively unaffected by Ti dopants in RuO2. The calculations also indicate that coordinatively unsaturated Ti sites on Ru-doped TiO2 and on Ru0.3Ti0.7O2 could form active and selective sites for Cl2 evolution....... These results suggest a reason for why DSA shows a higher chlorine selectivity than RuO2 and propose an experimental test of the hypothesis....

  4. Electrochemically activated water as an alternative to chlorine for decentralized disinfection

    Ghebremichael, Kebreab A.; Muchelemba, E.; Petruševski, Branislav; Amy, Gary L.

    2011-01-01

    Electrochemically activated (ECA) water is being extensively studied and considered as an alternative to chlorine for disinfection. Some researchers claim that ECA is by and large a chlorine solution, while others claim the presence of reactive

  5. A study of the characteristics of indium tin oxide after chlorine electro-chemical treatment

    Kim, Moonsoo; Kim, Jongmin; Cho, Jaehee; Kim, Hyunwoo; Lee, Nayoung; Choi, Byoungdeog, E-mail: bdchoi@skku.edu

    2016-10-15

    Graphical abstract: The presence of Chlorine in the outer surface resulted in a highly electro-negative surface states and an increase in the vacuum energy level. - Highlights: • We investigated the influence of chlorine surface treatment on ITO properties. • Chlorination induced the change of the electro-static potential in the outer surface. • Chlorine electro-chemical treatment of ITO is a simple, fast and effective technique. - Abstract: In this work, we investigate the influence of a chlorine-based electro-chemical surface treatment on the characteristics of indium tin oxide (ITO) including the work function, chemical composition, and phase transition. The treated ITOs were characterized using X-ray photoelectron spectroscopy (XPS), ultra-violet photoelectron spectroscopy (UPS), 4-point probe measurements, and grazing incidence X-ray diffraction (GI-XRD). We confirmed a change of the chemical composition in the near-surface region of the ITO and the formation of indium-chlorine (In-Cl) bonds and surface dipoles (via XPS). In particular, the change of the electro-static potential in the outer surface was caused by chlorination. Due to the vacuum-level shift after the electro-chemical treatment in a dilute hydrochloric acid, the ITO work function was increased by ∼0.43 eV (via UPS); furthermore, the electro-negativity of the chlorine anions attracted electrons to emit them from the hole transport layer (HTL) to the ITO anodes, resulting in an increase of the hole-injection efficiency.

  6. Comparison of electrochemical method with ozonation, chlorination and monochloramination in drinking water disinfection

    Li Hongna, E-mail: lihongna@gmail.com [Department of Environmental Engineering, Peking University, Key Laboratory of Water and Sediment Sciences, Ministry of Education, Beijing 100871 (China); Zhu Xiuping [Department of Environmental Engineering, Peking University, Key Laboratory of Water and Sediment Sciences, Ministry of Education, Beijing 100871 (China); Ni Jinren, E-mail: nijinren@iee.pku.edu.cn [Department of Environmental Engineering, Peking University, Key Laboratory of Water and Sediment Sciences, Ministry of Education, Beijing 100871 (China)

    2011-11-30

    Highlights: > Electrochemical, O{sub 3}, NaClO and NH{sub 2}Cl were compared at respective optimal condition. > Disinfection efficacy was similar for different bacteria in electrolysis. > Harsh Bacillus was inactivated more difficult in O{sub 3}, NaClO and NH{sub 2}Cl system. > Efficient disinfection of electrolysis was attributed to nonselectivity of {center_dot}OH. > Cell surface damage was more obvious in electrochemical process than the others. - Abstract: Electrochemical process in chloride-free electrolytes was proved to be powerful in disinfection due to the strong oxidants produced in the electrolysis and no formation of disinfection byproducts (DBPs). In this study, disinfection experiments were conducted by electrochemical treatment compared with ordinary and advanced methods (ozonation, chlorination and monochloramination), with Escherichia coli (E. coli) K-12, Staphylococcus aureus (S. aureus) A106, Bacillus subtilis (BST) and an isolated Bacillus as the representative microorganisms. Firstly, factor tests were performed on E. coli to obtain the optimal conditions of the four disinfection procedures. At their respective optimal condition, CT (concentration of disinfectant x contact time) value of a 4-log E. coli inactivation was 33.5, 1440, 1575, 1674 mg min L{sup -1} for electrochemical process, ozonation, chlorination and monochloramination, respectively. It was demonstrated that the disinfection availability was in the following order: electrochemical process > ozonation > chlorination > monochloramination, which could be attributed to the hydroxyl radical generated in the electrolysis, with strong oxidizing ability and non-selectivity compared with the other three disinfectants. Moreover, the disinfection efficacy of the four disinfection procedures was compared for four different bacteria. It was found that the disinfection efficacy was similar for the selected four bacteria in electrochemical process, while in the other three treatments

  7. Comparison of electrochemical method with ozonation, chlorination and monochloramination in drinking water disinfection

    Li Hongna; Zhu Xiuping; Ni Jinren

    2011-01-01

    Highlights: → Electrochemical, O 3 , NaClO and NH 2 Cl were compared at respective optimal condition. → Disinfection efficacy was similar for different bacteria in electrolysis. → Harsh Bacillus was inactivated more difficult in O 3 , NaClO and NH 2 Cl system. → Efficient disinfection of electrolysis was attributed to nonselectivity of ·OH. → Cell surface damage was more obvious in electrochemical process than the others. - Abstract: Electrochemical process in chloride-free electrolytes was proved to be powerful in disinfection due to the strong oxidants produced in the electrolysis and no formation of disinfection byproducts (DBPs). In this study, disinfection experiments were conducted by electrochemical treatment compared with ordinary and advanced methods (ozonation, chlorination and monochloramination), with Escherichia coli (E. coli) K-12, Staphylococcus aureus (S. aureus) A106, Bacillus subtilis (BST) and an isolated Bacillus as the representative microorganisms. Firstly, factor tests were performed on E. coli to obtain the optimal conditions of the four disinfection procedures. At their respective optimal condition, CT (concentration of disinfectant x contact time) value of a 4-log E. coli inactivation was 33.5, 1440, 1575, 1674 mg min L -1 for electrochemical process, ozonation, chlorination and monochloramination, respectively. It was demonstrated that the disinfection availability was in the following order: electrochemical process > ozonation > chlorination > monochloramination, which could be attributed to the hydroxyl radical generated in the electrolysis, with strong oxidizing ability and non-selectivity compared with the other three disinfectants. Moreover, the disinfection efficacy of the four disinfection procedures was compared for four different bacteria. It was found that the disinfection efficacy was similar for the selected four bacteria in electrochemical process, while in the other three treatments inactivation of the two

  8. A micromachined electrochemical sensor for free chlorine monitoring in drinking water.

    Mehta, A; Shekhar, H; Hyun, S H; Hong, S; Cho, H J

    2006-01-01

    In this work, we designed, fabricated and tested a disposable, flow-through amperometric sensor for free chlorine determination in water. The sensor is based on the principle of an electrochemical cell. The substrate, as well as the top microfluidic layer, is made up of a polymer material. The advantages include; (a) disposability from low cost; (b) stable operation range from three-electrode design; (c) fluidic interconnections that provide on line testing capabilities; and (d) transparent substrate which provides for future integration of on-chip optics. The sensor showed a good response and linearity in the chlorine concentration ranging from 0.3 to 1.6 ppm, which applies to common chlorination process for drinking water purification.

  9. Kinetic investigation of the chlorine reduction reaction on electrochemically oxidised ruthenium

    Thomassen, M.; Karlsen, C.; Borresen, B.; Tunold, R.

    2006-01-01

    The rate and mechanism of the electroreduction of chlorine on electrooxidised ruthenium has been investigated with focus on the effect of solution pH. Current/potential curves for the reduction process in solutions with constant chloride concentration of 1.0 mol dm -3 and varying H + concentration have been obtained with the use of the rotating disk electrode technique (RDE). It was found that the chlorine reduction rate is highly inhibited in solutions with high H + concentrations and that it can be satisfactorily described by the Erenburg mechanism, previously suggested for the chlorine evolution on RuO 2 and RTO. The expression of the kinetic current as a function of chlorine and H + concentration was obtained by solving the elementary rate equations of the kinetic mechanism. The kinetic constants obtained from the correlation of the kinetic current expression to the experimental data were used to simulate the dependence of the surface coverages and elementary reaction rates on overpotential

  10. Electrochemical production and use of free chlorine for pollutant removal: an experimental design approach.

    Antonelli, Raissa; de Araújo, Karla Santos; Pires, Ricardo Francisco; Fornazari, Ana Luiza de Toledo; Granato, Ana Claudia; Malpass, Geoffroy Roger Pointer

    2017-10-28

    The present paper presents the study of (1) the optimization of electrochemical-free chlorine production using an experimental design approach, and (2) the application of the optimum conditions obtained for the application in photo-assisted electrochemical degradation of simulated textile effluent. In the experimental design the influence of inter-electrode gap, pH, NaCl concentration and current was considered. It was observed that the four variables studied are significant for the process, with NaCl concentration and current being the most significant variables for free chlorine production. The maximum free chlorine production was obtained at a current of 2.33 A and NaCl concentrations in 0.96 mol dm -3 . The application of the optimized conditions with simultaneous UV irradiation resulted in up to 83.1% Total Organic Carbon removal and 100% of colour removal over 180 min of electrolysis. The results indicate that a systematic (statistical) approach to the electrochemical treatment of pollutants can save time and reagents.

  11. Application of an electrochemical chlorine-generation system combined with solar energy as appropriate technology for water disinfection.

    Choi, Jusol; Park, Chan Gyu; Yoon, Jeyong

    2013-02-01

    Affordable water disinfection is key to reducing the waterborne disease experienced worldwide where resources are limited. A simple electrochemical system that can generate chlorine as a disinfectant from the electrolysis of sodium chloride is an appropriate technology to produce clean water, particularly if driven by solar energy. This study examined the affordability of an electrochemical chlorine generation system using solar energy and developed the necessary design information for its implementation. A two-electrode batch reactor, equipped with commercial IrO(2)-coated electrodes and a solar panel (approximate area 0.2 m(2)), was used to produce chlorine from a 35g/L solution of NaCl. Within 1 h, sufficient chlorine (0.8 g) was generated to produce clean drinking water for about 80 people for 1 day (target microorganism: Escherichia coli; daily drinking water requirement: 2 L per person; chlorine demand: 4 mg/L; solar power: 650 W/m(2) in Seoul, Korea. Small household batteries were demonstrated to be a suitable alternative power source when there is insufficient solar irradiation. Using a 1 m(2) solar panel, the reactor would take only 15 min in Seoul, Korea, or 7 min in the tropics (solar power 1300 W/m(2)), to generate 1 g of chlorine. The solar-powered electrochemical chlorine generation system for which design information is provided here is a simple and affordable way to produce chlorine with which to convert contaminated water into clean drinking water.

  12. Electrochemically activated water as an alternative to chlorine for decentralized disinfection

    Ghebremichael, Kebreab A.

    2011-06-01

    Electrochemically activated (ECA) water is being extensively studied and considered as an alternative to chlorine for disinfection. Some researchers claim that ECA is by and large a chlorine solution, while others claim the presence of reactive oxygen species such as ozone and hydroxyl radicals in addition to chlorine. This study compares sodium hypochlorite (NaOCl) and ECA in terms of disinfection efficacy, trihalomethanes (THMs) formation, stability and composition. The studies were carried out under different process conditions (pH 5,7 and 9, disinfectant concentrations of 2-5 mg/L and dissolved organic carbon (DOC) concentration of 2-4 mg/L). The results indicated that in the presence of low DOC (<2 mg/L) ECA showed better disinfection efficacy for Escherichia coli inactivation, formed lower THM and had better stability compared with NaOCl at both pH 5 and 7. Stability studies of stock solutions showed that over a period of 30 days, ECA decayed by only 5% while NaOCl decayed by 37.5% at temperatures of 4 °C. In a fresh ECA of 200 mg/L chlorine, about 5.3 mg/L ozone and 36.9 mg/L ClO2 were detected. The study demonstrates that ECA could be a suitable alternative to NaOCl where decentralized production and use are required. © IWA Publishing 2011.

  13. Electrochemical dehalogenisation of chlorinated aromatics - from model substances to practice-relevant ''real life'' samples

    Voss, I.; Altrogge, M.; Francke, W.

    1993-01-01

    Building on methods for the dehalogenisation of chlorinated benzoles known from the literature, an investigation was carried out whether polychlorinated biphenyls, dibenzo furane and dibenzo-p-dioxin can be dehalogenated electrochemically. The experiments were carried out with pure substances and transferred to mixed substances (real life samples). The investigations showed that both pure substances and complex mixtures can be dehalogenated without problems. Even in the presence of a clear oil matrix (e.g.: Oil trickled through a deposit), dehalogenisation of the xenobiotica present is possible. First attempts at 'scaling up' show that the method is also suitable in principle, for the disposal of large quantities of contaminated liquids. (BBR) [de

  14. Chlorine

    ... your clothing, rapidly wash your entire body with soap and water, and get medical care as quickly as possible. Removing and disposing of clothing: Quickly take off clothing that has liquid chlorine on it. Any clothing that has to ...

  15. Passivation and electrochemical behavior of 316L stainless steel in chlorinated simulated concrete pore solution

    Luo, Hong; Su, Huaizhi; Dong, Chaofang; Li, Xiaogang

    2017-04-01

    In this paper, the passivation and electrochemical behavior of 316L stainless steel in chlorinated simulated concrete pore solutions at different pH was evaluated by potentiodynamic measurements, electrochemical impedance spectroscopy. The composition of the passive film and surface morphology were investigated by X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS), and scanning electron microscopy, respectively. The results reveal that metastable pitting susceptibility, stable pitting corrosion, and composition of the passive film are influenced by pH value. After long time immersion, a bilayer structure passive film can be formed in this environment. The appearance of molybdates on the outermost surface layer, further enhancing the stability of the passive film. Moreover, the good pitting corrosion resistance of 316L stainless steel in simulated concrete pore solution without carbonated is mainly due to the presence of high Cr/Fe ratio and molybdates ions within the passive film.

  16. Electrochemical treatment of wastewater: A case study of reduction of DNT and oxidation of chlorinated phenols

    Rodgers, J.D.; Bunce, N.J.; Jedral, W.

    1999-07-01

    Electrochemical treatment is under consideration as a treatment option for several recalcitrant compounds. In this work the authors investigate the oxidation of chlorophenols and the reduction of nitroaromatics. In the case of chlorinated phenols, they explore the problem of anode fouling which has hampered electrolytic treatment of phenolic compounds by examining phenols differing in the extent of chlorination, according to the mechanism of oxidation at different electrode types. Linear sweep voltammograms at a Pt anode were interpreted in terms of deposition of oligomers on the anode surface. Passivation increased in parallel with the uncompensated resistance of the solution and occurred only at potentials at which water is oxidized, suggesting that the formation of the oligomer film involves attack of hydroxyl radicals on electrochemically oxidized substrate. Relative reactivities of congeners were anode-dependent, due to different mechanisms of oxidation: direct electron transfer oxidation at PbO{sub 2} and hydroxyl radical attack at SnO{sub 2} and IrO{sub 2}. Voltammetry of 2,6-dinitrotoluene (DNT) was consistent with literature values. DNT was reduced at several cathodes with the most promising result at Ni-plated Ni wire. At current densities {lt} 0.1 mA cm{sup {minus}2}, current efficiencies {gt} 50% could be achieved with 4-chlorophenol at all three anodes and for 2,6-DNT at Ni-plated Ni wire.

  17. Chlorine Evolution Reaction on RuO2(110): Ab initio Atomistic Thermodynamics Study - Pourbaix Diagrams

    Exner, Kai S.; Anton, Josef; Jacob, Timo; Over, Herbert

    2014-01-01

    Graphical abstract: - Highlights: • Using the method Pourbaix diagram we identified the oxygen covered RuO 2 (110) surface as the catalytically active phase under chlorine evolution reaction (CER) conditions. This active phase is compared with the active phase in the Deacon process, the heterogeneous gas phase counterpart of the CER. - Abstract: Constrained ab initio thermodynamics in the form of a Pourbaix diagram can greatly assist kinetic modeling of a particular electrochemical reaction such as the chlorine evolution reaction (CER) over RuO 2 (110). Pourbaix diagrams reveal stable surface structures, as a function of pH and the potential. The present DFT study indicates that the Pourbaix diagram in the CER potential region above 1.36 V and pH values around zero is dominated by a stable surface structure in which all coordinatively undercoordinated Ru sites (Ru cus ) are capped by on-top oxygen (O ot ). This oxygen saturated RuO 2 (110) surface is considered to serve as the catalytically active phase in the CER, quite in contrast to the heterogeneously catalyzed HCl oxidation (Deacon process), for which the active RuO 2 (110) surface is mainly covered by on-top chlorine. The active sites in the CER are suggested to be Ru cus O ot surface complexes, while in the Deacon process both undercoordinated surface Ru and oxygen sites must be available for the activation of HCl molecules

  18. Passivation and electrochemical behavior of 316L stainless steel in chlorinated simulated concrete pore solution

    Luo, Hong, E-mail: luohong@hhu.edu.cn [College of Mechanics and Materials, Hohai University, Nanjing 210098 (China); Su, Huaizhi [State Key Laboratory of Hydrology-Water Resources and Hydraulic Engineering, Hohai University, Nanjing 210098,China (China); Dong, Chaofang; Li, Xiaogang [Institute of Advanced Materials and Technology, University of Science and Technology Beijing, Beijing 100083,China (China)

    2017-04-01

    Highlights: • The pH value play an important role on passive mechanism of stainless steel. • The relationship between Cr/Fe ratio within the passive film and pH is non-linear. • Better corrosion resistance due to high Cr/Fe ratio and molybdates ions. - Abstract: In this paper, the passivation and electrochemical behavior of 316L stainless steel in chlorinated simulated concrete pore solutions at different pH was evaluated by potentiodynamic measurements, electrochemical impedance spectroscopy. The composition of the passive film and surface morphology were investigated by X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS), and scanning electron microscopy, respectively. The results reveal that metastable pitting susceptibility, stable pitting corrosion, and composition of the passive film are influenced by pH value. After long time immersion, a bilayer structure passive film can be formed in this environment. The appearance of molybdates on the outermost surface layer, further enhancing the stability of the passive film. Moreover, the good pitting corrosion resistance of 316L stainless steel in simulated concrete pore solution without carbonated is mainly due to the presence of high Cr/Fe ratio and molybdates ions within the passive film.

  19. Passivation and electrochemical behavior of 316L stainless steel in chlorinated simulated concrete pore solution

    Luo, Hong; Su, Huaizhi; Dong, Chaofang; Li, Xiaogang

    2017-01-01

    Highlights: • The pH value play an important role on passive mechanism of stainless steel. • The relationship between Cr/Fe ratio within the passive film and pH is non-linear. • Better corrosion resistance due to high Cr/Fe ratio and molybdates ions. - Abstract: In this paper, the passivation and electrochemical behavior of 316L stainless steel in chlorinated simulated concrete pore solutions at different pH was evaluated by potentiodynamic measurements, electrochemical impedance spectroscopy. The composition of the passive film and surface morphology were investigated by X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS), and scanning electron microscopy, respectively. The results reveal that metastable pitting susceptibility, stable pitting corrosion, and composition of the passive film are influenced by pH value. After long time immersion, a bilayer structure passive film can be formed in this environment. The appearance of molybdates on the outermost surface layer, further enhancing the stability of the passive film. Moreover, the good pitting corrosion resistance of 316L stainless steel in simulated concrete pore solution without carbonated is mainly due to the presence of high Cr/Fe ratio and molybdates ions within the passive film.

  20. Selectivity of Nanocrystalline IrO2-Based Catalysts in Parallel Chlorine and Oxygen Evolution

    Kuznetsova, Elizaveta; Petrykin, Valery; Sunde, S.; Krtil, Petr

    2015-01-01

    Roč. 6, č. 2 (2015), s. 198-210 ISSN 1868-2529 EU Projects: European Commission(XE) 214936 Institutional support: RVO:61388955 Keywords : iridium dioxide * oxygen evolution * chlorine evolution Subject RIV: CG - Electrochemistry Impact factor: 2.347, year: 2015

  1. Sequential Combination of Electro-Fenton and Electrochemical Chlorination Processes for the Treatment of Anaerobically-Digested Food Wastewater.

    Shin, Yong-Uk; Yoo, Ha-Young; Kim, Seonghun; Chung, Kyung-Mi; Park, Yong-Gyun; Hwang, Kwang-Hyun; Hong, Seok Won; Park, Hyunwoong; Cho, Kangwoo; Lee, Jaesang

    2017-09-19

    A two-stage sequential electro-Fenton (E-Fenton) oxidation followed by electrochemical chlorination (EC) was demonstrated to concomitantly treat high concentrations of organic carbon and ammonium nitrogen (NH 4 + -N) in real anaerobically digested food wastewater (ADFW). The anodic Fenton process caused the rapid mineralization of phenol as a model substrate through the production of hydroxyl radical as the main oxidant. The electrochemical oxidation of NH 4 + by a dimensionally stable anode (DSA) resulted in temporal concentration profiles of combined and free chlorine species that were analogous to those during the conventional breakpoint chlorination of NH 4 + . Together with the minimal production of nitrate, this confirmed that the conversion of NH 4 + to nitrogen gas was electrochemically achievable. The monitoring of treatment performance with varying key parameters (e.g., current density, H 2 O 2 feeding rate, pH, NaCl loading, and DSA type) led to the optimization of two component systems. The comparative evaluation of two sequentially combined systems (i.e., the E-Fenton-EC system versus the EC-E-Fenton system) using the mixture of phenol and NH 4 + under the predetermined optimal conditions suggested the superiority of the E-Fenton-EC system in terms of treatment efficiency and energy consumption. Finally, the sequential E-Fenton-EC process effectively mineralized organic carbon and decomposed NH 4 + -N in the real ADFW without external supply of NaCl.

  2. Full Kinetics from First Principles of the Chlorine Evolution Reaction over a RuO2 (110) Model Electrode.

    Exner, Kai S; Anton, Josef; Jacob, Timo; Over, Herbert

    2016-06-20

    Current progress in modern electrocatalysis research is spurred by theory, frequently based on ab initio thermodynamics, where the stable reaction intermediates at the electrode surface are identified, while the actual energy barriers are ignored. This approach is popular in that a simple tool is available for searching for promising electrode materials. However, thermodynamics alone may be misleading to assess the catalytic activity of an electrochemical reaction as we exemplify with the chlorine evolution reaction (CER) over a RuO2 (110) model electrode. The full procedure is introduced, starting from the stable reaction intermediates, computing the energy barriers, and finally performing microkinetic simulations, all performed under the influence of the solvent and the electrode potential. Full kinetics from first-principles allows the rate-determining step in the CER to be identified and the experimentally observed change in the Tafel slope to be explained. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  3. Electrochemical Hydrogen Evolution: Sabatier's Principle and the Volcano Plot

    Laursen, Anders B.; Varela, Ana Sofia; Dionigi, Fabio; Fanchiu, Hank; Miller, Chandler; Trinhammer, Ole L.; Rossmeisl, Jan; Dahl, Soren

    2012-01-01

    The electrochemical hydrogen evolution reaction (HER) is growing in significance as society begins to rely more on renewable energy sources such as wind and solar power. Thus, research on designing new, inexpensive, and abundant HER catalysts is important. Here, we describe how a simple experiment combined with results from density functional…

  4. Corrosion-electrochemical behavior of nickel in an alkali metal carbonate melt under a chlorine-containing atmosphere

    Nikitina, E. V.; Kudyakov, V. Ya.; Malkov, V. B.; Plaksin, S. V.

    2013-08-01

    The corrosion-electrochemical behavior of a nickel electrode is studied in the melt of lithium, sodium, and potassium (40: 30: 30 mol %) carbonates in the temperature range 500-600°C under an oxidizing atmosphere CO2 + 0.5O2 (2: 1), which is partly replaced by gaseous chlorine (30, 50, 70%) in some experiments. In other experiments, up to 5 wt % chloride of sodium peroxide is introduced in a salt melt. A change in the gas-phase composition is shown to affect the mechanism of nickel corrosion.

  5. Novel Lead dioxide-Graphite-Polymer composite anode for electrochemical chlorine generation

    Gedam, N.; Neti, R.N.; Kormunda, M.; Šubrt, Jan; Bakardjieva, Snejana

    2015-01-01

    Roč. 169, JUL (2015), s. 109-116 ISSN 0013-4686 Institutional support: RVO:61388980 Keywords : beta-Lead dioxide * Graphite * Polymer composite anode * Chlorine generation * Cyclic voltammetry Subject RIV: CG - Electrochemistry Impact factor: 4.803, year: 2015

  6. Porous carbon nanospheres derived from chlorination of bis(cyclopentadienyl)titanium dichloride and their electrochemical capacitor performance

    Gonzalez-Garcia, Pedro, E-mail: pegonzal@quim.ucm.es [Departamento de Quimica Inorganica, Facultad de Ciencias Quimicas, Universidad Complutense, E-28040 Madrid (Spain); Centeno, T.A. [Instituto Nacional del Carbon-CSIC, Apartado 73, E-33080 Oviedo (Spain); Urones-Garrote, Esteban [Centro de Microscopia y Citometria, Universidad Complutense, E-28040 Madrid (Spain); Avila-Brande, David; Otero-Diaz, L. Carlos [Departamento de Quimica Inorganica, Facultad de Ciencias Quimicas, Universidad Complutense, E-28040 Madrid (Spain)

    2011-10-17

    Highlights: {yields} Microporous carbon nanospheres have been produced via chlorination reaction of bis(cyclopentadienyl)titanium dichloride. {yields} The materials present a structure formed by disordered arrangements of graphene-like layers, sp{sup 2}/sp{sup 3} ratio {approx}95-97% and mass-density below pure graphite. {yields} The increase in the reaction temperature decreases the particle size distribution and improves the surface area and the micropore volume. {yields} Electrochemical performance for the 900 deg. C sample shows a specific capacitance of 106 F g{sup -1} in H{sub 2}SO{sub 4} electrolyte and 80 F g{sup -1} in (C{sub 2}H{sub 5}){sub 4}NBF{sub 4}/acetonitrile medium. - Abstract: Conglomerated and accreted porous carbon spheres have been obtained by the chlorination reaction of bis(cyclopentadienyl)titanium dichloride as carbon precursor. The spheres size distribution, derived from scanning electron microscopy observations, shows that the diameter intervals decreases from 70-525 nm at 400 deg. C to 40-370 nm at 900 deg. C. High-resolution transmission electron microscopy observations indicate that the spheres are formed by open and curved randomly stacked graphene-like layers. Electron energy loss spectroscopy studies show relative sp{sup 2}/sp{sup 3} ratio higher than 95% and mass-density values (1.1-1.6 g cm{sup -3}) smaller than graphite. Nitrogen adsorption measurements reveal the presence of micro and mesopores whose contributions to the total porosity greatly depend on the preparation temperature. Galvanostatic charging-discharging measurements on the carbon material synthesized at 900 deg. C provide a specific capacitance of 106 F g{sup -1} in the aqueous H{sub 2}SO{sub 4} electrolyte and 80 F g{sup -1} in the aprotic (C{sub 2}H{sub 5}){sub 4}NBF{sub 4}/acetonitrile medium. These high values suggest the potentiality of this material for electrical energy storage in electrochemical double layer capacitors.

  7. Energy loss in electrochemical diaphragm process of chlorine and alkali industry - A collateral effect of the undesirable generation of chlorate

    Lima, Phabyanno Rodrigues; Mirapalheta, Almir; e Silva Zanta, Carmem Lucia de Paiva; Tonholo, Josealdo [Instituto de Quimica e Biotecnologia, Universidade Federal de Alagoas, 57072970 Maceio, AL (Brazil); Henrique dos Santos Andrade, Marcio [Instituto de Quimica e Biotecnologia, Universidade Federal de Alagoas, 57072970 Maceio, AL (Brazil); Braskem S/A, Maceio, AL (Brazil); Vilar, Eudesio Oliveira [Departamento de Engenharia Quimica, Universidade Federal de Campina, Grande, Campina Grande, PB (Brazil)

    2010-05-15

    Contamination of NaOH with chlorate constitutes a major problem for the chlorine-alkali industry, particularly when electrolytic cells based on the diaphragm process are employed. In this paper, pilot and laboratory cell experiments revealed that chlorate contamination in diaphragm cells also inhibits hydrogen evolution and gives rise to a significant increase in electrical energy consumption. Electrolysis carried out under conditions that simulated the industrial process (current density 240 mA cm{sup -2}; temperature 90 C; brine flux 23 L cm{sup -2} h{sup -1}) revealed that chlorate formation depends on brine flux and NaOH production. The inhibitory effect of chlorate on the main cathodic reaction was demonstrated in bench cell experiments, with cathodic displacement of the hydrogen evolution reaction by more than 100 mV in the presence of 0.4% chlorate compared with ideal conditions in which chlorate formation was absent. This hydrogen generation overpotential can charge the total electric energy balance in more than 5% of the total value, consisting of a critical loss for this process. (author)

  8. A high-porosity carbon molybdenum sulphide composite with enhanced electrochemical hydrogen evolution and stability

    Laursen, Anders B.; Vesborg, Peter C. K.; Chorkendorff, Ib

    2013-01-01

    This work describes a highly active and stable acid activated carbon fibre and amorphous MoSx composite hydrogen evolution catalyst. The increased electrochemical-surface area is demonstrated to cause increased catalyst electrodeposition and activity. These composite electrodes also show...

  9. Polar stratospheric cloud evolution and chlorine activation measured by CALIPSO and MLS, and modeled by ATLAS

    H. Nakajima

    2016-03-01

    Full Text Available We examined observations of polar stratospheric clouds (PSCs by CALIPSO, and of HCl and ClO by MLS along air mass trajectories, to investigate the dependence of the inferred PSC composition on the temperature history of the air parcels and the dependence of the level of chlorine activation on PSC composition. Several case studies based on individual trajectories from the Arctic winter 2009/2010 were conducted, with the trajectories chosen such that the first processing of the air mass by PSCs in this winter occurred on the trajectory. Transitions of PSC composition classes were observed to be highly dependent on the temperature history. In cases of a gradual temperature decrease, nitric acid trihydrate (NAT and super-cooled ternary solution (STS mixture clouds were observed. In cases of rapid temperature decrease, STS clouds were first observed, followed by NAT/STS mixture clouds. When temperatures dropped below the frost point, ice clouds formed and then transformed into NAT/STS mixture clouds when temperature increased above the frost point. The threshold temperature for rapid chlorine activation on PSCs is approximately 4 K below the NAT existence temperature, TNAT. Furthermore, simulations of the ATLAS chemistry and transport box model along the trajectories were used to corroborate the measurements and show good agreement with the observations. Rapid chlorine activation was observed when an air mass encountered PSCs. Usually, chlorine activation was limited by the amount of available ClONO2. Where ClONO2 was not the limiting factor, a large dependence on temperature was evident.

  10. Mechanical and Electrochemical Performance of Carbon Fiber Reinforced Polymer in Oxygen Evolution Environment

    Ji-Hua Zhu

    2016-11-01

    Full Text Available Carbon fiber-reinforced polymer (CFRP is recognized as a promising anode material to prevent steel corrosion in reinforced concrete. However, the electrochemical performance of CFRP itself is unclear. This paper focuses on the understanding of electrochemical and mechanical properties of CFRP in an oxygen evolution environment by conducting accelerated polarization tests. Different amounts of current density were applied in polarization tests with various test durations, and feeding voltage and potential were measured. Afterwards, tensile tests were carried out to investigate the failure modes for the post-polarization CFRP specimens. Results show that CFRP specimens had two typical tensile-failure modes and had a stable anodic performance in an oxygen evolution environment. As such, CFRP can be potentially used as an anode material for impressed current cathodic protection (ICCP of reinforced concrete structures, besides the fact that CFRP can strengthen the structural properties of reinforced concrete.

  11. Electrochemical and Integrated Process Opportunities for On-Site/On-Demand Generation of Chlorine Dioxide - Final Report - 08/02/1996 - 08/01/1999; FINAL

    Tatarchuk, Bruce J.; Krishnagopalan, G.; Nickell, Ryan A.

    2000-01-01

    Due to continued evidence of environmental harm from elemental chlorine bleaching, the nation's paper industry continues to search for cost effective alternative bleaching. A practical and cost effective bleaching alternative is chlorine dioxide manufactured entirely from sodium chlorate. Sodium chlorate is produced by the electrolysis of brine in an undivided cell with steel plate cathodes and dimensionally stable anodes. Although the overpotential at the anode is only 50 mV, the cathodic overpotential is 940 mV. Thus, nearly one volt of electricity is wasted in driving hydrogen evolution at the cathode. Auburn University's Center for Microfibrous Materials Manufacturing has demonstrated that high performance, three dimensional, microfibrous electrodes can improve the performance of capacitors, batteries, hybrid power cells, and electrolysis electrodes in a variety of applications. The goal of this research was to apply this technology to a chlorate cell's cathode and reduce the overpotential between 200 and 400 mV. An economic analysis of the industry has shown that for every 100 mV reduction in overpotential,$100 per square meter of electrode can be saved annually. Due to their enhanced surface area over plates, corrosion of microfibrous electrodes is a major issue in this research. Samples based on chromium protection (i.e. stainless steel) have proved unfeasible for chlorate application. However, samples based on stainless steel and nickel show dramatic performance improvements over industry status quo in chlor-alkali application. Building microfibrous electrodes on a titanium base protected with a silver coating alleviates the corrosion problem and provides 100 mV or more of overpotential reduction. Further reduction is realized by impregnating silver-titanium microfibrous mesh with a PVDF binder and dispersed platinum on activated carbon. The resulting electrodes are mechanically sound, active towards hydrogen evolution, and hold promise for practical

  12. Hydrogen evolution activity and electrochemical stability of selected transition metal carbides in concentrated phosphoric acid

    Tomás García, Antonio Luis; Jensen, Jens Oluf; Bjerrum, Niels J.

    2014-01-01

    phosphoric acid were investigated in a temperature range from 80 to 170°C. A significant dependence of the activities on temperature was observed for all five carbide samples. Through the entire temperature range Group 6 metal carbides showed higher activity than that of the Group 5 metal carbides......Alternative catalysts based on carbides of Group 5 (niobium and tantalum) and 6 (chromium, molybdenum and tungsten) metals were prepared as films on the metallic substrates. The electrochemical activities of these carbide electrodes towards the hydrogen evolution reaction (HER) in concentrated...

  13. Boosting the Performance of the Nickel Anode in the Oxygen Evolution Reaction by Simple Electrochemical Activation

    Shinagawa, Tatsuya

    2017-03-27

    The development of cost-effective and active water-splitting electrocatalysts that work at mild pH is an essential step towards the realization of sustainable energy and material circulation in our society. Its success requires a drastic improvement in the kinetics of the anodic half-reaction of the oxygen evolution reaction (OER), which determines the overall system efficiency to a large extent. A simple electrochemical protocol has been developed to activate Ni electrodes, by which a stable NiOOH phase was formed, which could weakly bind to alkali-metal cations. The electrochemically activated (ECA) Ni electrode reached a current of 10 mA at <1.40 V vs. the reversible hydrogen electrode (RHE) at practical operation temperatures (>75 °C) and a mild pH of ca. 10 with excellent stability (>24 h), greatly surpassing that of the state-of-the-art NiFeOx electrodes under analogous conditions. Water electrolysis was demonstrated with ECA-Ni and NiMo, which required an iR-free overall voltage of only 1.44 V to reach 10 mA cmgeo(-2) .

  14. Boosting the performance of the nickel anode in the oxygen evolution reaction by simple electrochemical activation

    Shinagawa, Tatsuya; Ng, Marcus Tze-Kiat; Takanabe, Kazuhiro [King Abdullah Univ. of Science and Technology (KAUST), KAUST Catalysis Center (KCC) and Physical Sciences and Engineering Div. PSE, Thuwal (Saudi Arabia)

    2017-04-24

    The development of cost-effective and active water-splitting electrocatalysts that work at mild pH is an essential step towards the realization of sustainable energy and material circulation in our society. Its success requires a drastic improvement in the kinetics of the anodic half-reaction of the oxygen evolution reaction (OER), which determines the overall system efficiency to a large extent. A simple electrochemical protocol has been developed to activate Ni electrodes, by which a stable NiOOH phase was formed, which could weakly bind to alkali-metal cations. The electrochemically activated (ECA) Ni electrode reached a current of 10 mA at <1.40 V vs. the reversible hydrogen electrode (RHE) at practical operation temperatures (>75 C) and a mild pH of ca. 10 with excellent stability (>24 h), greatly surpassing that of the state-of-the-art NiFeO{sub x} electrodes under analogous conditions. Water electrolysis was demonstrated with ECA-Ni and NiMo, which required an iR-free overall voltage of only 1.44 V to reach 10 mA cm{sub geo}{sup -2}. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

  15. A mathematical model for hydrogen evolution in an electrochemical cell and experimental validation

    Mahmut D Mat; Yuksel Kaplan; Beycan Ibrahimoglu; Nejat Veziroglu; Rafig Alibeyli; Sadiq Kuliyev

    2006-01-01

    Electrochemical reaction is largely employed in various industrial areas such as hydrogen production, chlorate process, electroplating, metal purification etc. Most of these processes often take place with gas evaluation on the electrodes. Presence of gas phase in the liquid phase makes the problem two-phase flow which is much knowledge available from heat transfer and fluid mechanics studies. The motivation of this study is to investigate hydrogen release in an electrolysis processes from two-phase flow point of view and investigate effect of gas release on the electrolysis process. Hydrogen evolution, flow field and current density distribution in an electrochemical cell are investigated with a two-phase flow model. The mathematical model involves solutions of transport equations for the variables of each phase with allowance for inter phase transfer of mass and momentum. An experimental set-up is established to collect data to validate and improve the mathematical model. Void fraction is determined from measurement of resistivity changes in the system due to the presence of bubbles. A good agreement is obtained between numerical results and experimental data. (authors)

  16. Effect of electrochemical corrosion on the subsurface microstructure evolution of a CoCrMo alloy in albumin containing environment

    Wang, Zhongwei; Yan, Yu; Su, Yanjing; Qiao, Lijie

    2017-01-01

    Highlights: • Accelerated electrochemical corrosion results in severer plastic deformation with finer grains. • Lower applied potential can increase protein adsorption on sample surfaces. • The tribo-film decreases the shear stresses and relief subsurface deformation. • Tribocorrosion induced passive film can suppress the annihilation of stacking faults. - Abstract: The subsurface microstructures of metallic implants play a key role in bio-tribocorrosion. Due to wear or change of local environment, the implant surface can have inhomogeneous electrochemical corrosion properties. In this work, the effect of electrochemical corrosion conditions on the subsurface microstructure evolution of CoCrMo alloys for artificial joints was investigated. Transmission electron microscope (TEM) was employed to observe the subsurface microstructures of worn areas at different applied potentials in a simulated physiological solution. The results showed that applied potentials could affect the severity of the subsurface deformation not only by changing the surface passivation but also affecting the adsorption of protein on the alloy surface.

  17. Effect of electrochemical corrosion on the subsurface microstructure evolution of a CoCrMo alloy in albumin containing environment

    Wang, Zhongwei; Yan, Yu, E-mail: yanyu@ustb.edu.cn; Su, Yanjing; Qiao, Lijie

    2017-06-01

    Highlights: • Accelerated electrochemical corrosion results in severer plastic deformation with finer grains. • Lower applied potential can increase protein adsorption on sample surfaces. • The tribo-film decreases the shear stresses and relief subsurface deformation. • Tribocorrosion induced passive film can suppress the annihilation of stacking faults. - Abstract: The subsurface microstructures of metallic implants play a key role in bio-tribocorrosion. Due to wear or change of local environment, the implant surface can have inhomogeneous electrochemical corrosion properties. In this work, the effect of electrochemical corrosion conditions on the subsurface microstructure evolution of CoCrMo alloys for artificial joints was investigated. Transmission electron microscope (TEM) was employed to observe the subsurface microstructures of worn areas at different applied potentials in a simulated physiological solution. The results showed that applied potentials could affect the severity of the subsurface deformation not only by changing the surface passivation but also affecting the adsorption of protein on the alloy surface.

  18. Identifying the Active Surfaces of Electrochemically Tuned LiCoO2 for Oxygen Evolution Reaction

    Lu, Zhiyi; Chen, Guangxu; Li, Yanbin; Wang, Haotian; Xie, Jin

    2017-01-01

    Identification of active sites for catalytic processes has both fundamental and technological implications for rational design of future catalysts. Herein, we study the active surfaces of layered lithium cobalt oxide (LCO) for the oxygen evolution reaction (OER) using the enhancement effect of electrochemical delithiation (De-LCO). Our theoretical results indicate that the most stable (0001) surface has a very large overpotential for OER independent of lithium content. In contrast, edge sites such as the nonpolar (1120) and polar (0112) surfaces are predicted to be highly active and dependent on (de)lithiation. The effect of lithium extraction from LCO on the surfaces and their OER activities can be understood by the increase of Co 4+ sites relative to Co 3+ and by the shift of active oxygen 2p states. Experimentally, it is demonstrated that LCO nanosheets, which dominantly expose the (0001) surface show negligible OER enhancement upon delithiation. However, a noticeable increase in OER activity (~0.1 V in overpotential shift at 10 mA cm –2 ) is observed for the LCO nanoparticles, where the basal plane is greatly diminished to expose the edge sites, consistent with the theoretical simulations. In addition, we find that the OER activity of De-LCO nanosheets can be improved if we adopt an acid etching method on LCO to create more active edge sites, which in turn provides a strong evidence for the theoretical indication.

  19. Molybdenum carbide-carbon nanocomposites synthesized from a reactive template for electrochemical hydrogen evolution

    Alhajri, Nawal Saad

    2014-01-01

    Molybdenum carbide nanocrystals (Mo2C) with sizes ranging from 3 to 20 nm were synthesized within a carbon matrix starting from a mesoporous graphitic carbon nitride (mpg-C3N4) template with confined pores. A molybdenum carbide phase (Mo2C) with a hexagonal structure was formed using a novel synthetic method involving the reaction of a molybdenum precursor with the carbon residue originating from C3N4 under nitrogen at various temperatures. The synthesized nanocomposites were characterized using powder X-ray diffraction (XRD), temperature-programmed reaction with mass spectroscopy (MS), CHN elemental analyses, thermogravimetric analyses (TGA), nitrogen sorption, X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The results indicated that the synthesized samples have different surface structures and compositions, which are accordingly expected to exhibit different electrocatalytic activities toward the hydrogen evolution reaction (HER). Electrochemical measurements demonstrated that the sample synthesized at 1323 K exhibited the highest and most stable HER current in acidic media, with an onset potential of -100 mV vs. RHE, among the samples prepared in this study. This result is attributed to the sufficiently small particle size (∼8 nm on average) and accordingly high surface area (308 m2 g-1), with less oxidized surface entrapped within the graphitized carbon matrix. © 2014 the Partner Organisations.

  20. Enhanced activity of gold-supported cobalt oxide for the electrochemical evolution of oxygen.

    Yeo, Boon Siang; Bell, Alexis T

    2011-04-13

    Scanning electron microscopy, linear sweep voltammetry, chronoamperometry, and in situ surface-enhanced Raman spectroscopy were used to investigate the electrochemical oxygen evolution reaction (OER) occurring on cobalt oxide films deposited on Au and other metal substrates. All experiments were carried out in 0.1 M KOH. A remarkable finding is that the turnover frequency for the OER exhibited by ∼0.4 ML of cobalt oxide deposited on Au is 40 times higher than that of bulk cobalt oxide. The activity of small amounts of cobalt oxide deposited on Pt, Pd, Cu, and Co decreased monotonically in the order Au > Pt > Pd > Cu > Co, paralleling the decreasing electronegativity of the substrate metal. Another notable finding is that the OER turnover frequency for ∼0.4 ML of cobalt oxide deposited on Au is nearly three times higher than that for bulk Ir. Raman spectroscopy revealed that the as-deposited cobalt oxide is present as Co(3)O(4) but undergoes progressive oxidation to CoO(OH) with increasing anodic potential. The higher OER activity of cobalt oxide deposited on Au is attributed to an increase in fraction of the Co sites present as Co(IV) cations, a state of cobalt believed to be essential for OER to occur. A hypothesis for how Co(IV) cations contribute to OER is proposed and discussed. © 2011 American Chemical Society

  1. Hydrogen evolution reaction on electrodes with different PT/C loadings by electrochemical impedance spectroscopy

    Ortega-Chavez, L. [Inst. Tecnologico de Chihuahua 2, Chihuahua, Chih (Mexico); Ortega-Chavez, L.; Herrera-Peraza, E. [Centro de Investigacion en Materiales Avanzados, Chiuahua, Chih (Mexico); Verde, Y. [Inst. Tecnologico de Cancun, Cancun, Quintana Roo (Mexico)

    2008-04-15

    One of the most widely studied reactions in electrochemistry is the hydrogen evolution reaction (HER). HER is important for the development of water hydrolysis and fuel cell technologies. Because hydrogen-substrate interaction determines oxygen reduction efficiency, an understanding of the chemical and electronic state of hydrogen adsorbed on the electrocatalyst surface is required. Electrochemical impedance spectroscopy (EIS) is a proven highly efficient technique for interface characterization and kinetic parameter determination for different reactions carried out on interfaces. This article presented a study that utilized EIS for characterizing electrodes under HER by implementing a rotating disc electrode with different carbon supported platinum nanoparticles loadings and different potentials in acidic solutions. The results collected by EIS were analyzed in terms of equivalent circuits to calculate different parameters which were compared by statistical analysis. The study also considered the Volmer, Heyrovsky and Tafel steps in the HER reaction as well as a single electro-absorbed intermediate species. The article discussed the experimental set-up with reference to measurements, simulation and fitting. Parameters analysis using ANOVA were reviewed. It was concluded that an increase in impedance occurs when platinum loading decreases in both high and low frequencies. 22 refs., 1 tab., 5 figs.

  2. Cold Incineration of Chlorophenols in Aqueous Solution by Advanced Electrochemical Process Electro-Fenton. Effect of Number and Position of Chlorine Atoms on the Degradation Kinetics

    Oturan, Nihal; Panizza, Marco; Oturan, Mehmet A.

    2009-09-01

    This study reports the kinetics of the degradation of several chlorophenols (CPs), such as monochlorophenols (2-chlorophenol and 4-chlorophenol), dichlorophenols (2,4-dichlorophenol and 2,6- dichlorophenol), trichlorophenols (2,3,5- trichlorophenol and 2,4,5-trichlorophenol), 2,3,5,6-tetrachlorophenol, and pentachlorophenol, by the electro-Fenton process using a carbon felt cathode and a Pt anode. The effect of number and the position of the chlorine atoms in the aromatic ring on the oxidative degradation rate was evaluated and discussed. The oxidation reaction of all the CPs with hydroxyl radicals evidenced a pseudo-first-order kinetics and the rate constant decreased with increasing the number of chlorine atoms. The absolute rate constant of second-order reaction kinetics between CPs and •OH was determined by the competition kinetics method in the range of (3.56-7.75) × 109 M-1 s-1 and follows the same sequence of the apparent rate constants. The mineralization of several CPs and of a mixture of all CPs under study was monitored by the total organic carbon (TOC) removal and the chlorine release during mineralization was followed by ion chromatography. Our results demonstrated that more chlorinated phenols are more difficult to mineralize; however for all the tested CPs, almost quantitative release of chloride ions was obtained after 6 h of treatment.

  3. Electrochemical preparation and characteristics of Ni-Co-LaNi{sub 5} composite coatings as electrode materials for hydrogen evolution

    Wu Gang; Li Ning; Dai Changsong; Zhou Derui

    2004-02-15

    Electrocatalytic activity for the hydrogen evolution reaction on Ni-Co-LaNi{sub 5} composite electrodes prepared by electrochemical codeposition technique was evaluated. The relationship between the current density for hydrogen evolution reaction and the amount of LaNi{sub 5} particles in Ni-Co baths is like the well-known 'volcano plot'. The Surface morphology and microstructure of Ni-Co-LaNi{sub 5} coatings were determined by means of scanning electron microscopy (SEM) and X-ray diffraction (XRD). The kinetic parameters were determined from electrochemical steady-state Tafel polarization and electrochemical impedance spectroscopy technology in 1 M NaOH solution. The values obtained for the apparent energies of activation are 32.48, 46.29 and 57.03 kJ mol{sup -1} for the Ni-Co-LaNi{sub 5}, Ni-Co and Ni electrodes, respectively. The hydrogen evolution reaction on Ni-Co-LaNi{sub 5} proceeds via Volmer-Tafel reaction route with the mixed rate determining characteristics. The composite coating Ni-Co-LaNi{sub 5} is catalytically more active than Ni and Ni-Co electrodes due to the increase in its real surface areas and the decrease in the apparent free energy of activation caused by the electrocatalytic synergistic effect of the Ni-Co alloys and the hydrogen storage intermetallic particles on the electrode surface.

  4. Electrochemical preparation and characteristics of Ni-Co-LaNi5 composite coatings as electrode materials for hydrogen evolution

    Wu Gang; Li Ning; Dai Changsong; Zhou Derui

    2004-01-01

    Electrocatalytic activity for the hydrogen evolution reaction on Ni-Co-LaNi 5 composite electrodes prepared by electrochemical codeposition technique was evaluated. The relationship between the current density for hydrogen evolution reaction and the amount of LaNi 5 particles in Ni-Co baths is like the well-known 'volcano plot'. The Surface morphology and microstructure of Ni-Co-LaNi 5 coatings were determined by means of scanning electron microscopy (SEM) and X-ray diffraction (XRD). The kinetic parameters were determined from electrochemical steady-state Tafel polarization and electrochemical impedance spectroscopy technology in 1 M NaOH solution. The values obtained for the apparent energies of activation are 32.48, 46.29 and 57.03 kJ mol -1 for the Ni-Co-LaNi 5 , Ni-Co and Ni electrodes, respectively. The hydrogen evolution reaction on Ni-Co-LaNi 5 proceeds via Volmer-Tafel reaction route with the mixed rate determining characteristics. The composite coating Ni-Co-LaNi 5 is catalytically more active than Ni and Ni-Co electrodes due to the increase in its real surface areas and the decrease in the apparent free energy of activation caused by the electrocatalytic synergistic effect of the Ni-Co alloys and the hydrogen storage intermetallic particles on the electrode surface

  5. Electrocatalytic oxygen reduction and hydrogen evolution reactions on phthalocyanine modified electrodes: Electrochemical, in situ spectroelectrochemical, and in situ electrocolorimetric monitoring

    Koca, Atif, E-mail: akoca@eng.marmara.edu.tr [Department of Chemical Engineering, Faculty of Engineering, Marmara University, Goeztepe, 34722 Istanbul (Turkey); Kalkan, Ayfer; Bayir, Zehra Altuntas [Department of Chemistry, Technical University of Istanbul, Maslak, 34469 Istanbul (Turkey)

    2011-06-30

    Highlights: > Electrochemical and in situ spectroelectrochemical characterizations of the metallophthalocyanines were performed. > The presence of O{sub 2} influences both oxygen reduction reaction and the electrochemical behaviors of the complexes. > Homogeneous catalytic ORR process occurs via an 'inner sphere' chemical catalysis process. > CoPc and CuPc coated on a glassy carbon electrode decrease the overpotential of the working electrode for H{sup +} reduction. - Abstract: This study describes electrochemical, in situ spectroelectrochemical, and in situ electrocolorimetric monitoring of the electrocatalytic reduction of molecular oxygen and hydronium ion on the phthalocyanine-modified electrodes. For this purpose, electrochemical and in situ spectroelectrochemical characterizations of the metallophthalocyanines (MPc) bearing tetrakis-[4-((4'-trifluoromethyl)phenoxy)phenoxy] groups were performed. While CoPc gives both metal-based and ring-based redox processes, H{sub 2}Pc, ZnPc and CuPc show only ring-based electron transfer processes. In situ electrocolorimetric method was applied to investigate the color of the electrogenerated anionic and cationic forms of the complexes. The presence of O{sub 2} in the electrolyte system influences both oxygen reduction reaction and the electrochemical and spectral behaviors of the complexes, which indicate electrocatalytic activity of the complexes for the oxygen reduction reaction. Perchloric acid titrations monitored by voltammetry represent possible electrocatalytic activities of the complexes for hydrogen evolution reaction. CoPc and CuPc coated on a glassy carbon electrode decrease the overpotential of the working electrode for H{sup +} reduction. The nature of the metal center changes the electrocatalytic activities for hydrogen evolution reaction in aqueous solution. Although CuPc has an inactive metal center, its electrocatalytic activity is recorded more than CoPc for H{sup +} reduction in aqueous

  6. Electrochemical Impedance Spectroscopy Illuminating Performance Evolution of Porous Core–Shell Structured Nickel/Nickel Oxide Anode Materials

    Yan, Bo; Li, Minsi; Li, Xifei; Bai, Zhimin; Dong, Lei; Li, Dejun

    2015-01-01

    Highlights: • The electrochemical reaction kinetics of the Ni/NiO anode was studied for the first time. • Charge transfer resistance is main contribution to total resistance during discharge process. • The slow growth of the SEI film is responsible for the capacity fading upon cycling. • Some promising strategies to optimize NiO anode performance were summarized. - Abstract: The electrochemical reaction kinetics of the porous core–shell structured Ni/NiO anode for Li ion battery application is systematically investigated by monitoring the electrochemical impedance evolution for the first time. The electrochemical impedance under prescribed condition is measured by using impedance spectroscopy in equilibrium conditions at various depths of discharge (DOD) during charge–discharge cycles. The Nyquist plots of the binder-free porous Ni/NiO electrode are interpreted with a selective equivalent circuit composed of solution resistance, solid electrolyte interphase (SEI) film, charge transfer and solid state diffusion. The impedance analysis shows that the change of charge transfer resistance is the main contribution to the total resistance change during discharge, and the surface configuration of the obtained electrode may experience significant change during the first two cycles. Meanwhile, the increase of internal resistance reduced the utilization efficiency of the active material may be another convincing factor to increase the irreversible capacity. In addition, the impedance evolution of the as-prepared electrode during charge–discharge cycles reveals that the slow growth of the SEI film is responsible for the capacity fading after long term cycling. As a result, several strategies are summarized to optimize the electrochemical performances of transition metal oxide anodes for lithium ion batteries

  7. Chlorine poisoning

    ... gas) Gas released when opening a partially filled industrial container of chlorine tablets that have been sitting ... change in acid level of the blood (pH balance), which leads to damage in all of the ...

  8. Moessbauer spectroscopy characterization and electrochemical study of the kinetics of oxidation of iron in chlorinated aqueous media: structure and equilibrium diagram of green rust one

    Genin, J.M.R.; Rezel, D.; Bauer, Ph.; Olowe, A.; Beral, A.

    1986-01-01

    Moessbauer spectroscopy allows to precise the structure of akaganeite, lepidocrocite, green rust I and initial hydroxide of a simulated corrosion process of iron in chlorinated aqueous media. The characterization of the compounds during the process is coupled with E - pH recordings, yielding the kinetics of the various reactions (order and activation energy) as well as the Pourbaix diagram of Green Rust I by scanning the [Cl - ]/[OH - ] ratio. (author) 16 refs., 15 figs

  9. Cathodic electrochemical activation of Co3O4 nanoarrays: a smart strategy to significantly boost the hydrogen evolution activity.

    Yang, Li; Zhou, Huang; Qin, Xin; Guo, Xiaodong; Cui, Guanwei; Asiri, Abdullah M; Sun, Xuping

    2018-02-22

    Co(hydro)oxides show unsatisfactory catalytic activity for the hydrogen evolution reaction (HER) in alkaline media, and it is thus highly desirable but still remains a challenge to design and develop Co(hydro)oxide derived materials as superb hydrogen-evolving catalysts using a facile, rapid and less energy-intensive method. Here, we propose a cathodic electrochemical activation strategy toward greatly boosted HER activity of a Co 3 O 4 nanoarray via room-temperature cathodic polarization in sodium hypophosphite solution. After activation, the overpotential significantly decreases from 260 to 73 mV to drive a geometrical catalytic current density of 10 mA cm -2 in 1.0 M KOH. Notably, this activated electrode also shows strong long-term electrochemical durability with the retention of its catalytic activity at 100 mA cm -2 for at least 40 h.

  10. Regulation of Electrochemically Generated H2O2 in Situ from a Novel CB-PTFE Cathode for Transformation of Chlorine Benzene in Groundwater

    Jiang, J.; Zhang, X.; Li, G.

    2014-12-01

    Fenton's reagents (H2O2 and Fe2+ catalyst commonly) have been widely used in soil and groundwater remediation. But the excessive H2O2 decomposition and the pH modification (acidification) problem have been limitations for Fenton based remediation strategies. The Electro-Fenton (E- Fenton) processes has been recently developed to solve the problems, in which Fe2+ or H2O2are generated in situ as continuing source of Fenton's reagents. In this study, a novel CB-PTFE cathode and a Fe cathode were employed to generate H2O2 and Fe2+ in situ simultaneously. The generated reactive oxidizing species, i.e., O2,H2O2 and hydroxyl radical (HO•), oxidized bio-refractory organics to nontoxic matters in groundwater. Automatic pH adjustments are achieved by appropriately arraying the electrodes. Laboratory batch tests and column tests for the E-Fenton oxidation and hybrid electrolysis system were conducted to evaluate the transformation efficiency of chlorine benzene. Results from batch experiments suggested the CB-PTFE cathode was effective for reducing O2 to H2O2. The H2O2 concentration reached 468 mg/L under the condition of pH 3.0 and 30mA/cm2 in 60 minutes, which was 5 and 10 times of that with a graphite and C-felt cathode. The removal efficiency of chlorine benzene reached 80% in 20 minutes. Both chlorine benzene degradation and H2O2 production increased with decreasing solution pH and increasing current density. The results from the columns tests proved that the in situ E-Fenton system is a feasible method for groundwater remediation.

  11. Structurally Deformed MoS2 for Electrochemically Stable, Thermally Resistant, and Highly Efficient Hydrogen Evolution Reaction

    Chen, Yen-Chang; Lu, Ang-Yu; Lu, Ping; Yang, Xiulin; Jiang, Chang-Ming; Mariano, Marina; Kaehr, Brian; Lin, Oliver; Taylor, André ; Sharp, Ian D.; Li, Lain-Jong; Chou, Stanley S.; Tung, Vincent

    2017-01-01

    The emerging molybdenum disulfide (MoS2) offers intriguing possibilities for realizing a transformative new catalyst for driving the hydrogen evolution reaction (HER). However, the trade-off between catalytic activity and long-term stability represents a formidable challenge and has not been extensively addressed. This study reports that metastable and temperature-sensitive chemically exfoliated MoS2 (ce-MoS2) can be made into electrochemically stable (5000 cycles), and thermally robust (300 °C) while maintaining synthetic scalability and excellent catalytic activity through physical-transformation into 3D structurally deformed nanostructures. The dimensional transition enabled by a high throughput electrohydrodynamic process provides highly accessible, and electrochemically active surface area and facilitates efficient transport across various interfaces. Meanwhile, the hierarchically strained morphology is found to improve electronic coupling between active sites and current collecting substrates without the need for selective engineering the electronically heterogeneous interfaces. Specifically, the synergistic combination of high strain load stemmed from capillarity-induced-self-crumpling and sulfur (S) vacancies intrinsic to chemical exfoliation enables simultaneous modulation of active site density and intrinsic HER activity regardless of continuous operation or elevated temperature. These results provide new insights into how catalytic activity, electrochemical-, and thermal stability can be concurrently enhanced through the physical transformation that is reminiscent of nature, in which properties of biological materials emerge from evolved dimensional transitions.

  12. Structurally Deformed MoS2 for Electrochemically Stable, Thermally Resistant, and Highly Efficient Hydrogen Evolution Reaction

    Chen, Yen-Chang

    2017-10-12

    The emerging molybdenum disulfide (MoS2) offers intriguing possibilities for realizing a transformative new catalyst for driving the hydrogen evolution reaction (HER). However, the trade-off between catalytic activity and long-term stability represents a formidable challenge and has not been extensively addressed. This study reports that metastable and temperature-sensitive chemically exfoliated MoS2 (ce-MoS2) can be made into electrochemically stable (5000 cycles), and thermally robust (300 °C) while maintaining synthetic scalability and excellent catalytic activity through physical-transformation into 3D structurally deformed nanostructures. The dimensional transition enabled by a high throughput electrohydrodynamic process provides highly accessible, and electrochemically active surface area and facilitates efficient transport across various interfaces. Meanwhile, the hierarchically strained morphology is found to improve electronic coupling between active sites and current collecting substrates without the need for selective engineering the electronically heterogeneous interfaces. Specifically, the synergistic combination of high strain load stemmed from capillarity-induced-self-crumpling and sulfur (S) vacancies intrinsic to chemical exfoliation enables simultaneous modulation of active site density and intrinsic HER activity regardless of continuous operation or elevated temperature. These results provide new insights into how catalytic activity, electrochemical-, and thermal stability can be concurrently enhanced through the physical transformation that is reminiscent of nature, in which properties of biological materials emerge from evolved dimensional transitions.

  13. Electrochemical behavior of NixW1−x materials as catalyst for hydrogen evolution reaction in alkaline media

    Oliver-Tolentino, Miguel A.; Arce-Estrada, Elsa M.; Cortés-Escobedo, Claudia A.; Bolarín-Miro, Ana M.; Sánchez-De Jesús, Félix; González-Huerta, Rosa de G.; Manzo-Robledo, Arturo

    2012-01-01

    Highlights: ► The electrochemical techniques used in this study elucidated the Ni–W surface state. ► The Ni–W materials were effective for the hydrogen evolution reaction. ► The prepared alloys exhibited higher catalytic activity than their precursors. ► The preparation method is relatively simple and effective procedure. - Abstract: In the present work, results of electrochemical evaluation, as well as morphological and structural characterization of Ni x W 1−x materials with x = 0.77, 0.64, 0.4, 0.19 and 0.07 processed by means of high energy ball milling from high purity powders are presented. Also, the electrocatalytic performance on the hydrogen evolution reaction (HER) of the Ni x W 1−x materials evaluated by linear polarization and cyclic voltammetry techniques in alkaline media at room temperature is discussed. The structural and morphological characterization of the as-prepared materials was carried out using X-ray diffraction (XRD) and scanning electron microscopy (SEM). Results indicated a small-particle clusters and solid solution formation. According to the kinetics parameters the best electrocatalytic activity was observed at Ni 64 W 36 .

  14. A Study of the Mechanism of the Hydrogen Evolution Reaction on Nickel by Surface Interrogation Scanning Electrochemical Microscopy.

    Liang, Zhenxing; Ahn, Hyun S; Bard, Allen J

    2017-04-05

    The hydrogen evolution reaction (HER) on Ni in alkaline media was investigated by scanning electrochemical microscopy under two operating modes. First, the substrate generation/tip collection mode was employed to extract the "true" cathodic current associated with the HER from the total current in the polarization curve. Compared to metallic Ni, the electrocatalytic activity of the HER is improved in the presence of the low-valence-state oxide of Ni. This result is in agreement with a previous claim that the dissociative adsorption of water can be enhanced at the Ni/Ni oxide interface. Second, the surface-interrogation scanning electrochemical microscopy (SI-SECM) mode was used to directly measure the coverage of the adsorbed hydrogen on Ni at given potentials. Simulation indicates that the hydrogen coverage follows a Frumkin isotherm with respect to the applied potential. On the basis of the combined analysis of the Tafel slope and surface hydrogen coverage, the rate-determining step is suggested to be the adsorption of hydrogen (Volmer step) in the investigated potential window.

  15. Free-standing, flexible β-Ni(OH)2/electrochemically-exfoliated graphene film electrode for efficient oxygen evolution

    Wang, Lanlan; Zhang, Jian; Jiang, Weitao; Zhao, Hong; Liu, Hongzhong

    2018-03-01

    The oxidation of water into molecular oxygen (oxygen evolution reaction, OER) is a pivotal reaction in many energy conversion devices. The high cost of IrO2, however, seriously hinder its large-scale applications in water oxidation. Here, we have at first reported a free-standing and flexible film electrode consisting of 2D β-Ni(OH)2/electrochemically-exfoliated graphene hybrid nanosheets (NiG-2), which is synthesized by a solvothermal reaction and an assembly process. The as-obtained NiG-2 film electrode exhibited an excellent electrocatalytic OER activity with an extremely low OER onset overpotential of ∼250 mV in a 1 M KOH aqueous solution, which is lower than these of the commercial Ir/C (370 mV at 10 mA cm-2) catalyst.

  16. Controllable synthesis, morphology evolution and electrochemical properties of LiFePO4 cathode materials for Li-ion batteries.

    Song, Jianjun; Wang, Lin; Shao, Guangjie; Shi, Meiwu; Ma, Zhipeng; Wang, Guiling; Song, Wei; Liu, Shuang; Wang, Caixia

    2014-05-07

    Monodispersed LiFePO4 nanocrystals with diverse morphologies were successfully synthesized via a mild and controllable solvothermal approach with a mixture of ethylene glycol and oleic acid as the solvent. Morphology evolution of LiFePO4 nanoparticles from nanoplates to nanorods can be simply realized by varying the volume ratio of oleic acid to ethylene glycol. Moreover, the mechanism of competitive adsorption between ethylene glycol and oleic acid was proposed for the formation of different morphologies. Electrochemical measurements show that the LiFePO4/C nanorods have an initial discharge capacity of 155 mA h g(-1) at 0.5 C with a capacity retention of 80% at a high rate of 5 C, which confirms that LiFePO4/C nanorods exhibit excellent rate capability and cycling stability.

  17. Stress evolution in elastic-plastic electrodes during electrochemical processes: A numerical method and its applications

    Wen, Jici; Wei, Yujie; Cheng, Yang-Tse

    2018-07-01

    Monitoring in real time the stress state in high capacity electrodes during charge-discharge processes is pivotal to the performance assessment and structural optimization of advanced batteries. The wafer curvature measurement technique broadly employed in thin-film industry, together with stress analysis using the Stoney equation, has been successfully adopted to measure in situ the stress in thin film electrodes. How large plastic deformation or interfacial delamination during electrochemical cycles in such electrodes affects the applicability of Stoney equation remains unclear. Here we develop a robust electrochemical-mechanical coupled numerical procedure to investigate the influence of large plastic deformation and interfacial failure on the measured stress in thin film electrodes. We identify how the constitutive behavior of electrode materials and film-substrate interfacial properties affect the measured stress-capacity curves of electrodes, and hence establish the relationship of electrode material parameters with the characteristics of stress-capacity curves. Using Li-ions batteries as examples, we show that plastic deformation and interfacial delamination account for the asymmetric stress-capacity loops seen in in situ stress measurements. The methods used here, along with the finite-element code in the supplementary material, may be used to model the electrode behavior as a function of the state of charge.

  18. Exfoliated MoS2 nanosheets as efficient catalysts for electrochemical hydrogen evolution

    Ji, Shanshan; Yang, Zhe; Zhang, Chao; Liu, Zhenyan; Tjiu, Weng Weei; Phang, In Yee; Zhang, Zheng; Pan, Jisheng; Liu, Tianxi

    2013-01-01

    Graphical abstract: An efficient electrocatalyst for hydrogen evolution has been developed based on exfoliation of bulk MoS 2 crystals via a direct dispersion and ultrasonication method. Drop-casting method is used to fabricate the exfoliated MoS 2 nanosheets modified glass carbon electrode (E-MoS 2 /GCE) with various loadings. The E-MoS 2 /GCE with electrode loading of 48 μg cm −1 exhibits high catalytic activity for hydrogen evolution with a low overpotential (−0.12 V) and a high current density (1.26 mA cm −2 , at η = 150 mV). -- Highlights: • Two-dimensional MoS 2 nanosheets have been obtained by exfoliation of bulk MoS 2 crystals. • Exfoliated MoS 2 nanosheets show high electrocatalytic activity for H 2 production. • This study provides a new approach for renewable and economic H 2 production. -- Abstract: An efficient electrocatalyst for hydrogen evolution has been developed based on liquid exfoliation of bulk MoS 2 via a direct dispersion and ultrasonication method. Transmission electron microscopy and atomic force microscopy measurements show that the exfoliated MoS 2 consists of two-dimensional nanosheets. The exfoliated MoS 2 nanosheets modified glass carbon electrode (E-MoS 2 /GCE) with various loadings is fabricated via a drop-casting method. The electrocatalytic activity of E-MoS 2 /GCE toward hydrogen evolution reaction is examined using linear sweep voltammetry. It is shown that the E-MoS 2 /GCE with an electrode loading of 48 μg cm −2 exhibits a high catalytic activity for hydrogen evolution with a low overpotential (−0.12 V) and a high current density (1.26 mA cm −2 , at η = 150 mV)

  19. Luminescence evolution of porous GaN thin films prepared via UV-assisted electrochemical etching

    Cheah, S.F.; Lee, S.C.; Ng, S.S.; Yam, F.K.; Abu Hassan, H.; Hassan, Z.

    2015-01-01

    Porous gallium nitride (GaN) thin films with different surface morphologies and free carriers properties were fabricated from Si-doped GaN thin films using ultra-violet assisted electrochemical etching approach under various etching voltages. Fluctuation of luminescence signals was observed in the photoluminescence spectra of porous GaN thin films. Taking advantage of the spectral sensitivity of infrared attenuated total reflection spectroscopy on semiconductor materials, roles of free carriers and porous structure in controlling luminescence properties of GaN were investigated thoroughly. The results revealed that enhancement in luminescence signal is not always attained upon porosification. Although porosification is correlated to the luminescence enhancement, however, free carrier is the primary factor to enhance luminescence intensity. Due to unavoidable significant reduction of free carriers from Si-doped GaN in the porosification process, control of etching depth (i.e., thickness of porous layer formed from the Si-doped layer) is critical in fabricating porous GaN thin film with enhanced luminescence response. - Highlights: • Various pore morphologies with free carrier properties are produced by Si-doped GaN. • Free carriers are important to control the luminescence signal of porous GaN. • Enhancement of luminescence signal relies on the pore depth of Si-doped layer

  20. Chlorine in the stratosphere

    VON CLARMANN, T.

    2013-01-01

    This paper reviews the various aspects of chlorine compounds in the stratosphere, both their roles as reactants and as tracers of dynamical processes. In the stratosphere, reactive chlorine is released from chlorofluorocarbons and other chlorine-containing organic source gases. To a large extent reactive chlorine is then sequestered in reservoir species ClONO2 and HCl. Re-activation of chlorine happens predominantly in polar winter vortices by heterogeneous reaction in combination with sunlig...

  1. Characterization of electrochemically deposited films from aqueous and ionic liquid cobalt precursors toward hydrogen evolution reactions

    Dushatinski, Thomas; Huff, Clay; Abdel-Fattah, Tarek M., E-mail: fattah@cnu.edu

    2016-11-01

    Highlights: • Co films deposition via aqueous and ionic liquid Precursors. • Hydrogen evolution produced from reactive surfaces. • Co deposited films characterized by SEM, AFM, EDX and XRD techniques. - Abstract: Electrodepositions of cobalt films were achieved using an aqueous or an ethylene glycol based non-aqueous solution containing choline chloride (vitamin B4) with cobalt chloride hexahydrate precursor toward hydrogen evolution reactions from sodium borohydride (NaBH{sub 4}) as solid hydrogen feedstock (SHF). The resulting cobalt films had reflectivity at 550 nm of 2.2% for aqueously deposited films (ACoF) and 1.3% for non-aqueously deposited films (NCoF). Surface morphology studied by scanning electron microscopy showed a positive correlation between particle size and thickness. The film thicknesses were tunable between >100 μm and <300 μm for each film. The roughness (Ra) value measurements by Dektak surface profiling showed that the NCoF (Ra = 165 nm) was smoother than the ACoF (Ra = 418 nm). The NCoFs and ACoFs contained only α phase (FCC) crystallites. The NCoFs were crystalline while the ACoFs were largely amorphous from X-ray diffraction analysis. The NCoF had an average Vickers hardness value of 84 MPa as compared to 176 MPa for ACoF. The aqueous precursor has a single absorption maximum at 510 nm and the non-aqueous precursor had three absorption maxima at 630, 670, and 695 nm. The hydrogen evolution reactions over a 1 cm{sup 2} catalytic surface with aqueous NaBH{sub 4} solutions generated rate constants (K) = equal to 4.9 × 10{sup −3} min{sup −1}, 4.6 × 10{sup −3} min{sup −1}, and 3.3 × 10{sup −3} min{sup −1} for ACoF, NCoF, and copper substrate respectively.

  2. Evolution of the microstructure in electrochemically deposited copper films at room temperature

    Pantleon, Karen; Somers, Marcel A. J.

    2007-01-01

    The room temperature evolution of the microstructure in copper electrodeposits (self-annealing) was investigated by means of X-ray diffraction analysis and simultaneous measurement of the electrical resistivity as a function of time with an unprecedented time resolution. Independent of the copper...... the crystallographic texture changes by a multiple twinning mechanism. The kinetics of self-annealing is strongly affected by the thickness of the deposit. Storage of the copper films at sub-zero temperatures effectively hinders self-annealing and does not affect the kinetics of self-annealing upon reheating to room...... temperature....

  3. Correlation of electrical and physical properties of photoanode with hydrogen evolution in enzymatic photo-electrochemical cell

    Bae, Sanghyun; Kang, Junwon [Department of Environmental Engineering, Yonsei University, 234 Maeji-ri, Hungub-myun, Wonju, Gangwon-do 220-710 (Korea); Shim, Eunjung [Department of Chemistry, Chungnam National University, 220 Gung-dong, Yuseong-gu, Daejeon 305-764 (Korea); Yoon, Jaekyung; Joo, Hyunku [Fossil Energy and Environment Research Department, Korea Institute of Energy Research, 71-2 Jang-dong, Yuseong-gu, Daejeon 305-343 (Korea)

    2008-05-01

    In this study, the electrical and physical properties, including the current density, open-circuit voltage, morphology and crystalline structure, of an anodized TiO{sub 2} electrode on a titanium foil are correlated with the hydrogen production rate in an enzymatic photo-electrochemical system. The effect of light intensity at ca. 74 and ca. 146 mW cm{sup -2} on the properties is also examined. Anodizing (20 V; bath temperature 5 C; anodizing time 45 min) and subsequent annealing (350-850 C for 5 h) of the Ti foils in an O{sub 2} atmosphere led to the formation of a tube-shaped, or a compact layered, TiO{sub 2} film on the Ti substrate depending on the annealing temperature. The annealing temperature has a similar effect on the properties of the sample and the hydrogen evolution rate. The generated electrical value, the chronoamperometry (CA), is +13 to -229 and +13 to -247 {mu}A for light intensities of ca. 74 and ca. 146 mW cm{sup -2}, while the corresponding open-circuit voltage (OCV) is in the range of -41 to -687 and -144 to 738 mV, respectively. In the absence of light (dark), the CA is 13-29 {mu}A and the OCV is +258 to -126 mW cm{sup -2}. The trend in the electrical properties for the different samples is well matched with the rate of hydrogen evolution. The samples with higher activities (450, 550, and 650 C) have similar X-ray diffraction (XRD) patterns, which clearly indicates that the samples showing the highest evolution rate are composed of both anatase and rutile, while those showing a lower evolution rate are made of either anatase or rutile. Increasing the intensity of the irradiated light causes a remarkable enhancement in the rate of hydrogen production from 71 to 153 {mu}mol h{sup -1} cm{sup -2}. (author)

  4. Synthesis of tantalum carbide and nitride nanoparticles using a reactive mesoporous template for electrochemical hydrogen evolution

    Alhajri, Nawal Saad; Yoshida, Hiroshi; Anjum, Dalaver H.; Garcia Esparza, Angel T.; Kubota, Jun; Domen, Kazunari; Takanabe, Kazuhiro

    2013-01-01

    Tantalum carbide and nitride nanocrystals were prepared through the reaction of a tantalum precursor with mesoporous graphitic (mpg)-C 3N4. The effects of the reaction temperature, the ratio of the Ta precursor to the reactive template (mpg-C3N4), and the selection of the carrier gas (Ar, N2 and NH3) on the resultant crystal phases and structures were investigated. The produced samples were characterized using powder X-ray diffraction (XRD), CHN elemental analyses, thermogravimetric analyses (TGA), nitrogen sorption, a temperature-programmed reaction with mass spectroscopy (MS), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM). The results indicate that the different tantalum phases with cubic structure, TaN, Ta2CN, and TaC, can be formed under a flow of nitrogen when formed at different temperatures. The Ta3N5 phase with a Ta5+ oxidation state was solely obtained at 1023 K under a flow of ammonia, which gasified the C 3N4 template and was confirmed by detecting the decomposed gaseous products via MS. Significantly, the formation of TaC, Ta2CN, and TaN can be controlled by altering the weight ratio of the C 3N4 template relative to the Ta precursor at 1573 K under a flow of nitrogen. The high C3N4/Ta precursor ratio generally resulted in high carbide content rather than a nitride one, consistent with the role of mpg-C3N4 as a carbon source. Electrochemical measurements revealed that the synthesized nanomaterials were consistently able to produce hydrogen under acidic conditions (pH 1). The obtained Tafel slope indicates that the rate-determining step is the Volmer discharge step, which is consistent with adsorbed hydrogen being weakly bound to the surface during electrocatalysis. © 2013 The Royal Society of Chemistry.

  5. Pulse-reverse electrodeposition for mesoporous metal films: combination of hydrogen evolution assisted deposition and electrochemical dealloying.

    Cherevko, Serhiy; Kulyk, Nadiia; Chung, Chan-Hwa

    2012-01-21

    Hydrogen evolution assisted electrodeposition is a new bottom-up technique allowing the fast and simple synthesis of nanometals. Electrochemical dealloying is a top-down approach with the same purpose. In this work, we show that a combination of these two methods in sequence by pulse-reverse electrodeposition can be used to prepare high-surface-area nanostructured metals. Highly porous adherent platinum is obtained by the deposition of CuPt alloy during the cathodic cycles and the selective dissolution of copper during the anodic cycles. The convection created by the movement of the hydrogen bubbles increases the deposition rate and removes the dissolved copper ions from the diffusion layer, which ensures the deposition of a film with the same stoichiometry throughout the whole process. Due to the relatively high ratio of copper atoms on the surface in the as-deposited layer, it is proposed that the dealloying kinetics is significantly higher than that usually observed during the dealloying process in a model system. The proposed approach has several advantages over other methods, such as a very high growth rate and needlessness of any post-treatment processes. A detailed analysis of the effect of pulse-reverse waveform parameters on the properties of the films is presented. Mesoporous platinum with pores and ligaments having characteristic sizes of less than 10 nm, an equivalent surface area of up to ca. 220 m(2) cm(-3), and a roughness factor of more than 1000 is fabricated.

  6. MoS₂ nanocube structures as catalysts for electrochemical H₂ evolution from acidic aqueous solutions.

    Maijenburg, A Wouter; Regis, Morrisa; Hattori, Azusa N; Tanaka, Hidekazu; Choi, Kyoung-Shin; ten Elshof, Johan E

    2014-02-12

    Core-shell PMMA-Au nanocube structures made by a combination of nanoimprint lithography and sidewall deposition were used as template for electrodeposition of MoS2, Ni, and Pt. Linear sweep voltammetry experiments obtained in an aqueous solution containing 0.29 M H2SO4 (pH 0.24) showed that the onset potential of the core-shell-shell PMMA-Au-MoS2 nanocube electrode for the hydrogen evolution reaction (HER) was shifted to the positive direction (i.e., requiring a lower overpotential) by 20-40 mV compared to planar MoS2 films. This indicates that the nanocube electrodes have a significantly increased HER activity, which is probably because of a higher density of catalytically active edge sites available at the nanocube surface. It was also found that the HER activity initially increased with increasing MoS2 deposition time, but decreased after deposition for 60 min because the edges of the nanocubes became rounded, thereby decreasing the number of active edge sites. By depositing Ni and Pt on top of PMMA-Au nanocubes, it was shown that this method can also be used for the synthesis of nanocube structures with varying compositions.

  7. In Situ Characterization of Ni and Ni/Fe Thin Film Electrodes for Oxygen Evolution in Alkaline Media by a Raman-Coupled Scanning Electrochemical Microscope Setup.

    Steimecke, Matthias; Seiffarth, Gerda; Bron, Michael

    2017-10-17

    We present a spectroelectrochemical setup, in which Raman microscopy is combined with scanning electrochemical microscopy (SECM) in order to provide both spectroscopic and electrochemical information on the very same location of an electrode at the same time. The setup is applied to a subject of high academic and practical interest, namely, the oxygen evolution reaction at Ni and Ni/Fe electrodes. It comprises a transparent substrate electrode, onto which Ni and Ni/Fe thin films are deposited. An ultramicroelectrode (UME) is placed closely above the substrate to obtain electrochemical information, while a Raman microscope probes the same sample spot from below. To obtain information on oxygen evolution activity and structural changes, increasingly positive potentials from 0.1 up to 0.7 V vs Hg|HgO|1 M KOH were applied to the Ni/Fe-electrodes in 0.1 M KOH solution. Evolved oxygen is detected by reduction at a Pt UME, allowing for the determination of onset potentials, while the substrate current, which is recorded in parallel, is due to both overlapping oxygen evolution and the oxidation of Ni(OH) 2 to NiOOH. An optimum of 15% Fe in Ni/Fe films with respect to oxygen evolution activity was determined. At the same time, the potential-dependent formation of γ-NiOOH characterized by the Raman double band at 475 and 557 cm -1 allows for the conclusion that a certain amount of disorder introduced by Fe atoms is necessary to obtain high oxygen evolution reaction (OER) activity.

  8. A facile approach to prepare crumpled CoTMPyP/electrochemically reduced graphene oxide nanohybrid as an efficient electrocatalyst for hydrogen evolution reaction

    Ma, Juanjuan, E-mail: majj0518@hotmail.com [Department of Chemical Engineering, Huaihai Institute of Technology, Lianyungang 222005 (China); School of Materials Science and Engineering, Nanyang Technological University, 639798, Singapore (Singapore); Liu, Lin; Chen, Qian; Yang, Min [Department of Chemical Engineering, Huaihai Institute of Technology, Lianyungang 222005 (China); Wang, Danping [School of Materials Science and Engineering, Nanyang Technological University, 639798, Singapore (Singapore); Tong, Zhiwei [Department of Chemical Engineering, Huaihai Institute of Technology, Lianyungang 222005 (China); Chen, Zhong, E-mail: aszchen@ntu.edu.sg [School of Materials Science and Engineering, Nanyang Technological University, 639798, Singapore (Singapore)

    2017-03-31

    Highlights: • Crumpled CoTMPyP/ERGO hybrid was successfully prepared by a facile two-step process. • CoTMPyP nanoaggregates are homogeneously distributed over the graphene surface. • CoTMPyP/ERGO hybrid film shows good electrocatalytic activity and stability for HER. - Abstract: Elaborate design and synthesis of efficient and stable non-Pt electrocatalysts for some renewable energy related conversion/storage processes are one of the major goals of sustainable chemistry. Herein, we report a facile method to fabricate Co porphyrin functionalized electrochemically reduced graphene oxide (CoTMPyP/ERGO) thin film by direct assembly of oppositely charged tetrakis(N-methylpyridyl) porphyrinato cobalt (CoTMPyP) and GO nanosheets under mild conditions followed by an electrochemical reduction procedure. STEM analysis confirms that CoTMPyP nanoaggregates are homogeneously distributed over the graphene surface. The electrochemical properties of CoTMPyP/ERGO were investigated by cyclic voltammetry, linear sweep voltammetry and electrochemical impedance spectroscopy. The results demonstrate that CoTMPyP/ERGO nanohybrid film can serve as excellent electrocatalyst for hydrogen evolution in alkaline solution with high activity and stability. The intimate contact and efficient electron transfer between CoTMPyP and ERGO, as well as the crumpled structure, contribute to the improvement of the electrocatalytic performance.

  9. An investigation of thin-film Ni-Fe oxide catalysts for the electrochemical evolution of oxygen.

    Louie, Mary W; Bell, Alexis T

    2013-08-21

    A detailed investigation has been carried out of the structure and electrochemical activity of electrodeposited Ni-Fe films for the oxygen evolution reaction (OER) in alkaline electrolytes. Ni-Fe films with a bulk and surface composition of 40% Fe exhibit OER activities that are roughly 2 orders of magnitude higher than that of a freshly deposited Ni film and about 3 orders of magnitude higher than that of an Fe film. The freshly deposited Ni film increases in activity by as much as 20-fold during exposure to the electrolyte (KOH); however, all films containing Fe are stable as deposited. The oxidation of Ni(OH)2 to NiOOH in Ni films occurs at potentials below the onset of the OER. Incorporation of Fe into the film increases the potential at which Ni(OH)2/NiOOH redox occurs and decreases the average oxidation state of Ni in NiOOH. The Tafel slope (40 mV dec(-1)) and reaction order in OH(-) (1) for the mixed Ni-Fe films (containing up to 95% Fe) are the same as those for aged Ni films. In situ Raman spectra acquired in 0.1 M KOH at OER potentials show two bands characteristic of NiOOH. The relative intensities of these bands vary with Fe content, indicating a change in the local environment of Ni-O. Similar changes in the relative intensities of the bands and an increase in OER activity are observed when pure Ni films are aged. These observations suggest that the OER is catalyzed by Ni in Ni-Fe films and that the presence of Fe alters the redox properties of Ni, causing a positive shift in the potential at which Ni(OH)2/NiOOH redox occurs, a decrease in the average oxidation state of the Ni sites, and a concurrent increase in the activity of Ni cations for the OER.

  10. Evolution of microstructure of epoxy coating during UV degradation progress studied by slow positron annihilation spectroscopy and electrochemical impedance spectroscopy

    Liu, Fuwei; Yin, Mingxi; Xiong, Bangyun; Zheng, Feng; Mao, Wenfeng; Chen, Zhe; He, Chunqing; Zhao, Xipo; Fang, Pengfei

    2014-01-01

    Graphical abstract: - Highlights: • Decrements in S value and water uptake coefficient confirm the post-cure process. • Molecular chain scission leads to the formation of microporous structure. • The formation of an aged layer with high density is verified by EIS. - Abstract: Evolution of chemical functional groups, microstructure and water barrier properties of a polyamide-cured epoxy (diglycidyl ether of bisphenol-A epoxy resin, DGEBA) coating during ultraviolet A (UV-A) photo-oxidative aging is systematically investigated. At the early stage of aging, decrements of S parameter and water uptake coefficient indicate the formation of a more compact structure induced by the post-curing process. After 208 hours (h) of UV irradiation, a novel time constant at relatively high frequency (3.5 × 10 2 Hz) appears in the electrochemical impedance spectroscopy (EIS) spectra suggesting that a microporous layer generates near the surface of DGEBA film. With the increase in irradiation time, overlap of two time constants at frequencies around 18 Hz and 3.7 × 10 3 Hz is observed after 1.33 h of immersion, indicating that the micropores grow towards the bulk and form more characteristic layers with microporous structures. After irradiation for 399 h, a low S parameter region near the sample surface is observed, which implies that a surface layer with low free volume may have formed. With longer exposure, EIS results also reveal that the water barrier property of the coating can be improved, which confirms the formation of the denser surface layer near the surface as a result of radical recombination during UV-A treatment

  11. Evolution of the Corrosion Morphology on AZ31B Tracked Electrochemically and by In Situ Microscopy in Chloride-Containing Media

    Melia, M. A.; Cain, T. W.; Briglia, B. F.; Scully, J. R.; Fitz-Gerald, J. M.

    2017-11-01

    The evolution of open-circuit corrosion morphology as a function of immersion time for Mg alloy AZ31B in 0.6-M NaCl solution was investigated. Real-time optical microscopy accompanied by simultaneous electrochemical characterization was used to characterize the filiform corrosion (FFC) of AZ31B. Specifically, the behavior of propagating corrosion filaments on the metal surface was observed, and correlations among polarization resistance, filament propagation rates, open-circuit potential, and active coverage of local corrosion sites were revealed. Three distinct stages of corrosion were observed in 0.6-M NaCl. An initial passive region, during which a slow potential rise occurred (termed stage I), a second FFC region (termed stage II) with shallow penetrating, distinct filaments, and a final FFC region (termed stage III) with deeper penetrating filaments, aligned to form a linear front. The electrochemical properties of each stage are discussed, providing insights into the penetration rates and corrosion model.

  12. Technology assessment: Chlorine chemistry

    Wolff, H.; Alwast, H.; Buttgereit, R.

    1994-01-01

    Chlorine is not just one of many chemical feedstocks which is used in a few definitely harmful products like PVC or CFC but is irrelevant in all other respects. Just the opposite is true: There is hardly any product line of the chemical industry that can do without chlorine, from herbicides and pesticides to dyes, plastics, pharmaceuticals, photographic atricles, and cosmetics. Chlorine is not only a key element of chemical production but also an ubiquitous element of everyday life in civilisation. There are even many who would agree that the volume of chlorine production is an indicator of the competitive strength and national wealth of a modern society. By now, however, it has become evident that the unreflected use of chlorine is no longer ecologically acceptable. The consequences of a chlorine phase-out as compared to the continued chlorine production at the present level were investigated scientifically by a PROGNOS team. They are presented in this book. (orig.) [de

  13. Alternative methods for chlorination

    Fiessinger, F; Rook, J J; Duguet, J P

    1985-12-01

    Existing disinfectants are oxidative agents which all present negative effects on subsequent treatment processes. None of them has decisive advantages over chlorine, although chlorine-dioxide and chloramines might at times be preferable. Optimum treatment practices will improve the removal of organic precursors before final disinfection which could then consist in a light chlorine addition. A philosophy of radical change in water treatment technology encompassing physical treatment without chemicals such as membrane filtration, solid disinfectants is presented.

  14. Enhanced activity of CaFeMg layered double hydroxides-supported gold nanodendrites for the electrochemical evolution of oxygen and hydrogen in alkaline media

    Havakeshian, Elaheh; Salavati, Hossein; Taei, Masoumeh; Hasheminasab, Fatemeh; Seddighi, Mohadeseh

    2018-02-01

    In this study, Au was electrodeposited on a support of CaFeMg layered double hydroxide and then, its catalytic activity was investigated for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Field emission scanning electron microscopy images showed that a uniform porous film of aggregated nano-particles of the LDH has been decorated with Au nanodendrite-like structures (AuNDs@LDH). The results obtained from polarization curves, Tafel plots and electrochemical impedance spectroscopy showed that the AuNDs@LDH exhibits lower overpotential, higher current density, faster kinetics and enhanced stability for both of the OER and HER, in comparison with the single AuNPs and LDH catalysts.

  15. Chlorination and chloramines formation

    Yee, Lim Fang; Mohd Pauzi Abdullah; Sadia Ata; Abbas Abdullah; Basar IShak; Khairul Nidzham

    2008-01-01

    Chlorination is the most important method of disinfection in Malaysia which aims at ensuring an acceptable and safe drinking water quality. The dosing of chlorine to surface water containing ammonia and nitrogen compounds may form chloramines in the treated water. During this reaction, inorganic and organic chloramines are formed. The recommended maximum acceptable concentration (MAC) for chloramines in drinking water is 3000 μg/L. The production of monochloramine, dichloramine and trichloramine is highly dependent upon pH, contact time and the chlorine to ammonia molar ratio. The purpose of this study is to examine the formation of chloramines that occur upon the chlorination during the treatment process. Chloramines were determined using the N,N-diethyl-p-phenylenediamine (DPD) colorimetric method. The influences of ammonia, pH and chlorine dosage on the chloramines formation were also studied. This paper presents a modeling approach based on regression analysis which is designed to estimate the formation of chloramines. The correlation between the concentration of chloramines and the ammonia, pH and chlorine dosage was examined. In all cases, the quantity of chloramines formed depended linearly upon the amount of chlorine dosage. On the basis of this study it reveals that the concentration of chloramines is a function of chlorine dosage and the ammonia concentration to the chlorination process. PH seems to not significantly affect the formation of chloramines. (author)

  16. Electrochemical behavior of Ni{sub x}W{sub 1-x} materials as catalyst for hydrogen evolution reaction in alkaline media

    Oliver-Tolentino, Miguel A. [UPIBI-IPN, Departamento de Ciencias Basicas, Av. Acueducto s/n, Barrio La Laguna, Col. Ticoman, Mexico D.F. 07340 (Mexico); Arce-Estrada, Elsa M. [ESIQIE-IPN Departamento de Ingenieria en Metalurgia y Materiales, UPALM, UPALM, Mexico D.F. 07738 (Mexico); Cortes-Escobedo, Claudia A. [Centro de Investigacion e Innovacion Tecnologica del IPN, Cda. Cecati s/n, Col. Sta. Catarina, CP 02250 Azcapotzalco D.F. (Mexico); Bolarin-Miro, Ana M.; Sanchez-De Jesus, Felix [Area Academica de Ciencias de la Tierra y Materiales, Universidad Autonoma del Estado de Hidalgo, CU, Carr. Pachuca-Tulancingo Km. 4.5, Mineral de la Reforma, CP 42184 Hidalgo (Mexico); Gonzalez-Huerta, Rosa de G. [ESIQIE-IPN, Departamento de Ingenieria Quimica - Laboratorio de Electroquimica y Corrosion, Edif. Z-5 3er piso, UPALM, Mexico D.F. 07738 (Mexico); Manzo-Robledo, Arturo, E-mail: amanzor@ipn.mx [ESIQIE-IPN, Departamento de Ingenieria Quimica - Laboratorio de Electroquimica y Corrosion, Edif. Z-5 3er piso, UPALM, Mexico D.F. 07738 (Mexico)

    2012-09-25

    Highlights: Black-Right-Pointing-Pointer The electrochemical techniques used in this study elucidated the Ni-W surface state. Black-Right-Pointing-Pointer The Ni-W materials were effective for the hydrogen evolution reaction. Black-Right-Pointing-Pointer The prepared alloys exhibited higher catalytic activity than their precursors. Black-Right-Pointing-Pointer The preparation method is relatively simple and effective procedure. - Abstract: In the present work, results of electrochemical evaluation, as well as morphological and structural characterization of Ni{sub x}W{sub 1-x} materials with x = 0.77, 0.64, 0.4, 0.19 and 0.07 processed by means of high energy ball milling from high purity powders are presented. Also, the electrocatalytic performance on the hydrogen evolution reaction (HER) of the Ni{sub x}W{sub 1-x} materials evaluated by linear polarization and cyclic voltammetry techniques in alkaline media at room temperature is discussed. The structural and morphological characterization of the as-prepared materials was carried out using X-ray diffraction (XRD) and scanning electron microscopy (SEM). Results indicated a small-particle clusters and solid solution formation. According to the kinetics parameters the best electrocatalytic activity was observed at Ni{sub 64}W{sub 36}.

  17. Electrolysis of an acidic NaCl solution with a graphite anode : IV. Chlorine evolution at a graphite electrode after switching off current

    Janssen, L.J.J.; Hoogland, J.G.

    1970-01-01

    During electrolysis of an acid chloride soln., at. Cl is taken up by a graphite anode. After switching off the current, the evolution of mol. Cl continues. This phenomenon is designated as residual gas evolution (RGE). The mol. Cl is formed according to the Volmer-Heyrovsky mechanism, Clads + e ->

  18. Chlorine solar neutrino experiment

    Rowley, J.K.; Cleveland, B.T.; Davis, R. Jr.

    1984-01-01

    The chlorine solar neutrino experiment in the Homestake Gold Mine is described and the results obtained with the chlorine detector over the last fourteen years are summarized and discussed. Background processes producing 37 Ar and the question of the constancy of the production rate of 37 Ar are given special emphasis

  19. Electrochemical maps and movies of the hydrogen evolution reaction on natural crystals of molybdenite (MoS2): basal vs. edge plane activity.

    Bentley, Cameron L; Kang, Minkyung; Maddar, Faduma M; Li, Fengwang; Walker, Marc; Zhang, Jie; Unwin, Patrick R

    2017-09-01

    Two dimensional (2D) semiconductor materials, such as molybdenum disulfide (MoS 2 ) have attracted considerable interest in a range of chemical and electrochemical applications, for example, as an abundant and low-cost alternative electrocatalyst to platinum for the hydrogen evolution reaction (HER). While it has been proposed that the edge plane of MoS 2 possesses high catalytic activity for the HER relative to the "catalytically inert" basal plane, this conclusion has been drawn mainly from macroscale electrochemical (voltammetric) measurements, which reflect the "average" electrocatalytic behavior of complex electrode ensembles. In this work, we report the first spatially-resolved measurements of HER activity on natural crystals of molybdenite, achieved using voltammetric scanning electrochemical cell microscopy (SECCM), whereby pixel-resolved linear-sweep voltammogram (LSV) measurements have allowed the HER to be visualized at multiple different potentials to construct electrochemical flux movies with nanoscale resolution. Key features of the SECCM technique are that characteristic surface sites can be targeted and analyzed in detail and, further, that the electrocatalyst area is known with good precision (in contrast to many macroscale measurements on supported catalysts). Through correlation of the local voltammetric response with information from scanning electron microscopy (SEM) and atomic force microscopy (AFM) in a multi-microscopy approach , it is demonstrated unequivocally that while the basal plane of bulk MoS 2 (2H crystal phase) possesses significant activity, the HER is greatly facilitated at the edge plane ( e.g. , surface defects such as steps, edges or crevices). Semi-quantitative treatment of the voltammetric data reveals that the HER at the basal plane of MoS 2 has a Tafel slope and exchange current density ( J 0 ) of ∼120 mV per decade and 2.5 × 10 -6 A cm -2 (comparable to polycrystalline Co, Ni, Cu and Au), respectively, while the edge

  20. Evolution of electrochemical performance in Li3V2(PO4)3/C composites caused by cation incorporation

    Zhang, Lu-Lu; Liang, Gan; Peng, Gang; Jiang, Yan; Fang, Hui; Huang, Yun-Hui; Croft, Mark C.; Ignatov, Alexander

    2013-01-01

    Graphical abstract: Four electrochemically active cations (M = Fe, Co, Ni, Mn) are doped into Li 3 V 2 (PO 4 ) 3 . M-incorporation does not change the monoclinic structure of Li 3 V 2 (PO 4 ) 3 , but forms some solid solutions. Minor LiMPO 4 impurity phases can be formed in the LVMP/C samples. Moreover, FePO 4 also exists as impurity in the LVFeP/C sample. Compared with pristine LVP/C, LVNiP/C electrode exhibits the lowest capacity, resulting from the decreased electronic conductivity and the lowest Li-ion diffusion coefficient, whereas LVFeP/C shows the best electrochemical performance. -- Highlights: • Cation-incorporated Li 3 V 2 (PO 4 ) 3 /C have been systematically investigated. • Cation incorporation in Li 3 V 2 (PO 4 ) 3 does not change the monoclinic structure but form solid solution. • Fe-incorporation shows the best electrochemical performance whereas Ni-incorporation shows the poorest performance. • A clear profile of cation incorporation with Fe, Co, Ni, Mn ions in Li 3 V 2 (PO 4 ) 3 /C is obtained. -- Abstract: Li 3 V 2 (PO 4 ) 3 /C (LVP/C) composites incorporated by a series of electrochemically active cations (Fe, Co, Ni, Mn) have been successfully prepared by a conventional solid-state reaction. M-incorporation (M = Fe, Co, Ni, Mn) in Li 3 V 2 (PO 4 ) 3 does not change the monoclinic structure. Analyzed with X-ray photoelectron spectroscopy, X-ray absorption spectroscopy and high-resolution transmission electron microscopy, we find that the valence is between +2.67 and +3 for Fe, and is +2 for Co, Ni and Mn. M-doped LVP and LiMPO 4 phases coexist in the incorporated LVP/C composites. Compared with pristine LVP/C, Fe-incorporated LVP/C shows the best electrochemical performance with the highest initial discharge capacity of 131.4 mAh g −1 at 0.1 C between 2.5 and 4.3 V. The Fe-incorporated LVP/C sample also exhibits excellent rate capability with an average capacity of 122.4 mAh g −1 at 1 C and 93.5 mAh g −1 at 5 C, resulting from the

  1. MOF-derived Cu-Pd/nanoporous carbon composite as an efficient catalyst for hydrogen evolution reaction: A comparison between hydrothermal and electrochemical synthesis

    Mandegarzad, Sakineh; Raoof, Jahan Bakhsh; Hosseini, Sayed Reza; Ojani, Reza

    2018-04-01

    In this study, a novel catalyst based on Cu-Pd bimetallic nanoparticles supported on nanoporous carbon composite (NPCC) is successfully fabricated through three-step process and used as an electrocatalyst towards hydrogen evolution reaction (HER). At the first step, MOF-199 is synthesized via two distinct strategies; (1) hydrothermal (HT) and (2) electrochemical (EC). Next, the synthesized MOF-199 is used as a template in order to prepare Cu/NPCC by direct carbonization under N2 atmosphere followed by galvanic replacement reaction of Cu metals by PdII ions. All the prepared materials are characterized by X-ray diffraction (XRD), energy-dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), and nitrogen adsorption/desorption measurements. The effect of synthesis method of MOF-199 on the electrocatalytic activity of the final product towards HER is investigated. The electrochemical measurements indicate that Cu-Pd/NPCC derived from the MOF prepared by EC method (Cu-Pd/NPCC/EC) exhibits an enhanced catalytic activity towards HER in H2SO4 solution than the Cu-Pd/NPCC/HT. This improvement may be attributed to using of supporting electrolyte in the preparation of Cu-Pd/NPCC/EC.

  2. One-step and low-temperature synthesis of iodine-doped graphene and its multifunctional applications for hydrogen evolution reaction and electrochemical sensing

    Chu, Ke; Wang, Fan; Zhao, Xiao-lin; Wei, Xiao-ping; Wang, Xin-wei; Tian, Ye

    2017-01-01

    Iodine (I) has emerged as a powerful heteroatom dopant for efficiently tailoring the electrocatalytic properties of graphene. However, the preparation methods of I-doped graphene (I-G) and its electrocatalysis applications remain largely unexplored. Herein, a one-step and low-temperature hydrothermal approach was developed for the successful synthesis of I-G with a high I-doping level (0.52 at.%). The resulting I-G was then applied as a metal-free catalyst for hydrogen evolution reaction (HER) and electrochemical sensing. It was shown that the I-G exhibited a dramatically enhanced HER activity compared to undoped graphene, attributed to the critical role of I-doping in offering large exposed active sites and high electron transfer capability. Furthermore, I-G also displayed attractive sensing performances for highly sensitive and selective detection of dopamine. These findings demonstrate that the hydrothermally synthesized I-G can be a promising electrocatalyst for multifunctional applications in water-splitting and electrochemical sensing.

  3. Exploring the kinetic and thermodynamic aspects of four-electron electrochemical reactions: electrocatalysis of oxygen evolution by metal oxides and biological systems.

    Wang, Vincent C-C

    2016-08-10

    Finding fundamental and general mechanisms for electrochemical reactions, such as the oxygen evolution reaction (OER) from water and reduction of CO2, plays vital roles in developing the desired electrocatalysts for facilitating solar fuel production. Recently, density functional theory (DFT) calculations have shown that there is a universal scaling relation of adsorption energy between key intermediate species, HO(ad) and HOO(ad), on the surface of metal oxides as OER electrocatalysts. In this paper, a kinetic and thermodynamic model for the four-electron electrochemical reaction based on previous OER mechanisms proposed by DFT calculations is developed to further investigate the electrocatalytic properties over a wide range of metal oxides and photosystem II. The OER activity of metal oxides (i.e. electrocatalytic current) calculated from the DFT-calculated equilibrium potentials with kinetic properties, such as the rate constants for interfacial electron transfer and catalytic turnover, can lead to a volcano-shaped trend that agrees with the results observed in experiments. In addition, the kinetic aspects of the impact on the electrocatalysts are evaluated. Finally, comparing the results of metal oxides and photosystem II, and fitting experimental voltammograms give further insights into kinetic and thermodynamic roles. Here, the general guidelines for designing OER electrocatalysts with unified kinetic and thermodynamic properties are presented.

  4. Automatic devices for electrochemical water treatment with cooling of electrolyte

    Trišović Tomislav Lj.

    2016-01-01

    Full Text Available The most common disinfectants for water treatment are based on chlorine and its compounds. Practically, water treatments with chlorine compounds have no alternative, since they provide, in comparison to other effective processes such as ozonization or ultraviolet irradiation, high residual disinfection capacity. Unfortunately, all of chlorine-based compounds for disinfection tend to degrade during storage, thus reducing the concentration of active chlorine. Apart from degradation, additional problems are transportation, storage and handling of such hazardous compounds. Nowadays, a lot of attention is paid to the development of electrochemical devices for in situ production of chlorine dioxide or sodium hypochlorite as efficient disinfectants for water treatment. The most important part of such a device is the electrochemical reactor. Electrochemical reactor uses external source of direct current in order to produce disinfectants in electrochemical reactions occurring at the electrodes. Construction of an electrochemical device for water treatment is based on evaluation of optimal conditions for electrochemical reactions during continues production of disinfectants. The aim of this study was to develop a low-cost electrochemical device for the production of disinfectant, active chlorine, at the place of its usage, based on newly developed technical solutions and newest commercial components. The projected electrochemical device was constructed and mounted, and its operation was investigated. Investigations involved both functionality of individual components and device in general. The major goal of these investigations was to achieve maximal efficiency in extreme condition of elevated room temperature and humidity with a novel device construction involving coaxial heat exchanger at the solution inlet. Room operation of the proposed device was investigated when relative humidity was set to 90% and the ambient temperature of 38°C. The obtained

  5. Zirconia concentrate chlorination

    Costa, N.G.; Albuquerque Brocchi, E. de

    1990-01-01

    Chlorination experiments were conducted in order to study the kinetics of gasification of the zirconium oxide present in the zirconia concentrate. The variables studied are temperature (1173 to 1373 K), percentage of reducing agent (12 to 36%) and porosity (22 to 30%). The results indicated a greater influence of temperature and percentage of reducing agent as well as allowed the conclusion that a balance between the levels of these variables is an important factor in the appropriate chlorination conditions. (author)

  6. Chlorine trifluoride (1963)

    Vincent, L.M.; Gillardeau, J.

    1963-01-01

    This monograph on chlorine trifluoride may be considered as a working tool useful in gaseous diffusion research. It consists of data gathered from the literature and includes furthermore a certain amount of original data. This monograph groups together the physical, chemical and physiological properties of chlorine trifluoride, as well as the preparation and analytical methods. It has been thought wise to add some technological information, and the safety regulations governing its use. (authors) [fr

  7. Study of organic chlorine in soils and formation in biotic and abiotic conditions

    Osswald, Aurelie

    2016-01-01

    Chlorine has long been considered as the predominantly chlorine form present in the environment. However, recent studies have shown that chlorine is retained in the soil as an organic form and is formed by a natural process of chlorination mainly from the microbial activity of the soil still poorly documented. The aim of this study is to estimate the organic and inorganic forms of chlorine in contrasting soil and highlight the evolution of these forms according to certain environmental parameters or terms of incubations and to the activity of microorganisms. For this, the organo-mineral horizons of contrasting soil were studied (i) in situ: The amounts of chlorine and physico-chemical and microbiological parameters of soil were measured; (ii) in two experimental devices incubations under different conditions. Measurements of chlorine levels between the beginning and the end of the first experiment were measured by AOX analyzer. For the second experiment, the soil was previously enriched with Na 37 Cl and 37 Cl levels were measured by HR ICP MS. Soil samples from these incubations were analyzed by Xanes spectrometry to identify the speciation of chlorine forms in soils. Soil non-extractable organic chlorine contents represent almost all of the chlorine. The parameters that influence the distribution of chlorine contents in soils correspond to vegetation cover, pH, organic carbon content and quantities of microorganisms. The chlorine contents measured by AOX analyzer and by HR ICP MS highlight an organic chlorine formation over time in relation to the microorganisms in the soil. The measures carried out by HR ICP MS show also an organic chlorine formation in abiotic conditions. Conversely, XANES spectrometry measurements have shown any organic chlorine formation. In conclusion, the parameters that influence the distribution of chlorine contents in soils have been targeted. Similarly, the microbial origin of the chlorination process has been demonstrated, although a

  8. A carbon nanotube based resettable sensor for measuring free chlorine in drinking water

    Hsu, Leo H. H.; Hoque, Enamul; Kruse, Peter; Ravi Selvaganapathy, P.

    2015-01-01

    Free chlorine from dissolved chlorine gas is widely used as a disinfectant for drinking water. The residual chlorine concentration has to be continuously monitored and accurately controlled in a certain range around 0.5–2 mg/l to ensure drinking water safety and quality. However, simple, reliable, and reagent free monitoring devices are currently not available. Here, we present a free chlorine sensor that uses oxidation of a phenyl-capped aniline tetramer (PCAT) to dope single wall carbon nanotubes (SWCNTs) and to change their resistance. The oxidation of PCAT by chlorine switches the PCAT-SWCNT system into a low resistance (p-doped) state which can be detected by probing it with a small voltage. The change in resistance is found to be proportional to the log-scale concentration of the free chlorine in the sample. The p-doping of the PCAT-SWCNT film then can be electrochemically reversed by polarizing it cathodically. This sensor not only shows good sensing response in the whole concentration range of free chlorine in drinking water but is also able to be electrochemically reset back many times without the use of any reagents. This simple sensor is ideally suited for measuring free chlorine in drinking water continuously

  9. Widely available active sites on Ni2P for electrochemical hydrogen evolution - insights from first principles calculations

    Hansen, Martin Hangaard; Stern, Lucas-Alexandre; Feng, Ligang

    2015-01-01

    We present insights into the mechanism and the active site for hydrogen evolution on nickel phosphide (Ni2P). Ni2P was recently discovered to be a very active non-precious hydrogen evolution catalyst. Current literature attributes the activity of Ni2P to a particular site on the (0001) facet....... In the present study, using Density Functional Theory (DFT) calculations, we show that several widely available low index crystal facets on Ni2P have better properties for a high catalytic activity. DFT calculations were used to identify moderately bonding nickel bridge sites and nickel hollow sites for hydrogen...... adsorption and to calculate barriers for the Tafel pathway. The investigated surfaces in this study were the (10 (1) over bar0), ((1) over bar(1) over bar 20), (11 (2) over bar0), (11 (2) over bar1) and (0001) facets of the hexagonal Ni2P crystal. In addition to the DFT results, we present experiments on Ni2...

  10. Chlorine transportation risk assessment

    Lautkaski, Risto; Mankamo, Tuomas.

    1977-02-01

    An assessment has been made on the toxication risk of the population due to the bulk rail transportation of liquid chlorine in Finland. Fourteen typical rail accidents were selected and their probability was estimated using the accident file of the Finnish State Railways. The probability of a chlorine leak was assessed for each type of accident separately using four leak size categories. The assessed leakage probability was dominated by station accidents, especially by collisions of a chlorine tanker and a locomotive. Toxication hazard areas were estimated for the leak categories. A simple model was constructed to describe the centring of the densely populated areas along the railway line. A comparison was made between the obtained risk and some other risks including those due to nuclear reactor accidents. (author)

  11. Chlorination leaching of cadmium

    Lach, E.; Pajak, I.; Bojanowska, A.

    1978-01-01

    The results of the investigations on chlorination leaching of cadmium from dust coming from dry dust collector of sinter belt, that is leaching with water saturated with gaseous chlorine and leaching with solutions of ammonium chloride and sodium chloride were given. The optimum conditions for these processes were established. It was found, that the method of leaching in the presence of gaseous chlorine is more effective, as it allows to report into the solution over 90% cadmium contained in dust. Owing to technical difficulties, environmental protection and safety conditions more advantageous seems to be the use as leaching agent of the ammonium chloride solutions. When applying 20% NH 4 Cl and temperature of 60 0 C, the time of 2 hours and the ratio of solid to liquid of 1:5, 70% cadmium contained in the dust can be reported into the solution. (auth.)

  12. MoS2 Nanocube structures as catalysts for electrochemical H2 evolution from acidic aqueous solutions

    Maijenburg, A.W.; Regis, M.; Hattori, A.N.; Tanaka, H.; Choi, K.-S.; ten Elshof, Johan E.

    2014-01-01

    Core–shell PMMA–Au nanocube structures made by a combination of nanoimprint lithography and sidewall deposition were used as template for electrodeposition of MoS2, Ni, and Pt. Linear sweep voltammetry experiments obtained in an aqueous solution containing 0.29 M H2SO4 (pH 0.24) showed that the onset potential of the core–shell–shell PMMA–Au–MoS2 nanocube electrode for the hydrogen evolution reaction (HER) was shifted to the positive direction (i.e., requiring a lower overpotential) by 20–40 ...

  13. Survey of potential chlorine production processes. Final report

    1979-04-01

    This report is part of the ongoing study of industrial electrochemical processes for the purpose of identifying methods of improving energy efficiencies. A computerized literature search of past and current chlorine generation methods was performed to identify basic chlorine production processes. Over 200 pertinent references are cited involving 20 separate and distinct chlorine processes. Each basic process is evaluated for its engineering and economic viability and energy efficiency. A flow diagram is provided for each basic process. Four criteria are used to determine the most promising processes: raw material availability, type and amount of energy required, by-product demand/disposal and status of development. The most promising processes are determined to be the membrane process (with and without catalytic electrodes), Kel-Chlor, Mobay (direct electrolysis of hydrogen chloride), the Shell process (catalytic oxidation of hydrogen chloride) and oxidation of ammonium chloride. Each of these processes is further studied to determine what activities may be pursued.

  14. Formation and evolution of nanoporous bimetallic Ag-Cu alloy by electrochemically dealloying Mg-(Ag-Cu)-Y metallic glass

    Li, Ran; Wu, Na; Liu, Jijuan; Jin, Yu; Chen, Xiao-Bo; Zhang, Tao

    2017-01-01

    Highlights: • Uniform nanoporous Ag-Cu alloy was fabricated by dealloying Mg-based metallic glass. • The nanoporous structure was built up with numerous Ag-Cu ligaments. • The nanoporous ligaments show two-stage coarsening behavior with dealloying time. • The formation and evolution mechanisms of the nanoporous structure were clarified. • It could provide new guidance to the synthesis of nanoporous multi-component alloys. - Abstract: A three-dimensional nanoporous bimetallic Ag-Cu alloy with uniform chemical composition has been fabricated by dealloying Mg_6_5Ag_1_2_._5Cu_1_2_._5Y_1_0 metallic glass in dilute (0.04 M) H_2SO_4 aqueous solution under free-corrosion conditions. The nanoporous Ag-Cu evolves through two distinct stages. First, ligaments of the nanoporous structure, consisting of supersaturated Ag(Cu) solid solution with a constant Ag/Cu mole ratio of 1:1, are yielded. Second, with excessive immersion, some Cu atoms separate from the metastable nanoporous matrix and form spherical Cu particles on the sample surface. Formation and evolution mechanisms of the nanoporous structure are proposed.

  15. Synthesis of Galaxite, Mn0.9Co0.1Al2O4, and its application as a novel nanocatalyst for electrochemical hydrogen evolution reaction

    Saeidfirozeh, Homa; Shafiekhani, Azizollah; Beheshti-Marnani, Amirkhosro; Askari, Mohammad Bagher

    2018-06-01

    A new compound Mn0.9Co0.1Al2O4 nanowires were synthesized by thermal method. The resulting powder samples were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and X-ray diffraction (XRD). We found that a set of phase transformation occurred during the process. Eventually, five phases including three spinal phases, the corundum (á-Al2O3) and MnO were formed at 1100 °C.As dominant morphology, the cubic galaxite nanowires were identified by X-ray analysis. Moreover, X-ray analysis showed that Mn3O4 and Co3O4 nanoparticles were formed in tetragonal and cubic symmetry respectively. The SEM image revealed that a dominate morphology of product has cubic nanowires shape with an average diameter in range 38-43 nm. Furthermore, we observed that influence of temperature was very important in the nanowire formation process. Electrochemical hydrogen evolution reaction (HER) of synthetic composite was evaluated and the over potential of HER was calculated about 110 mV with low Tafel slope equal to 42 mV dec-1, which was comparable with amounts reported transition metal dichalcogenides with satisfying durability.

  16. Where does Chlorine-36 go?

    Anon.

    2000-01-01

    Chlorine-36 and Iodine-129 are the unique long-life radionuclides in the halogen family and halogens are known to be very mobile in the environment. Chlorine-36 is present in slight quantities in radioactive wastes containing carbon or issued from spent fuel reprocessing. The migration of Chlorine-36 in the environment has been very little studied, so a collaboration between the French institute of protection and nuclear safety (IPSN) and the Ukrainian institute for agricultural radioecology (UIAR) has been launched. IPSN will study the migration of Chlorine-36 in soils and UIAR will be in charge of studying the transfer of Chlorine-36 from soil to plants. (A.C.)

  17. Effect of the temperature and the chlorine pressure, over the aluminium chlorides obtained by direct chlorination of the 6061 alloy

    Alvarez, Fabiola J.; Bohe, Ana E.; Pasquevich, Daniel M.

    2003-01-01

    The aluminium chloride is synthesized by direct chlorination of aluminium, in agreement with the following reaction: Al(s) + 3/2 Cl 2 AlCl 3 (s,g).The present work focuses on the preparation of aluminium chlorides by two methods: (a) Chlorination of 6061 aluminium alloy with gaseous chlorine in sealed containers, filled with different pressures of gas, from 0.8 to 74 Kpa and in the range of temperature between 200 0 and 500 0 C.(b) Chlorination of the same alloy in chlorine flow between 150 0 and 400 0 C.In the sealed systems, the hexahydrated aluminium trichloride predominated over the anhydrous form. For pressures lower than 14 Kpa and temperatures under 250 0 C, the chloride didn't appear.The residues were rich in aluminium, chlorine and magnesium.In the other systems, the anhydrous chloride was found in the areas of the reactor of temperatures above 100 0 C, for all the thermal treatments. The waste was composed by CrCl 3 and AlCl 3 .6H 2 O.The influence of the chlorine pressures and the heating temperature over the characteristics of the product, was studied.The characterization techniques were x-ray diffraction and energy dispersive spectroscopy, and the evolution of the structure was followed by scanning electron microscopy

  18. Edge-rich MoS_2 Naonosheets Rooting into Polyaniline Nanofibers as Effective Catalyst for Electrochemical Hydrogen Evolution

    Zhang, Nan; Ma, Weiguang; Wu, Tongshun; Wang, Haoyu; Han, Dongxue; Niu, Li

    2015-01-01

    Graphical abstract: For the first time polyaniline (PANI) was employed as an admirable substrate to construct the hierarchical integrative hybrid with MoS_2 (MoS_2/PANI) for hydrogen evolution reaction (HER), which achieved great active edges exposure and excellent HER performance. - Highlights: • PANI is first applied as the support of MoS_2 for enhanced HER performance. • Great active edges exposure of the hybrid significantly benefits the HER activity. • Superior HER activity and excellent stability of MoS_2/PANI have been achieved. - Abstract: Conductive polymer polyaniline (PANI) with abundant protonated sites which are beneficial to hydrogen evolution reaction (HER), was applied as the support of MoS_2 for enhanced HER performance for the first time. The novel three dimensional (3D) HER catalyst (MoS_2/PANI) was constructed with two dimensional (2D) MoS_2 building blocks rooting into the integrative nanowires. PANI nanofibers acted as excellent substrates for the uniform, dense and approximate vertical growth of MoS_2 nanosheets exposing abundant active edges. Consequently, excellent HER performance has been achieved with a low onset overpotential of 100 mV and a small Tafel slope of 45 mV dec"−"1. Most importantly, it only needed 200 and 247 mV overpotential to reach the current density of 30 and 100 mA/cm"2 respectively. Additionally, MoS_2/PANI has achieved superior stability over other MoS_2-polymer-based HER electrocatalyst. In general, for the first time, employing PANI for the construction of the edge-rich integrative hybrid has successfully achieved an outstanding HER performance.

  19. In situ electrodeposition of CoP nanoparticles on carbon nanomaterial doped polyphenylene sulfide flexible electrode for electrochemical hydrogen evolution

    Wang, Tingxia; Jiang, Yimin; Zhou, Yaxin; Du, Yongling; Wang, Chunming

    2018-06-01

    Active and durable electrocatalyst for hydrogen evolution reaction (HER) is pivotal to generate molecular hydrogen more energy-efficient, but directly grafting electrocatalyst on electrode material by a single-step method without compromising the catalytic activity and stability remains a challenge. Herein, an intriguing electrode, reduced graphene oxide modified carbon nanotube/reduced graphene oxide/polyphenylene sulfide (RGO-CNT/RGO/PPS) film, is used to replace conventional electrodes. In situ electrodeposition is proposed to fabricate CoP on the RGO-CNT/RGO/PPS (CoP-RGO-CNT/RGO/PPS) electrode and achieves a favorably electrical contact between CoP nanoparticles and RGO-CNT/RGO/PPS electrode due to without any polymer binder. Additionally, the coupling of different electrodeposition stages with scanning electron microscope (SEM) can investigate the nanostructure evolution of CoP nanoparticles, which gives valuable insights into the optimized electrodeposition cycles. The rational integration of RGO onto CNT/RGO/PPS film is an effective approach for enhancing its intrinsic electrical conductivity and favoring the formation of a high density of dispersive CoP nanoparticles. The CoP-RGO-CNT/RGO/PPS film has shown outstanding HER electrocatalytic behaviors performed a current density of 10 mA cm-2 at a relatively low overpotential of 160 mV with a Tafel slope of 60 mV dec-1 in acidic medium, which can be mainly attributed to the synergistic effect between optimized morphology and accelerated kinetics. Additionally, this film electrocatalyst exhibits a good HER activity and stability under both neutral and basic conditions.

  20. IDENTIFICATION OF CHLOROMETHANE FORMATION PATHS DURING ELECTROCHEMICAL DECHLORINATION OF TCE USING GRAPHITE ELECTRODES

    The purpose of this research is to investigate the formation of chloromethane during TCE dechlorination in a mixed electrochemical reactor using graphite electrodes. Chloromethane was the major chlorinated organic compound detected in previous dechlorination experiments. In order...

  1. IDENTIFICATION OF CHLOROMETHANE FROMATION PATHS DURING ELECTROCHEMICAL DECHLORINATION OF TCE USING GRAPHITE ELECTRODES

    The purpose of this research is to investigate the formation of chloromethane during TCE dechlorination in a mixed electrochemical reactor using graphite electrodes. Chloromethane was the major chlorinated organic compound detected in previous dechlorination experiments. In order...

  2. Fe/Ni-N-CNFs electrochemical catalyst for oxygen reduction reaction/oxygen evolution reaction in alkaline media

    Wang, Zhuang [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001 (China); Li, Mian [Faculty of Chemistry, Northeast Normal University, Changchun 130024 (China); Fan, Liquan; Han, Jianan [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001 (China); Xiong, Yueping, E-mail: ypxiong@hit.edu.cn [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001 (China)

    2017-04-15

    Highlights: • Novel Fe/Ni-N-CNFs electrocatalysts are prepared by electrospinning technique. • The Fe1Ni1-N-CNFs catalyst exhibits the excellent ORR and OER catalytic activity. • Synergy of Fe/Ni alloy is responsible for the excellent catalytic performance. - Abstract: The novel of iron, nickel and nitrogen doped carbon nanofibers (Fe/Ni-N-CNFs) as bifunctional electrocatalysts are prepared by electrospinning technique. In alkaline media, the Fe/Ni-N-CNFs catalysts (especially for Fe1Ni1-N-CNFs) exhibit remarkable electrocatalytic performances of oxygen reduction reaction (ORR)/oxygen evolution reaction (OER). For ORR catalytic activity, Fe1Ni1-N-CNFs catalyst offers a higher onset potential of 0.903 V, a similar four-electron reaction pathway, and excellent stability. For OER catalytic activity, Fe1Ni1-N-CNFs catalyst possesses a lower onset potential of 1.528 V and a smaller charge transfer resistance of 48.14 Ω. The unparalleled catalytic activity of ORR and OER for the Fe1Ni1-N-CNFs is attributed to the 3D porous cross-linked microstructures of carbon nanofibers with Fe/Ni alloy, N dopant, and abundant M-N{sub x} and NiOOH as catalytic active sites. Thus, Fe1Ni1-N-CNFs catalyst can be acted as one of the efficient and inexpensive catalysts of metal-air batteries.

  3. Recovery of Actinides from Actinide-Aluminium Alloys: Chlorination Route

    Mendes, E.; Malmbeck, R.; Soucek, P.; Jardin, R.; Glatz, J.P.; Cassayre, L.

    2008-01-01

    A method for recovery of actinides (An) from An-Al alloys formed by electrochemical separation of metallic spent nuclear fuel on solid aluminium electrodes in molten chloride salts is described. The proposed route consists of three main steps: -) vacuum distillation of salt adhered on the electrodes, -) chlorination of An-Al alloy by pure chlorine gas and -) sublimation of formed AlCl 3 . A thermochemical study of the route was performed to determine important chemical reactions and to find optimum experimental conditions for all process steps. Vacuum distillation of the electrode is efficient for complete removal of remaining salt and most fission products, full chlorination of the An-Al alloys is possible at any working temperature and evaporation of AlCl 3 is achieved by heating under argon. Experiments have been carried out using U-Al alloy in order to define parameters providing full alloy chlorination without formation of volatile UCl 5 and UCl 6 . It was shown that full chlorination of An-Al alloys without An losses should be possible at a temperature approx. 150 deg. C. (authors)

  4. Recovery of Actinides from Actinide-Aluminium Alloys: Chlorination Route

    Mendes, E.; Malmbeck, R.; Soucek, P.; Jardin, R.; Glatz, J.P. [European Commission, JRC, Institute for Transuranium Elements, Postfach 2340, 76125 Karlsruhe (Germany); Cassayre, L. [Laboratoire de Genie Chimique (LGC), Universite Paul Sabatier, UMR CNRS 5503, 118 route de Narbonne, 31062 Toulouse Cedex 04 (France)

    2008-07-01

    A method for recovery of actinides (An) from An-Al alloys formed by electrochemical separation of metallic spent nuclear fuel on solid aluminium electrodes in molten chloride salts is described. The proposed route consists of three main steps: -) vacuum distillation of salt adhered on the electrodes, -) chlorination of An-Al alloy by pure chlorine gas and -) sublimation of formed AlCl{sub 3}. A thermochemical study of the route was performed to determine important chemical reactions and to find optimum experimental conditions for all process steps. Vacuum distillation of the electrode is efficient for complete removal of remaining salt and most fission products, full chlorination of the An-Al alloys is possible at any working temperature and evaporation of AlCl{sub 3} is achieved by heating under argon. Experiments have been carried out using U-Al alloy in order to define parameters providing full alloy chlorination without formation of volatile UCl{sub 5} and UCl{sub 6}. It was shown that full chlorination of An-Al alloys without An losses should be possible at a temperature approx. 150 deg. C. (authors)

  5. Evolution of controllable urchin-like SrCO{sub 3} with enhanced electrochemical performance via an alternative processing

    Wang, Zhiwei, E-mail: wangzw0818@163.com; He, Geping, E-mail: hgping2013@126.com; Yin, Hongfeng; Bai, Wenyu; Ding, Donghai

    2017-07-31

    Graphical abstract: Strontium carbonate (SrCO{sub 3}) owning an urchin-like morphology with a hierarchical nanostructure was synthesized. Specific capacitance of SrCO{sub 3} was enhanced greatly by controllable urchin-like morphology through a mechanism of oxygen diffusion. - Highlights: • Urchin-like SrCO{sub 3} hierarchical nanostructure was prepared by hydrothermal route. • Morphology evolution of urchin-like SrCO{sub 3} with different preparation conditions. • Mechanism of nuclear aggregates—nanorods embellishment—urchin-like. • Specific capacitance of SrCO{sub 3} was enhanced greatly by controllable urchin-like morphology. - Abstract: Strontium carbonate (SrCO{sub 3}) owning an urchin-like morphology with a hierarchical nanostructure was synthesized by the reactants of strontium nitrate and urea via a facilitative, green initiative hydrothermal route. Samples characterization results of the structure showed that the surface of urchin-like SrCO{sub 3} was evenly distributed with nanorods with a diameter of about 50 nm and lengths of 1–2 μm. It was also found that the hydrothermal reaction time and reactants of trace concentrations changes will have an impact on the size and morphology. For these reasons we presented the crystal growth mechanism of “nuclear aggregates–nanorods embellishment–urchin-like” during the process of fabricating urchin-like SrCO{sub 3} crystal. Specific capacitance was enhanced more than 6 times, which dug out the optimal urchin-like SrCO{sub 3} influenced by a growth of surface nanorods.

  6. The effect of preparation parameters i thermal decomposition of ruthenium dioxide electrodes on chlorine elctro-catalytic activity

    Luu, Tran Le; Kim, Choon Soo; Kim, Ji Ye; Kim, Seong Hwan; Yoon, Je Yong

    2015-01-01

    When fabricating a RuO_2 electrode, the high electro-catalytic activity in chlorine evolution is considered as one of the most important factors. Thermal decomposition method carried out under various fabrication conditions including the types of solvents, precursors, and calcination times have led to the enhancement electro-catalytic activity of RuO_2 electrode in chlorine evolution. Nevertheless, it has not been fully investigated how these parameters directly affect to the chlorine evolution efficiency in the RuO_2 electrode. Therefore, the aim of this study was to investigate the effect on the chlorine evolution in RuO_2 electrodes, depending upon the preparation parameters including solvents, precursors, and calcination times. As major results, the chlorine evolution efficiency was dominantly affected by these three major preparation parameters. The RuO_2 electrode fabricated with ethanol as the solvent showed highest chlorine evolution efficiency. The choice of Ru(AcAc)_3 as precursor and the increase of the calcination time up to 3 h are also the good choices for increasing chlorine electrocatalytic activities. The chlorine evolution efficiency was not significantly related to the total voltammetric charge but to the outer voltammetric charge, which is affected by the morphology of the RuO_2 electrode surface. The size and number of cracks on the electrode surfaces or the outer voltammetric charges increased with easily evaporated solvents, decomposed precursors, and tensile stress from longer thermal treatments

  7. The effect of preparation parameters i thermal decomposition of ruthenium dioxide electrodes on chlorine elctro-catalytic activity

    Luu, Tran Le; Kim, Choon Soo; Kim, Ji Ye; Kim, Seong Hwan; Yoon, Je Yong [Dept. of Chemical and Biological Engineering, Institute of Chemical Process, Seoul National University,Seoul (Korea, Republic of)

    2015-05-15

    When fabricating a RuO{sub 2} electrode, the high electro-catalytic activity in chlorine evolution is considered as one of the most important factors. Thermal decomposition method carried out under various fabrication conditions including the types of solvents, precursors, and calcination times have led to the enhancement electro-catalytic activity of RuO{sub 2} electrode in chlorine evolution. Nevertheless, it has not been fully investigated how these parameters directly affect to the chlorine evolution efficiency in the RuO{sub 2} electrode. Therefore, the aim of this study was to investigate the effect on the chlorine evolution in RuO{sub 2} electrodes, depending upon the preparation parameters including solvents, precursors, and calcination times. As major results, the chlorine evolution efficiency was dominantly affected by these three major preparation parameters. The RuO{sub 2} electrode fabricated with ethanol as the solvent showed highest chlorine evolution efficiency. The choice of Ru(AcAc){sub 3} as precursor and the increase of the calcination time up to 3 h are also the good choices for increasing chlorine electrocatalytic activities. The chlorine evolution efficiency was not significantly related to the total voltammetric charge but to the outer voltammetric charge, which is affected by the morphology of the RuO{sub 2} electrode surface. The size and number of cracks on the electrode surfaces or the outer voltammetric charges increased with easily evaporated solvents, decomposed precursors, and tensile stress from longer thermal treatments.

  8. Chlorination of zirconyte concentrate

    Costa, N.G.

    1988-01-01

    Chlorination experiments with zirconyte concentrate were carried out in order to study the effects of temperature, percentage of reducing agent and porosity on the gasification of ZrO 2 for 10 and 20 minutes of reaction. Factorial analysis was applied and the results indicated that temperature and percentage of reducing agent were the two only variables effecting the ZrO 2 gasification. (author) [pt

  9. Structure evolution of the LiMnO{sub 2} lamellar oxide during electrochemical cycling; Evolution structurale de l`oxyde lamellaire LiMnO{sub 2} lors du cyclage electrochimique

    Delmas, C. [Centre National de la Recherche Scientifique (CNRS), 33 - Pessac (France). Institut de Chimie de la Matiere Condensee de Bordeaux; Capitaine, F.; Majastre [Bollore Technologies, 29 - Quimper (France); Baudry, P. [Electricite de France, 77 - Moret sur Loing (France). Direction des Etudes et Recherches

    1996-12-31

    The LiMnO{sub 2} lamellar oxide, obtained by exchange reaction from its sodium homologue {alpha}-NaMnO{sub 2}, has been used as a positive electrode for lithium batteries. After the first electrochemical cycle, the shape of the potential-composition curve changes and indicates a change in the structure. This modification changes imperceptibly at each cycle and after about 40 cycles, a stationary state is reached. Powder spectra refinement using the Rietvelt method shows a migration of manganese ions from the thin sheets towards the inter-sheet space. After a single cycle, 8% of the manganese ions are already present in the lithium site and this rate reaches 13% after 3 cycles. During long cycling, a redistribution of ions and vacancies inside the cfc oxygenated pile leads to a structure very similar to the LiMn{sub 2}O{sub 4} spinel. This structure evolution is to be compared with the one obtained from the orthorhombic variety of LiMnO{sub 2} but the modification is more progressive with lamellar LiMnO{sub 2}. Abstract only. (J.S.)

  10. Structure evolution of the LiMnO{sub 2} lamellar oxide during electrochemical cycling; Evolution structurale de l`oxyde lamellaire LiMnO{sub 2} lors du cyclage electrochimique

    Delmas, C [Centre National de la Recherche Scientifique (CNRS), 33 - Pessac (France). Institut de Chimie de la Matiere Condensee de Bordeaux; Capitaine, F; Majastre, [Bollore Technologies, 29 - Quimper (France); Baudry, P [Electricite de France, 77 - Moret sur Loing (France). Direction des Etudes et Recherches

    1997-12-31

    The LiMnO{sub 2} lamellar oxide, obtained by exchange reaction from its sodium homologue {alpha}-NaMnO{sub 2}, has been used as a positive electrode for lithium batteries. After the first electrochemical cycle, the shape of the potential-composition curve changes and indicates a change in the structure. This modification changes imperceptibly at each cycle and after about 40 cycles, a stationary state is reached. Powder spectra refinement using the Rietvelt method shows a migration of manganese ions from the thin sheets towards the inter-sheet space. After a single cycle, 8% of the manganese ions are already present in the lithium site and this rate reaches 13% after 3 cycles. During long cycling, a redistribution of ions and vacancies inside the cfc oxygenated pile leads to a structure very similar to the LiMn{sub 2}O{sub 4} spinel. This structure evolution is to be compared with the one obtained from the orthorhombic variety of LiMnO{sub 2} but the modification is more progressive with lamellar LiMnO{sub 2}. Abstract only. (J.S.)

  11. CHLORINE ABUNDANCES IN COOL STARS

    Maas, Z. G.; Pilachowski, C. A. [Indiana University Bloomington, Astronomy Department, Swain West 319, 727 East Third Street, Bloomington, IN 47405-7105 (United States); Hinkle, K., E-mail: zmaas@indiana.edu, E-mail: cpilacho@indiana.edu, E-mail: hinkle@noao.edu [National Optical Astronomy Observatory, P.O. Box 26732, Tucson, AZ 85726 (United States)

    2016-12-01

    Chlorine abundances are reported in 15 evolved giants and 1 M dwarf in the solar neighborhood. The Cl abundance was measured using the vibration-rotation 1-0 P8 line of H{sup 35}Cl at 3.69851 μ m. The high-resolution L -band spectra were observed using the Phoenix infrared spectrometer on the Kitt Peak Mayall 4 m telescope. The average [{sup 35}Cl/Fe] abundance in stars with −0.72 < [Fe/H] < 0.20 is [{sup 35}Cl/Fe] = (−0.10 ± 0.15) dex. The mean difference between the [{sup 35}Cl/Fe] ratios measured in our stars and chemical evolution model values is (0.16 ± 0.15) dex. The [{sup 35}Cl/Ca] ratio has an offset of ∼0.35 dex above model predictions, suggesting that chemical evolution models are underproducing Cl at the high metallicity range. Abundances of C, N, O, Si, and Ca were also measured in our spectral region and are consistent with F and G dwarfs. The Cl versus O abundances from our sample match Cl abundances measured in planetary nebula and H ii regions. In one star where both H{sup 35}Cl and H{sup 37}Cl could be measured, a {sup 35}Cl/{sup 37}Cl isotope ratio of 2.2 ± 0.4 was found, consistent with values found in the Galactic ISM and predicted chemical evolution models.

  12. One-pot synthesis of MoS2/In2S3 ultrathin nanoflakes with mesh-shaped structure on indium tin oxide as photocathode for enhanced photo-and electrochemical hydrogen evolution reaction

    Sun, Baoliang; Shan, Fei; Jiang, Xinxin; Ji, Jing; Wang, Feng

    2018-03-01

    A bifunctional MoS2/In2S3 hybrid composite that has both photo- and electrocatalytic activity toward hydrogen evolution reaction (HER) is prepared by a facile one pot hydrothermal method. The characterizations by scanning electron microscope (SEM), high resolution transmission electron microscope (HRTEM) and Photoluminescence (PL) shows that the MoS2/In2S3 hybrid exhibits ultrathin nanoflakes with mesh-shaped structure on transparent conductive substrates, and the as prepared catalyst composite obviously improves the separation of electro-hole pairs. The as prepared hybrid nanosheets with Mo:In of 1/2 integrate In-doped MoS2 to reduce the stacking and increase the active surface area. The novel mesh-shaped nanostructure with a moderate degree of disorder provides not only simultaneously intrinsic conductivity and defects but also higher electrochemically active surface area (ECSA). By electrochemical measurements, such as linear sweep voltammetry (LSV), electrochemical impedance spectroscope (EIS) and cyclic voltammetry (CV), we find that the MoS2/In2S3 hybrid possesses much better photo/electrochemical activity than pristine MoS2 or In2S3. MoS2/In2S3 ultrathin nanoflaks are anticipated to be a superior photoelectrocatalyst for PEC cells, and the rational use of the MoS2/In2S3 cathode offers a new avenue toward achieving effective photo-assistant electrocatalytic activity.

  13. Electrochemical biosensors

    Cosnier, Serge

    2015-01-01

    "This is an excellent book on modern electrochemical biosensors, edited by Professor Cosnier and written by leading international experts. It covers state-of-the-art topics of this important field in a clear and timely manner."-Prof. Joseph Wang, UC San Diego, USA  "This book covers, in 13 well-illustrated chapters, the potential of electrochemical methods intimately combined with a biological component for the assay of various analytes of biological and environmental interest. Particular attention is devoted to the description of electrochemical microtools in close contact with a biological cell for exocytosis monitoring and to the use of nanomaterials in the electrochemical biosensor architecture for signal improvement. Interestingly, one chapter describes the concept and design of self-powered biosensors derived from biofuel cells. Each topic is reviewed by experts very active in the field. This timely book is well suited for providing a good overview of current research trends devoted to electrochemical...

  14. Reagent-Free Quantification of Aqueous Free Chlorine via Electrical Readout of Colorimetrically Functionalized Pencil Lines.

    Mohtasebi, Amirmasoud; Broomfield, Andrew D; Chowdhury, Tanzina; Selvaganapathy, P Ravi; Kruse, Peter

    2017-06-21

    Colorimetric methods are commonly used to quantify free chlorine in drinking water. However, these methods are not suitable for reagent-free, continuous, and autonomous applications. Here, we demonstrate how functionalization of a pencil-drawn film with phenyl-capped aniline tetramer (PCAT) can be used for quantitative electric readout of free chlorine concentrations. The functionalized film can be implemented in a simple fluidic device for continuous sensing of aqueous free chlorine concentrations. The sensor is selective to free chlorine and can undergo a reagent-free reset for further measurements. Our sensor is superior to electrochemical methods in that it does not require a reference electrode. It is capable of quantification of free chlorine in the range of 0.1-12 ppm with higher precision than colorimetric (absorptivity) methods. The interactions of PCAT with the pencil-drawn film upon exposure to hypochlorite were characterized spectroscopically. A previously reported detection mechanism relied on the measurement of a baseline shift to quantify free chlorine concentrations. The new method demonstrated here measures initial spike size upon exposure to free chlorine. It relies on a fast charge built up on the sensor film due to intermittent PCAT salt formation. It has the advantage of being significantly faster than the measurement of baseline shift, but it cannot be used to detect gradual changes in free chlorine concentration without the use of frequent reset pulses. The stability of PCAT was examined in the presence of free chlorine as a function of pH. While most ions commonly present in drinking water do not interfere with the free chlorine detection, other oxidants may contribute to the signal. Our sensor is easy to fabricate and robust, operates reagent-free, and has very low power requirements and is thus suitable for remote deployment.

  15. Studies with solid chlorine chemical for chlorination of sea water systems

    Sankar, N.; Kumaraswamy, P.; Santhanam, V.S.; Jeena, P.; Hari Krishna, K.; Rajendran, D.

    2015-01-01

    Chlorination is one of the conventional methods to control biofouling of condenser cooling water systems using either river water, reservoir water or sea water. However, there are many safety concerns associated with handling, storage and application of gaseous chlorine. Studies were carried out with suitable alternative chlorine chemical compounds which do not involve majority of these concerns but meet the functional requirement of gas chlorine. Trichloroisocyanuric Acid (TCCA) is one of the suitable alternatives to Gas chlorine. TCCA is a chlorine stabilized compound, stabilized with Cyanuric acid, thus similar to Gas Chlorine in its functions except that it is available in solid form. Release of chlorine is a gradual process in TCCA unlike Gaseous chlorine. Field studies with TCCA indicated gradual and near uniform release rate of chlorine, for longer duration with the requisite free residual chlorine levels (FRC). Thus, use of TCCA could be considered as a suitable alternative for gas chlorine for regular chlorination requirements. (author)

  16. Electrochemical Processes

    Bech-Nielsen, Gregers

    1997-01-01

    The notes describe in detail primary and secondary galvanic cells, fuel cells, electrochemical synthesis and electroplating processes, corrosion: measurments, inhibitors, cathodic and anodic protection, details of metal dissolution reactions, Pourbaix diagrams and purification of waste water from...

  17. Electrochemical analysis

    Hwang, Hun

    2007-02-01

    This book explains potentiometry, voltametry, amperometry and basic conception of conductometry with eleven chapters. It gives the specific descriptions on electrochemical cell and its mode, basic conception of electrochemical analysis on oxidation-reduction reaction, standard electrode potential, formal potential, faradaic current and faradaic process, mass transfer and overvoltage, potentiometry and indirect potentiometry, polarography with TAST, normal pulse and deferential pulse, voltammetry, conductometry and conductometric titration.

  18. Photodynamic tissue adhesion with chlorin(e6) protein conjugates.

    Khadem, J; Veloso, A A; Tolentino, F; Hasan, T; Hamblin, M R

    1999-12-01

    To test the hypothesis that a photodynamic laser-activated tissue solder would perform better in sealing scleral incisions when the photosensitizer was covalently linked to the protein than when it was noncovalently mixed. Conjugates and mixtures were prepared between the photosensitizer chlorin(e6) and various proteins (albumin, fibrinogen, and gelatin) in different ratios and used to weld penetrating scleral incisions made in human cadaveric eyes. A blue-green (488-514 nm) argon laser activated the adhesive, and the strength of the closure was measured by increasing the intraocular pressure until the wound showed leakage. Both covalent conjugates and noncovalent mixtures showed a light dose-dependent increase in leaking pressure. A preparation of albumin chlorin(e6) conjugate with additional albumin added (2.5 protein to chlorin(e6) molar ratio) showed significantly higher weld strength than other protein conjugates and mixtures. This is the first report of dye-protein conjugates as tissue solders. These conjugates may have applications in ophthalmology.

  19. Electrochemical detection of DNA binding by tumor suppressor p53 protein using osmium-labeled oligonucleotide probes and catalytic hydrogen evolution at the mercury electrode

    Němcová, Kateřina; Šebest, Peter; Havran, Luděk; Orság, Petr; Fojta, Miroslav; Pivoňková, Hana

    2014-01-01

    Roč. 406, č. 24 (2014), s. 5843-5852 ISSN 1618-2642 R&D Projects: GA ČR(CZ) GAP301/11/2076; GA AV ČR(CZ) IAA400040901 Institutional support: RVO:68081707 Keywords : Electrochemical analysis * Labeled probes * Osmium complex Subject RIV: BO - Biophysics Impact factor: 3.436, year: 2014

  20. Grundfoss: Chlorination of Swimming Pools

    Hjorth, Poul G.; Hogan, John; Andreassen, Viggo

    1998-01-01

    Grundfos asked for a model, describing the problem of mixing chemicals, being dosed into water systems, to be developed. The application of the model should be dedicated to dosing aqueous solution of chlorine into swimming pools.......Grundfos asked for a model, describing the problem of mixing chemicals, being dosed into water systems, to be developed. The application of the model should be dedicated to dosing aqueous solution of chlorine into swimming pools....

  1. Electrochemical energy storage systems for solar thermal applications

    Krauthamer, S.; Frank, H.

    1980-01-01

    Existing and advanced electrochemical storage and inversion/conversion systems that may be used with terrestrial solar-thermal power systems are evaluated. The status, cost and performance of existing storage systems are assessed, and the cost, performance, and availability of advanced systems are projected. A prime consideration is the cost of delivered energy from plants utilizing electrochemical storage. Results indicate that the five most attractive electrochemical storage systems are the: iron-chromium redox (NASA LeRC), zinc-bromine (Exxon), sodium-sulfur (Ford), sodium-sulfur (Dow), and zinc-chlorine (EDA).

  2. Determination of Chlorine Dioxide and Chlorite in Water Supply Systems by Verified Methods

    Tkáčová Jana

    2014-07-01

    Full Text Available This work is dedicated to the development and optimization of appropriate analytical methods for the determination of chlorine dioxide and chlorite in drinking water in order to obtain accurate and correct results in the quality control of drinking water. The work deals with the development and optimization of a method for the determination of chlorine dioxide using chlorophenol red. Furthermore, a new spectrophotometric method for the determination of chlorite via bromometry using methyl orange was developed, optimized and validated. An electrochemical method for the determination of chlorite by flow coulometry was also developed, optimized and validated.

  3. Characterisation of Chlorine Behavior in French Graphite

    Blondel, A.; Moncoffre, N.; Toulhoat, N.; Bererd, N.; Petit, L.; Laurent, G.; Lamouroux, C.

    2016-01-01

    Chlorine 36 is one of the main radionuclides of concern for French graphite waste disposal. In order to help the understanding of its leaching behaviour under disposal conditions, the respective impact of temperature, irradiation and gas radiolysis on chlorine release in reactor has been studied. Chlorine 36 has been simulated through chlorine 37 ion implantation in virgin nuclear graphite samples. Results show that part of chlorine is highly mobile in graphite in the range of French reactors operating temperatures in relation with graphite structural recovering. Ballistic damage generated by irradiation also promotes chlorine release whereas no clear impact of the coolant gas radiolysis was observed in the absence of graphite radiolytic corrosion. (author)

  4. Recovery of actinides from actinide-aluminium alloys by chlorination: Part I

    Cassayre, L., E-mail: cassayre@chimie.ups-tlse.fr [Laboratoire de Genie Chimique (LGC), Departement Procedes Electrochimiques, CNRS-UMR 5503, Universite de Toulouse III - Paul Sabatier, 31062 Toulouse (France); Soucek, P.; Mendes, E.; Malmbeck, R.; Nourry, C.; Eloirdi, R.; Glatz, J.-P. [European Commission, JRC, Institute for Transuranium Elements, Postfach 2340, 76125 Karlsruhe (Germany)

    2011-07-01

    Pyrochemical processes in molten LiCl-KCl are being developed in ITU for recovery of actinides from spent nuclear fuel. The fuel is anodically dissolved to the molten salt electrolyte and actinides are electrochemically reduced on solid aluminium cathodes forming solid actinide-aluminium alloys. A chlorination route is being investigated for recovery of actinides from the alloys. This route consists in three steps: Vacuum distillation for removal of the salt adhered on the electrode, chlorination of the actinide-aluminium alloys by chlorine gas and sublimation of the formed AlCl{sub 3}. A thermochemical study showed thermodynamic feasibility of all three steps. On the basis of the conditions identified by the calculations, experiments using pure UAl{sub 3} alloy were carried out to evaluate and optimise the chlorination step. The work was focused on determination of the optimal temperature and Cl{sub 2}/UAl{sub 3} molar ratio, providing complete chlorination of the alloy without formation of volatile UCl{sub 5} and UCl{sub 6}. The results showed high efficient chlorination at a temperature of 150 deg. C.

  5. Recovery of actinides from actinide-aluminium alloys by chlorination: Part I

    Cassayre, L.; Soucek, P.; Mendes, E.; Malmbeck, R.; Nourry, C.; Eloirdi, R.; Glatz, J.-P.

    2011-01-01

    Pyrochemical processes in molten LiCl-KCl are being developed in ITU for recovery of actinides from spent nuclear fuel. The fuel is anodically dissolved to the molten salt electrolyte and actinides are electrochemically reduced on solid aluminium cathodes forming solid actinide-aluminium alloys. A chlorination route is being investigated for recovery of actinides from the alloys. This route consists in three steps: Vacuum distillation for removal of the salt adhered on the electrode, chlorination of the actinide-aluminium alloys by chlorine gas and sublimation of the formed AlCl 3 . A thermochemical study showed thermodynamic feasibility of all three steps. On the basis of the conditions identified by the calculations, experiments using pure UAl 3 alloy were carried out to evaluate and optimise the chlorination step. The work was focused on determination of the optimal temperature and Cl 2 /UAl 3 molar ratio, providing complete chlorination of the alloy without formation of volatile UCl 5 and UCl 6 . The results showed high efficient chlorination at a temperature of 150 deg. C.

  6. Electrochemical capacitor

    Anderson, Marc A.; Liu, Kuo -Chuan; Mohr, Charles M.

    1999-10-05

    An inexpensive porous metal oxide material having high surface area, good conductivity and high specific capacitance is advantageously used in an electrochemical capacitor. The materials are formed in a sol-gel process which affords control over the properties of the resultant metal oxide materials.

  7. Electrochemical construction

    Einstein, Harry; Grimes, Patrick G.

    1983-08-23

    An electrochemical cell construction features a novel co-extruded plastic electrode in an interleaved construction with a novel integral separator-spacer. Also featured is a leak and impact resistant construction for preventing the spill of corrosive materials in the event of rupture.

  8. Electrochemical device

    Grimes, Patrick G.; Einstein, Harry; Bellows, Richard J.

    1988-01-12

    A tunnel protected electrochemical device features channels fluidically communicating between manifold, tunnels and cells. The channels are designed to provide the most efficient use of auxiliary power. The channels have a greater hydraulic pressure drop and electrical resistance than the manifold. This will provide a design with the optimum auxiliary energy requirements.

  9. Electrochemical Cell

    1999-01-01

    The invention relates to a rechargeable electrochemical cell comprising a negative electrode, an electrolyte and a positive electrode in which the positive electrode structure comprises a lithium cobalt manganese oxide of the composition Li¿2?Co¿y?Mn¿2-y?O¿4? where 0 ... for capacity losses in lithium ion cells and lithium-alloy cells....

  10. The potential feasibility of chlorinic photosynthesis on exoplanets.

    Haas, Johnson R

    2010-11-01

    The modern search for life-bearing exoplanets emphasizes the potential detection of O(2) and O(3) absorption spectra in exoplanetary atmospheres as ideal signatures of biology. However, oxygenic photosynthesis may not arise ubiquitously in exoplanetary biospheres. Alternative evolutionary paths may yield planetary atmospheres tinted with the waste products of other dominant metabolisms, including potentially exotic biochemistries. This paper defines chlorinic photosynthesis (CPS) as biologically mediated photolytic oxidation of aqueous Cl(-) to form halocarbon or dihalogen products, coupled with CO(2) assimilation. This hypothetical metabolism appears to be feasible energetically, physically, and geochemically, and could potentially develop under conditions that approximate the terrestrial Archean. It is hypothesized that an exoplanetary biosphere in which chlorinic photosynthesis dominates primary production would tend to evolve a strongly oxidizing, halogen-enriched atmosphere over geologic time. It is recommended that astronomical observations of exoplanetary outgoing thermal emission spectra consider signs of halogenated chemical species as likely indicators of the presence of a chlorinic biosphere. Planets that favor the evolution of CPS would probably receive equivalent or greater surface UV flux than is produced by the Sun, which would promote stronger abiotic UV photolysis of aqueous halides than occurred during Earth's Archean era and impose stronger evolutionary selection pressures on endemic life to accommodate and utilize halogenated compounds. Ocean-bearing planets of stars with metallicities equivalent to, or greater than, the Sun should especially favor the evolution of chlorinic biospheres because of the higher relative seawater abundances of Cl, Br, and I such planets would tend to host. Directed searches for chlorinic biospheres should probably focus on G0-G2, F, and A spectral class stars that have bulk metallicities of +0.0 Dex or greater.

  11. Process for producing chlorinated polyethylene

    Nose, Shinji; Takayama, Shin-ichi; Kodama, Takashi.

    1970-01-01

    A process for chlorinated polyethylene by the chlorination of an aqueous suspension of polyethylene without the use catalysts is given, using 5-55% by gel content of cross-linked polyethylene powders. The products have favorable material workability, transparency, impact strength and tensile properties. In the case of peroxide cross-linking, a mixture of peroxides with polyethylene must be ground after heat treatment. The polyethylene may preferably have a gel content of 5-55%. The chlorination temperature may be 40 0 C or more, preferably 60 0 to 160 0 C. In one example, high pressure polymerized fine polyethylene powders of 15μ having a density of 0.935 g/cc, a softening point of 114 0 C, an average molecular weight of 35,000 were irradiated in air with 40 Mrad electron beams from a 2 MV Cockcroft-Walton type accelerator at room temperature. The thus irradiated polyethylene had a gel content of 55% and a softening point of 119 0 C. It was chlorinated upto a chlorine content of 33% at 100 0 C. Products were white crystals having a melting point of 122 0 C and a melting heat value of 32 mcal/mg. A sheet formed from this product showed a tensile strength of 280 kg/cm 2 , an elongation of 370% and a hardness of 90. (Iwakiri, K.)

  12. Investigation of electrochemical behaviour and structure of oxide films on Ni60Nb40 alloy in amorphous and crystalline states

    Tomashov, N.D.; Skvortsova, I.B.; Gorodetskij, A.E.; Bogomolov, D.B.

    1987-01-01

    Electrochemical properties of Ni 60 Nb 40 alloy in amorphous and crystalline states as well as structure of oxide films forming during anode polarization in electrolytes on the surface of this alloy in both its states are investigated. It is stated that increased passive ability of Ni 60 Nb 40 alloys in amorphous state and high efficiency of chlorine evolution (2 n NaCl+HCl up to pH=0) anode process in comparison with crystalline state are defined by increased homogeneity and uniformity of passive films forming on amorphous alloy and their increased electron conductivity, that is in direct dependence on different structure of passive films forming on alloys in amorphous and crystalline states

  13. Detection of chlorinated aromatic compounds

    Ekechukwu, A.A.

    1996-02-06

    A method for making a composition for measuring the concentration of chlorinated aromatic compounds in aqueous fluids, and an optical probe for use with the method are disclosed. The composition comprises a hydrophobic polymer matrix, preferably polyamide, with a fluorescent indicator uniformly dispersed therein. The indicator fluoresces in the presence of the chlorinated aromatic compounds with an intensity dependent on the concentration of these compounds in the fluid of interest, such as 8-amino-2-naphthalene sulfonate. The probe includes a hollow cylindrical housing that contains the composition in its distal end. The probe admits an aqueous fluid to the probe interior for exposure to the composition. An optical fiber transmits excitation light from a remote source to the composition while the indicator reacts with chlorinated aromatic compounds present in the fluid. The resulting fluorescence light signal is reflected to a second optical fiber that transmits the light to a spectrophotometer for analysis. 5 figs.

  14. Effects of Chlorine on Enterovirus RNA Degradation

    The primary mechanism of disinfection of waterborne pathogens by chlorine has always been believed to be due to the alteration of proteins by free chlorine and subsequent disruption of their biological structure.

  15. Kinetics of molybdenum and chlorine interaction

    Zelikman, A.N.; Nazarov, Yu.N.; Sarkarov, T.Eh.; Tulyakov, N.V.

    1977-01-01

    The kinetics is studied of molybdenite chlorination with gaseous chlorine. The time dependences of the depth and degree of molybdenite chlorination are given along with the dependence on chlorine concentration of molybdenite chlorination rate. Active interaction is shown to take place at 450-470 deg C. At 350-435 deg C, chlorination occurs in the kinetic range, the apparent activation energy being equal to 22.2 kcal/mole and the order of reaction by chlorine to 0.77. At 435-610 deg C, the process takes place in the diffusion range and is restricted by dissipation of the reaction products (activation energy - 4.05 kcal/mole; order of reaction by chlorine - 0.6)

  16. Formation of aryl-chlorinated aromatic acids and precursors for chloroform in chlorination of humic acid

    Sinninghe Damsté, J.S.; Leer, E.W.B. de; Galan, L.

    1985-01-01

    The formation of chloroform when humic substances are chlorinated is well known. Other chlorinated products that may be formed are chloral, di- and trichloroacetic acid, chlorinated C-4 diacids, and α-chlorinated aliphatic acids. Several of these compounds are formed in molar yields comparable

  17. Electrochemical degradation of Novacron Yellow C-RG using boron-doped diamond and platinum anodes: Direct and Indirect oxidation

    Rocha, J.H. Bezerra; Gomes, M.M. Soares; Santos, E. Vieira dos; Moura, E.C. Martins de; Silva, D. Ribeiro da; Quiroz, M.A.; Martínez-Huitle, C.A.

    2014-01-01

    Graphical abstract: - Highlights: • Nature of electrode material decides the electrocatalytic mechanism followed. • Electrogenerated strong oxidants on BDD surface improve the color and organic load removal. • Chlorine active species act in solution cage oxidizing organic matter. - Abstract: The present study discusses the electrochemical degradation process of a textile dye, Novacron Yellow C-RG (NY), dissolved in synthetic wastewaters, via direct and indirect oxidation. Experiments were conducted using boron-doped diamond (BDD) and platinum supported on Ti (Pt/Ti) electrodes in the absence and presence of NaCl in the solution. The direct process for removing color is relatively similar for both anodes, while the electrochemical degradation is significantly accelerated by the presence of halogen salt in the solution. Interestingly, it does not depend on applied current density, but rather on NaCl concentration. Therefore, the electrochemical processes (direct/indirect) favor specific oxidation pathways depending on electrocatalytic material. Whereas, the Pt/Ti anode favors preferentially color removal by direct and indirect oxidation (100% of color removal) due to the fragmentation of the azo dye group; BDD electrode favors color and organic load removals in both processes (95% and up to 87%, respectively), due to the rupture of dye in different parts of its chemical structure. Parameters of removal efficiency and energy consumption for the electrochemical process were estimated. Finally, an explanation has been attempted for the role of halide, in relation with the oxygen evolution reaction, concomitant with the electrochemical incineration as well as electrocatalytic mechanisms, for each one of the electrodes used

  18. Direct Chlorination of Zircon Sand

    Dwiretnani Sudjoko; Budi Sulistyo; Pristi Hartati; Sunardjo

    2002-01-01

    It was investigated the direct chlorination of zircon sand in a unit chlorination equipment. The process was in semi batch. The product gas was scrubbed in aqueous NaOH. It was search the influence of time, ratio of reactant and size of particle sand to the concentration of Zr and Si in the product. From these research it was found that as the times, ratio of reactant increased, the concentration of Zr increased, but the concentration of Si decreased, while as grain size of zircon sand decreased the concentration of Zr decreased, but the concentration of Si increased. (author)

  19. Metallic oxide reduction in molten chlorides: electrochemical solvent regeneration

    Martin, A.

    2005-11-01

    We consider the reaction MeO 2 + 2 Ca → Me + 2 CaO in CaCl 2 at 850 C. We want to re-use the molten media, which is a CaO-CaCl 2 melt at the end of the reaction. For that we want to de-oxidize it. When we electrolyse CaO we obtain Ca and O 2 ; it presents three difficult points that we want to solve: (1) it is difficult to oxidize O 2 - without oxidizing Cl - because their oxidation potential are very closed, (2) the chemical or electrochemical anodic corrosion, (3) the anodically produced gas dissolution in the mell One way of avoiding chlorine gas evolution is to prevent chloride ions from reaching the anode, for example using a selective membrane. Furthermore, the best prevention of the anodically produced gas dissolution in the melt can be done with a compartment, physically separating the anode from the rest of the reactional media. Thus in this work we have used an yttria stabilized zirconia membrane as a selective membrane for the deoxidation of a CaO-CaCl 2 melt at 850 C. (author)

  20. Detection of chlorine in water

    Kašík, Ivan; Mrázek, Jan; Podrazký, Ondřej; Seidl, Miroslav; Aubrecht, Jan; Tobiška, Petr; Pospíšilová, Marie; Matějec, Vlastimil; Kovács, B.; Markovics, A.; Szili, M.

    2009-01-01

    Roč. 139, č. 1 (2009), s. 139-142 ISSN 0925-4005 R&D Projects: GA MŠk(CZ) LC06034; GA ČR(CZ) GA102/05/0948 Institutional research plan: CEZ:AV0Z20670512 Keywords : optical fiber sensor * chlorine Subject RIV: JB - Sensors, Measurment, Regulation Impact factor: 3.083, year: 2009

  1. Electrochemical Implications of Defects in Carbon Nanotubes

    Hall, Jonathan Peter

    The electrochemical behavior of carbon nanotubes (CNTs) containing both intrinsic and extrinsically introduced defects has been investigated through the study of bamboo and hollow multi-walled CNT morphologies. The controlled addition of argon, hydrogen, and chlorine ions in addition to atomic hydrogen and magnesium vapor was used for varying the charge and type of extrinsic defects. To quantify changes in the CNTs upon treatment, Raman spectroscopy and electrochemical techniques were employed. It was indicated from Raman spectroscopy, cyclic voltammetry, electrochemical impedance spectroscopy, and chronopotentiometric experiments that the electrochemical response of hollow type CNTs could be tailored more significantly compared to bamboo type CNTs, which have innately high reactive site densities and are less amenable to modification. Total defect density and edge-plane-like defect concentrations monitored through Raman spectroscopy were used to correlate changes in the electrochemical response of the CNT electrodes as a function of treatment. The implementation of CNT electrodes in a prototypical electrolytic capacitor device was then explored and characterized. Dependencies on source current and redox couple concentration were evaluated, as well as changes in the total capacitance as a function of treatment. Cyclability studies were also performed as a function of source current magnitude to evaluate the longevity of the faradaic currents which typically decrease over time in other similar capacitors. This thesis then concludes with an overall summary of the themes and findings of the research presented in this work.

  2. Chlorination Revisited: Does Cl- Serve as a Catalyst in the Chlorination of Phenols?

    Lau, Stephanie S; Abraham, Sonali M; Roberts, A Lynn

    2016-12-20

    The aqueous chlorination of (chloro)phenols is one of the best-studied reactions in the environmental literature. Previous researchers have attributed these reactions to two chlorine species: HOCl (at circum-neutral and high pH) and H 2 OCl + (at low pH). In this study, we seek to examine the roles that two largely overlooked chlorine species, Cl 2 and Cl 2 O, may play in the chlorination of (chloro)phenols. Solution pH, chloride concentration, and chlorine dose were systematically varied in order to assess the importance of different chlorine species as chlorinating agents. Our findings indicate that chlorination rates at pH pH 6.0 and a chlorine dose representative of drinking water treatment, Cl 2 O is predicted to have at best a minor impact on chlorination reactions, whereas Cl 2 may contribute more than 80% to the overall chlorination rate depending on the (chloro)phenol identity and chloride concentration. While it is not possible to preclude H 2 OCl + as a chlorinating agent, we were able to model our low-pH data by considering Cl 2 only. Even traces of chloride can generate sufficient Cl 2 to influence chlorination kinetics, highlighting the role of chloride as a catalyst in chlorination reactions.

  3. Ultrafast measurements of chlorine dioxide photochemistry

    Ludowise, P.D.

    1997-08-01

    Time-resolved mass spectrometry and time-resolved photoelectron spectroscopy are used to study the ultrafast photodissociation dynamics of chlorine dioxide, an important constituent in stratospheric ozone depletion. Chapter 1 introduces these pump/probe techniques, in which a femtosecond pump pulse excites a molecule to a dissociative state. At a later time, a second femtosecond probe pulse ionizes the molecule. The resulting mass and photoelectron spectra are acquired as a function of the delay between the pump and probe pulses, which follows the evolution of the molecule on the excited state. A comparison to other techniques used to study reaction dynamics is discussed. Chapter 2 includes a detailed description of the design and construction of the experimental apparatus, which consists of a femtosecond laser system, a molecular beam time-of-flight spectrometer, and a data acquisition system. The time-of-flight spectrometer is specifically designed to have a short flight distance to maximize the photoelectron collection efficiency without degrading the resolution, which is limited by the bandwidth of the femtosecond laser system. Typical performance of the apparatus is demonstrated in a study of the time-resolved photoelectron spectroscopy of nitric oxide. The results of the time-resolved mass spectrometry experiments of chlorine dioxide are presented in Chapter 3. Upon excitation to the A {sup 2}A{sub 2} state near 3.2 eV, the molecule dissociates through an indirect two-step mechanism. The direct dissociation channel has been predicted to be open, but is not observed. A quantum beat is observed in the OClO{sup +} species, which is described as a vibrational coherence of the optically prepared A {sup 2}A{sub 2} state. Chapter 4 presents the results of the time-resolved photoelectron experiments of chlorine dioxide. At short delay time, the quantum beat of the OClO{sup +} species is observed in the X {sup 1}A{sub 1} state of the ion. At infinite delay, the signal

  4. Electrochemical cell

    Kaun, T.D.

    An improved secondary electrochemical cell is disclosed having a negative electrode of lithium aluminum, a positive electrode of iron sulfide, a molten electrolyte of lithium chloride and potassium chloride, and the combination that the fully charged theoretical capacity of the negative electrode is in the range of 0.5 to 1.0 that of the positive electrode. The cell thus is negative electrode limiting during discharge cycling. Preferably, the negative electrode contains therein, in the approximate range of 1 to 10 volume % of the electrode, an additive from the materials of graphitized carbon, aluminum-iron alloy, and/or magnesium oxide.

  5. Electrochemical attosyringe.

    Laforge, François O; Carpino, James; Rotenberg, Susan A; Mirkin, Michael V

    2007-07-17

    The ability to manipulate ultrasmall volumes of liquids is essential in such diverse fields as cell biology, microfluidics, capillary chromatography, and nanolithography. In cell biology, it is often necessary to inject material of high molecular weight (e.g., DNA, proteins) into living cells because their membranes are impermeable to such molecules. All techniques currently used for microinjection are plagued by two common problems: the relatively large injector size and volume of injected fluid, and poor control of the amount of injected material. Here we demonstrate the possibility of electrochemical control of the fluid motion that allows one to sample and dispense attoliter-to-picoliter (10(-18) to 10(-12) liter) volumes of either aqueous or nonaqueous solutions. By changing the voltage applied across the liquid/liquid interface, one can produce a sufficient force to draw solution inside a nanopipette and then inject it into an immobilized biological cell. A high success rate was achieved in injections of fluorescent dyes into cultured human breast cells. The injection of femtoliter-range volumes can be monitored by video microscopy, and current/resistance-based approaches can be used to control injections from very small pipettes. Other potential applications of the electrochemical syringe include fluid dispensing in nanolithography and pumping in microfluidic systems.

  6. Structural Dynamics and Evolution of Bismuth Electrodes during Electrochemical Reduction of CO 2 in Imidazolium-Based Ionic Liquid Solutions

    Medina-Ramos, Jonnathan [Chemical; Lee, Sang Soo [Chemical; Fister, Timothy T. [Chemical; Hubaud, Aude A. [Chemical; Sacci, Robert L.; Mullins, David R.; DiMeglio, John L. [Department; Pupillo, Rachel C. [Department; Velardo, Stephanie M. [Department; Lutterman, Daniel A.; Rosenthal, Joel [Department; Fenter, Paul [Chemical

    2017-09-14

    Real-time changes in the composition and structure of bismuth electrodes used for catalytic conversion of CO2 into CO were examined via X-ray absorption spectroscopy (including XANES and EXAFS), electrochemical quartz crystal microbalance (EQCM), and in situ X-ray reflectivity (XR). Measurements were performed with bismuth electrodes immersed in acetonitrile (MeCN) solutions containing a 1-butyl-3-methylimidazolium ([BMIM]+) ionic liquid promoter or electrochemically inactive tetrabutylammonium supporting electrolytes (TBAPF6 and TBAOTf). Altogether, these measurements show that bismuth electrodes are originally a mixture of bismuth oxides (including Bi2O3) and metallic bismuth (Bi0) and that the reduction of oxidized bismuth species to Bi0 is fully achieved under potentials at which CO2 activation takes place. Furthermore, EQCM measurements conducted during cyclic voltammetry revealed that a bismuth-coated quartz crystal exhibits significant shifts in resistance (ΔR) prior to the onset of CO2 reduction near -1.75 V vs Ag/AgCl and pronounced hysteresis in frequency (Δf) and ΔR, which suggests significant changes in roughness or viscosity at the Bi/[BMIM]+ solution interface. In situ XR performed on rhombohedral Bi (001) oriented films indicates that extensive restructuring of the bismuth film cathodes takes place upon polarization to potentials more negative than -1.6 V vs Ag/AgCl, which is characterized by a decrease of the Bi (001) Bragg peak intensity of ≥50% in [BMIM]OTf solutions in the presence and absence of CO2. Over 90% of the reflectivity is recovered during the anodic half-scan, suggesting that the structural changes are mostly reversible. In contrast, such a phenomenon is not observed for thin Bi (001) oriented films in solutions of tetrabutylammonium salts that do not promote CO2 reduction. Overall, these results highlight that Bi electrodes undergo significant potential-dependent chemical and structural transformations in the presence of [BMIM

  7. Water Chlorination for human consumption

    Innocenti, A.; Giacosa, D.; Segatori, M.

    1999-01-01

    Beginning from this issue, an initiative of Federgasacqua (Federal association dealing with the gas and the water) takes place through the activities of the Task Forces Water Quality Control and Materials and Processes, which aim is to offer to the water industry operators and updated information concerning some main subjects, emphasizing in particular the technical and management applied topics. The paper deals with the chlorination processes in drinking water treatment. An overview of the italian situation is presented, concerning disinfection as well as other oxidation processes, together with an historical background on chlorination. Concerning the applications, the chemical technologies and the main processes, the disinfectant effectiveness and the byproducts formation have been described. Further, the regulations in force have been reported and discussed on national and international bases [it

  8. Microstructural evolution of nanosized Ce0.8Gd0.2O1.9/Ni infiltrate in a Zr0.84Y0.16O1.92-Sr0.94Ti0.9Nb0.1O3-δ based SOFC anode under electrochemical evaluation

    Zhang, Wei; Kuhn, Luise Theil; Ramos, Tania

    are of paramount importance for performance and performance stability. Therefore an accurate understanding of the microstructure evolution during electrochemical operation will facilitate evaluating performances of SOFC anodes, and in turn optimize its design. Here we report a wealth of microstructural...... investigations of Ce0.8Gd0.2O1.9/Ni (hereafter CGO/Ni)-infiltrated Zr0.84Y0.16O1.92 composited Sr0.94Ti0.9Nb0.1O3-δ (STN94/8YSZ) anode in a symmetric cell design under a short electrochemical evaluation test (fingerprint test), applying electrochemical impedance spectroscopy (EIS) at mild 3% H2O/H2 and harsh 50...

  9. The effect of chlorine and combined chlorine/UV treatment on coliphages in drinking water disinfection.

    Zyara, Alyaa M; Torvinen, Eila; Veijalainen, Anna-Maria; Heinonen-Tanski, Helvi

    2016-08-01

    Chlorine disinfection is a globally used method to ensure the safety of drinking water. However, it has not always been successful against viruses and, therefore, it is important to find new methods to disinfect water. Seventeen different coliphages were isolated from the treated municipal wastewater. These coliphages and MS2 were treated with different dosages of chlorine in drinking water, and a combined chlorine/ultraviolet irradiation treatment for the chlorine-resistant coliphages. Chlorine disinfection with 0.3-0.5 mg/L total chlorine (free Cl-dosage 0.12-0.21 mg/L) for 10 min achieved 2.5-5.7 Log10-reductions for 11 sensitive coliphages. The six most resistant coliphages showed no reduction with these chlorine concentrations. MS2 was intermediate in chlorine resistance, and thus it is not a good indicator for viruses in chlorine disinfection. In the combined treatment total chlorine of 0.05-0.25 mg/L (free Cl-dosage 0.02-0.08 mg/L) and ultraviolet irradiation (14-22 mWs/cm(2)) were more effective than chlorine alone, and 3-5 Log10-reductions were achieved for the chlorine-resistant strains. The chlorination efficiency could be increased by higher dosages and longer contact times, but this could increase the formation of disinfection by-products. Therefore, the combination treatment is a recommended disinfection method.

  10. Metabolic fate of chlorinated paraffins

    Darnerud, P.O.; Biessmann, A.; Brandt, I.

    1982-01-01

    The disposition of three [1- 14 C]-chlorododecanes (MCDD, PCDD I and PCDD II; 17.4%, 55.9%, and 68.5% chlorination) was studied in C57Bl mice. [1- 14 C]-lauric acid (LA) was studied as reference compound. Fifty-two percent (MCDD), 32% (PCDD I), and 8% (PCDD II) of the radioactive doses were exhaled as 14 CO 2 during 12 h after i.v. injection. Similar results were obtained after p.o. administration. In addition to a marked labelling of the liver and fat, the distribution patterns observed at 24 h after administration revealed an uptake of radioactivity in tissues with high cell turnover/high metabolic activity, e.g., intestinal mucosa, bone marrow, salivary glands and thymus. The concentration of radioactivity in these sites and the exhalation of 14 CO 2 , which were inverse to the degree of chlorination, indicate that the chloroalkanes are degraded to metabolites which can be utilized in the intermediary metabolism. A similar, although more pronounced, distribution pattern and 14 CO 2 -exhalation (70% of i.v. dose) was observed after LA administration. The long time retention of heptane-soluble radioactivity in liver and fat (indicating unmetabolized substance) increased with degree of chlorination. On the contrary, the administration of LA and the chlorododecanes MCDD and PCDD I, but not of PCDD II, resulted in a selective labelling of the central nervous system 30-60 days after injection. (orig.)

  11. Electrochemical treatment of mixed and hazardous waste

    Dziewinski, J.; Marczak, S.; Smith, W.; Nuttall, E.

    1995-01-01

    Los Alamos National Laboratory (LANL) and The University of New Mexico are jointly developing an electrochemical process for treating hazardous and radioactive wastes. The wastes treatable by the process include toxic metal solutions, cyanide solutions, and various organic wastes that may contain chlorinated organic compounds. The main component of the process is a stack of electrolytic cells with peripheral equipment such as a rectifier, feed system, tanks with feed and treated solutions, and a gas-venting system. During the treatment, toxic metals are deposited on the cathode, cyanides are oxidized on the anode, and organic compounds are anodically oxidized by direct or mediated electrooxidation, depending on their type. Bench scale experimental studies have confirmed the feasibility of applying electrochemical systems to processing of a great variety of hazardous and mixed wastes. The operating parameters have been defined for different waste compositions using surrogate wastes. Mixed wastes are currently treated at bench scale as part of the treatability study

  12. Study on removing chlorin by conversion-aborption of chlorin resin

    Huang Yunbai; Zhao Jinfang; Tang Zhijuan; Huang Qijin; Deng Jianguo

    2012-01-01

    Theon version of chlorin resin and the reclamation of acid and uranium in converting solution were investigated. The results indicated the residual chlorin can meet the requirement after converting, acid and uranium in converting solution can be reclaimed. (authors)

  13. Structural evolution, thermomechanical recrystallization and electrochemical corrosion properties of Ni-Cu-Mg amorphous coating on mild steel fabricated by dual-anode electrolytic processing

    Abdulwahab, M., E-mail: mabdulwahab@abu.edu.ng [Department of Chemical, Metallurgical and Materials Engineering, Tshwane University of Technology, Pretoria (South Africa); Department of Metallurgical and Materials Engineering, Ahmadu Bello University, Zaria (Nigeria); Fayomi, O.S.I., E-mail: ojosundayfayomi3@gmail.com [Department of Chemical, Metallurgical and Materials Engineering, Tshwane University of Technology, Pretoria (South Africa); Department of Mechanical Engineering, Covenant University, Ota (Nigeria); Popoola, A.P.I., E-mail: popoolaapi@tut.ac.za [Department of Chemical, Metallurgical and Materials Engineering, Tshwane University of Technology, Pretoria (South Africa)

    2016-07-01

    Highlights: • The surface of the coat containing Ni-Cu-Mg alloy on mild steel have sufficiently enhanced the properties. • Isothermally treated composites demonstrated 45% increase in the micro-hardness and 79.6% corrosion resistance. • The thermal stability of the developed Ni-Cu-Mg thin films on mild steel was excellent. - Abstract: The electrolytic Ni-Cu based alloy coating with admixed interfacial blend of Mg have been successfully prepared on mild steel substrate by dual anode electroplating processes over a range of applied current density and dwell time. The electrocodeposition of Ni-Cu-Mg coating was investigated in the presence of other bath additives. The influence of deposition current on surface morphology, adhesion behavior, preferred crystal orientation, surface topography and electrochemical activity of Ni-Cu-Mg alloy coating on mild steel were systematically examined. The thermal stability of the developed composite materials was examined via isothermal treatment. Scanning electron microscope equipped with EDS, X-ray diffraction, Atomic force microscope, micro-hardness tester and 3 μmetrohm Potentiostat/galvanostat were used to compare untreated and isothermally treated electrocodeposited composite. The induced activity of the Ni-Cu-Mg alloy changed the surface modification and results to crystal precipitation within the structural interface by the formation of Cu{sub ,} Ni{sub 2}Mg{sub 3} phase. The obtained results showed that the introduction of Mg particles in the plating bath generally modified the surface and brings an increase in the hardness and corrosion resistance of Ni-Cu-Mg layers fabricated. Equally, isothermally treated composites demonstrated an improved properties indicating 45% increase in the micro-hardness and 79.6% corrosion resistance which further showed that the developed composite is thermally stable.

  14. Mediated electrochemical hazardous waste destruction

    Hickman, R.G.; Farmer, J.C.; Wang, F.T.

    1992-03-01

    There are few permitted processes for mixed waste (radioactive plus chemically hazardous) treatment. We are developing an electrochemical process, based upon mediated electrochemical oxidation (MEO), that converts toxic organic components of mixed waste to water, carbon dioxide, and chloride or chloride precipitates. Aggressive oxidizer ions such as Ag 2+ , Co 3+ , or Fe 3+ are produced at an anode. These can attack organic molecules directly, and may also produce hydroxyl free radicals that promote destruction. Solid and liquid radioactive waste streams containing only inorganic radionuclide forms may be treated with existing technology and prepared for final disposal. The coulombic efficiency of the process has been determined, as well as the destruction efficiency for ethylene glycol, a surrogate waste. In addition, hazardous organic materials are becoming very expensive to dispose of and when they are combined with transuranic radioactive elements no processes are presently permitted. Mediated electrochemical oxidation is an ambient- temperature aqueous-phase process that can be used to oxidize organic components of mixed wastes. Problems associated with incineration, such as high-temperature volatilization of radionuclides, are avoided. Historically, Ag(II) has been used as a mediator in this process. Fe(III) and Co(III) are attractive alternatives to Ag(II) since they form soluble chlorides during the destruction of chlorinated solvents. Furthermore, silver itself is toxic heavy metal. Quantitative data have been obtained for the complete oxidation of ethylene glycol by Fe(III) and Co(III). Though ethylene glycol is a nonhalogenated organic, these data have enabled us to make direct comparisons of activities of Fe(III) and Co(III) with Ag(II). Very good quantitative data for the oxidation of ethylene glycol by Ag(II) had already been collected

  15. Potassium chloride production by microcline chlorination

    Orosco, Pablo, E-mail: porosco@unsl.edu.ar [Instituto de Investigaciones en Tecnología Química (INTEQUI), Chacabuco y Pedernera, San Luis (Argentina); Facultad de Química, Bioquímica y Farmacia, Universidad Nacional de San Luis, Chacabuco y Pedernera, San Luis (Argentina); Ruiz, María del Carmen [Instituto de Investigaciones en Tecnología Química (INTEQUI), Chacabuco y Pedernera, San Luis (Argentina)

    2015-08-10

    Highlights: • Use of chlorination for the KCl production. • The reagents used were microcline, hydromagnesite and chlorine. • Isothermal and non-isothermal assays were performed in Cl{sub 2}–N{sub 2} mixture. • The chlorination generated KCl at 700 °C. • The chlorination products promote KCl formation. - Abstract: The potassium chloride is one of the most important fertilizers used in agriculture. The current demand of this salt makes interesting the study of potassium chloride production from unconventional potassium resources. In this work the potassium chloride production by chlorination of microcline was investigated. The starting reagents were microcline, hydromagnesite and chlorine. Non-isothermal and isothermal chlorination assays were carried out in a thermogravimetric device adapted to work in corrosive atmospheres. The temperature effect on potassium extraction and the phase transformations produced during chlorination of microcline were studied. The reagents and reaction products were analyzed by X-ray fluorescence (XRF) and X-ray diffraction (XRD). The experimental results indicated that by chlorination of microcline an important extraction of potassium in the temperature range from 800 to 900 °C was produced. Moreover, at 800 °C the forsterite, enstatite and magnesium aluminate spinel phases were generated.

  16. Chlorine-36 investigations of salt lakes

    Chivas, A.R.; Kiss, E.

    1987-01-01

    The first chlorine-36 measurements are reported for surficial halite in lakes from a west-to-east traverse in Western Australia and from Lake Amadeus NT. Measurements of chlorine-36 were made using a 14 MV tandem accelerator. Isotopic chlorine ratios ranged from 8 to 53 x 10 exp-15, with no clear evidence for bomb-spike chlorine-36. The Western Australian samples have values close to secular equilibrium values for typical granite and groundwaters in this rock type. Studies are aimed at calculating the residence time of chloride in the surficial environment. 1 tab

  17. Chlorination of cooling water: a source of chlorine-containing organic compounds with possible environmental significance

    Jolley, R.L.; Gehrs, C.W.; Pitt, W.W. Jr.

    1976-01-01

    Chlorination of cooling waters may be a source of environmentally significant pollutants. Many water-soluble chlorine-containing organic compounds of low volatility were found in a sample of cooling water chlorinated to a 2-mg/l chlorine concentration in the laboratory. The compounds were separated and detected using a coupled 36 Cl-tracer--high-resolution liquid chromatographic technique developed at the Oak Ridge National Laboratory for determination of chlorinated organics in process effluents. For a chlorination contact time of 75 min at 25 0 C, the yield of chlorine in the form of chloro-organics amounted to 0.78% of the chlorine dosage. It is estimated that the yield is about 0.5% under typical reaction conditions in the electric power plant cooling system chosen for study. Because chlorine is commonly used to remove slime films from the cooling systems of electric power plants, as a means of maintaining high operational efficiency, it is estimated that several hundred tons of chlorinated organics are produced annually in the nation by this antifoulant process. The chromatographic elution positions of some of the separated constituents correspond to those of compounds separated and partially identified from chlorinated sewage treatment plant effluents. The results of this study indicate the formation of chloro-organics during the chlorination of cooling waters should be thoroughly examined, particularly with respect to their identification and determination of possible toxicological properties

  18. Data for comparison of chlorine dioxide and chlorine disinfection power in a real dairy wastewater effluent

    Maliheh Akhlaghi

    2018-06-01

    Full Text Available Disinfection of water refers to a special operation that is doing to kill or disable causative organisms (i.e. Pathogens and in particular, intestinal bacteria. The aim of this pilot study is comparison of disinfection power of Chlorine dioxide and chlorine in a real dairy wastewater effluent. In this regard, firstly prepared two 220-l tanks made of polyethylene as reaction tanks and filled by effluent of a dairy wastewater treatment plant. Both tanks were equipped with mechanical stirrer. Then a Diaphragm dosing pumps with the maximum capacity of 3.9 l per hour were used for the chlorine dioxide and chlorine (Calcium hypochlorite 0.5 up to 3 ppm injection. Residual level of Chlorine dioxide and Chlorine were measured by portable photometric method DT4B kit, Germany. Finally, the Multiple-Tube Fermentation, Brilliant Green Bile Broth (BGB and Eosin methylene blue Agar (EMB technique was used for microbial analysis and the results were reported as the most probable number index (MPN respectively. The data showed that the residual of chlorine dioxide could stood more active than residual of chlorine in the aqueous environment significantly. Therefore, Use of chlorine dioxide is more effective than chlorine for removal fecal and total coliform from dairy wastewater effluent. Keywords: Disinfection, Chlorine dioxide, Chlorine, Total coliform, Fecal coliform

  19. Development of a model for the anodic behavior of T60 titanium in chlorinated and oxygenated aqueous media. Application to the specific conditions of hydrothermal oxidation (1 MPa

    Frayret, C.; Jaszay, Th.; Lestienne, B.; Delville, M.H.

    2003-01-01

    This work evaluates the anodic electrochemical behavior of titanium metal in hydrothermal oxidation conditions (up to 400 deg. C and 28 MPa) in chlorinated media in order to estimate the supercritical water oxidation reactors reliability for the treatment of less than 10% organic-waste waters. The titanium room temperature dissolution mechanism in chlorinated acidic medium (pH 2 oxide formation with a very limited tetravalent dissolution). In hydrothermal oxidation (pH>1), only the second branch is effective. The titanium protection is directly related to the oxide stability in high pH systems. The mechanism model is expressed in terms of 'current-potential' laws, which provide kinetic parameters using optimization calculations. The different elementary steps reaction rates were estimated as well as the evolution of the reaction intermediates coverage ratios with the potential. The quantification of each elementary step was performed to understand and/or orient the materials behavior according to different factors (pH, chloride ions contents, potentials...)

  20. Behavior of chlorine in lake water

    Sriraman, A.K.

    2006-01-01

    Water from monsoon fed Sagre lake is being used as a source of raw water for Tarapur Atomic Power Station (TAPS--1 and 2). The raw water from the lake is initially pumped to Sagre water treatment plant (SWTP) operated by Maharashtra Industrial Development Corporation (MIDC) from where, the processed water is sent to cater the needs of both the units of TAPS-1 and 2, townships of TAPS and MIDC, and the nearby villages. At the SWTP the raw water is treated with alum to remove the turbidity, filtered and chlorinated using bleaching powder. All these years the raw water is chlorinated in such a way whereby a residual chlorine level of 0.5-1.0 mg/l, is maintained at the outlet of water treatment plant. The adequacy of the current chlorination practice was investigated, at the request of the NPC-500 MWe group during 1990, so that the future requirements of raw water for TAPP-3 and 4, can be met from the expanded SWTP. In this connection experiments on chlorine dose -- residual chlorine relationship and the decay pattern of chlorine with time was carried out in the lake water (with low value of total dissolved solids and total hardness 3 sample at the site. The total bacterial count in the raw water observed to be 10 7 counts/ml originally came down to 10 3 counts/ml at the end of one-hour exposure time to chlorine. It was found that the chlorine demand of the water was around 6 mg/l. In addition Jar test to evaluate the aluminum dose was also carried out. Based on these experiments a chlorine dose of 6 mg/l for one hour contact time was arrived at. The experimental findings were in agreement with the current chlorination practices. (author)

  1. Anaerobic biodegradability and toxicity of wastewaters from chlorine and total chlorine-free bleaching of eucalyptus kraft pulps.

    Vidal, G.; Soto, M.; Field, J.; Mendez-Pampin, R.; Lema, J.M.

    1997-01-01

    Chlorine bleaching effluents are problematic for anaerobic wastewater treatment due to their high methanogenic toxicity and low biodegradability. Presently, alternative bleaching processes are being introduced, such as elemental chlorine-free (ECF) and total chlorine-free (TCF) bleaching. The

  2. Electrochemical Oxidation of Propene with a LSF15/CGO10 Electrochemical Reactor

    Ippolito, Davide; Kammer Hansen, Kent

    2014-01-01

    A porous electrochemical reactor, made of La0.85Sr0.15FeO3 (LSF) as electrode and Ce0.9Gd0.1O1.95 (CGO) as electrolyte, was studied for the electrochemical oxidation of propene over a wide range of temperatures. Polarization was found to enhance propene oxidation rate. Ce0.9Gd0.1O1.95 was used...... as infiltration material to enhance the effect of polarization on propene oxidation rate, especially at low temperatures. The influence of infiltrated material, as a function of heat treatment, on the reactor electrochemical behavior has been evaluated by using electrochemical impedance spectroscopy...... in suppressing the competing oxygen evolution reaction and promoting the oxidation of propene under polarization, with faradaic efficiencies above 70% at 250◦C. © 2014 The Electrochemical Society....

  3. Chlorine demand and residual chlorine decay kinetics of Kali river water at Kaiga project area

    Krishna Bhat, D.; Prakash, T.R.; Thimme Gowda, B.; Sherigara, B.S.; Khader, A.M.A.

    1995-01-01

    The nuclear power plant at Kaiga would use Kali river water for condenser cooling. This necessitated studies on the chemistry of chlorination such as chlorine demand, kinetics of chlorination and other water characteristics aimed at obtaining base line data. The study revealed significant seasonal variation of chlorine demand ranging from 0.5 ppm to 1.7 ppm (3.0 ppm dose, 30 min contact time) and total consumption of 5.0 ppm (10.0 ppm dose, 48 hours contact time). The reaction follows first order kinetics in chlorine. High correlation of chlorine demand with chlorophyll a, suspended matter, turbidity, silica, nitrite, phosphate and sulphate indicated that chlorine demand is greatly influenced by water quality. (author). 3 refs., 1 tab

  4. Effectiveness of Chlorinated Water, Sodium Hypochlorite, Sodium ...

    This study evaluated the efficacy of chlorinated water, sodium hypochlorite solution, sodium chloride solution and sterile distilled water in eliminating pathogenic bacteria on the surfaces of raw vegetables. Lettuce vegetables were dipped in different concentrations of chlorinated water, sodium hypochlorite solution, sodium ...

  5. Monitoring chlorination practices during operation at TAPS

    Sriraman, A.K.; Wani, B.N.; Gokhale, A.S.; Yuvaraju, B.

    1995-01-01

    Chlorination of cooling waters is aimed at the condenser surfaces to minimize the biogrowth, while the residual oxidants in the effluents are negligible. This paper describes the fulfillment of the above criteria, as observed during the monitoring of chlorination practices at Tarapur Atomic Power Station (TAPS) during 1990. (author). 4 refs., 2 tabs

  6. Elements from chlorine to calcium nuclear reactions

    Kunz, Wunibald

    1968-01-01

    Nuclear Tables: Part II Nuclear Reactions, Volume 3: The Elements from Chlorine to Calcium contains tabulations of the nuclear reaction values of elements chlorine, argon, potassium, and calcium. These tabulations provide the calculated Q-values of the elements and their isotopes. This book will be of value to general chemistry researchers.

  7. The Synthesis of Carbon Nanomaterials using Chlorinated ...

    The effect of chlorine on the morphology of carbon nanotubes (CNTs) prepared from a Fe-Co/CaCO3 catalyst was investigated using chlorobenzene (CB), dichlorobenzene (DCB), trichlorobenzene (TCB), dichloroethane (DCE), trichloroethane (TCE) and tetrachloroethane (TTCE) as chlorine sources using a catalytic ...

  8. Synthesis and evaluation of MoWCoS/G and MoWCuS/G as new transition metal dichalcogenide nanocatalysts for electrochemical hydrogen evolution reaction

    Askari, Mohammad Bagher; Beheshti-Marnani, Amirkhosro; Banizi, Zoha Tavakoli; Seifi, Majid; Ramezan zadeh, Mohammad Hassan

    2018-01-01

    New nanocomposites based on transition metal dichalcogenides, MoWCoS and MoWCuS, were synthesized through one step hydrothermal method. X-ray diffraction (XRD) and energy dispersive X-ray (EDX) techniques as well as field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) images confirmed the synthesis of nanocomposites. For investigation of hydrogen evolution reaction (HER) properties of new nanocomposites, linear sweep voltammetry (LSV) was applied for this purpose. According to the results of similar previous works, the prepared nanocomposites showed promising HER properties as low overpotential equal to 41.4 mV/dec for MoWCoS hybridized with reduced graphene (G) and a little higher one equal to 49 mV/dec for MoWCuS hybridized with reduced graphene. Based on obtained Tafel slopes 38 and 53 mV/dec for MoWCoS/G and MoWCuS/G, respectively, the "Heyrovsky-Volmer" mechanism was suggested for the new HER three component nanocatalysts as the first effort to this purpose.

  9. Internal chlorination of Ni-Cr alloys

    Berztiss, D.; Hennesen, K.; Grabke, H.J. [Max-Planck-Institut fuer Eisenforschung GmbH, Duesseldorf (Germany)

    1998-12-31

    In contrast to internal oxidation, sulfidation and carburization, very little information is available regarding internal chlorination, especially diffusion of chlorine in metallic alloys. This paper describes results of experiments on Ni-Cr alloys (<10 wt% Cr) exposed in an atmosphere containing radioactive HCl. The diffusion of chlorine in the alloy can be determined by measurement of residual {beta}-activity from the sample surface. Successively thin layers (0.5-10 {mu}m) of the alloy were removed by lapping and the surface activity was measured to obtain a depth profile. Both single and polycrystalline materials were tested. Through this work it should be determined if there is in fact solubility and diffusion of chlorine in Ni-based alloys as some authors have proposed or if the ingress of chlorine is mainly a grain boundary phenomenon. (orig.)

  10. Chlorine signal attenuation in concrete.

    Naqvi, A A; Maslehuddin, M; Ur-Rehman, Khateeb; Al-Amoudi, O S B

    2015-11-01

    The intensity of prompt gamma-ray was measured at various depths from chlorine-contaminated silica fume (SF) concrete slab concrete specimens using portable neutron generator-based prompt gamma-ray setup. The intensity of 6.11MeV chloride gamma-rays was measured from the chloride contaminated slab at distance of 15.25, 20.25, 25.25, 30.25 and 35.25cm from neutron target in a SF cement concrete slab specimens. Due to attenuation of thermal neutron flux and emitted gamma-ray intensity in SF cement concrete at various depths, the measured intensity of chlorine gamma-rays decreases non-linearly with increasing depth in concrete. A good agreement was noted between the experimental results and the results of Monte Carlo simulation. This study has provided useful experimental data for evaluating the chloride contamination in the SF concrete utilizing gamma-ray attenuation method. Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. Minimization of zirconium chlorinator residues

    Green, G.K.; Harbuck, D.D.

    1995-01-01

    Zirconium chlorinator residues contain an array of rare earths, scandium, unreacted coke, and radioactive thorium and radium. Because of the radioactivity, the residues must be disposed in special waste containment facilities. As these sites become more congested, and with stricter environmental regulations, disposal of large volumes of wastes may become more difficult. To reduce the mass of disposed material, the US Bureau of Mines (USBM) developed technology to recover rare earths, thorium and radium, and unreacted coke from these residues. This technology employs an HCl leach to solubilize over 99% of the scandium and thorium, and over 90% of the rare earths. The leach liquor is processed through several solvent extraction stages to selectively recover scandium, thorium, and rare earths. The leach residue is further leached with an organic acid to solubilize radium, thus allowing unreacted coke to be recycled to the chlorinator. The thorium and radium waste products, which comprise only 2.1% of the original residue mass, can then be sent to the radioactive waste facility

  12. Radiochemical analysis of chlorine-36

    Rodriguez, M.; Pina, G.; Lara, E.

    2006-01-01

    The radioactive chlorine isotope, 36 Cl, decays with a half-life of 3x10 5 years by emitting a beta particle (98 %) and by electron capture. The aim of this paper is to propose a radiochemical separation method of 36 Cl from the other beta-gamma emitters present in low and medium radioactive wastes such as spent ion exchange resins and evaporator concentrates, that arise from Nuclear Power Plants and particularly in the wastes that come from decommissioning activities of graphite reactors, in order to provide data for 36 Cl inventory calculations. The separation method proposed is based on an oxidation technique where chlorine is trapped by NaOH. 36 Cl beta emissions are measured by liquid scintillation counting by the dual label technique in order to avoid the contamination produced by 14 C which is also trapped by NaOH and which is the main contaminant present in graphite samples. The sensitivity of this method is sufficient to achieve the needed thresholds for the radiological characterization of the radioactive materials to which this method can be applied. (author)

  13. Chlorination of irradiated polyethylene single crystals

    Grimm, H.J.

    1978-01-01

    The chlorination of electron beam-irradiation polyethylene (PE) single crystals was studied for a range of irradiation doses, temperatures, and chlorine interaction times. The results presented show that PE chlorination was quite extensive, even in unirradiated PE single crystals at 25 0 C in the dark. Electron Spin Resonance (ESR, EPR) was used in this study in order to determine the alkyl radical concentration, decay constant, and diffusivity for (unchlorinated) specimens. An alkyl radical diffusivity D/sub a/ = 1.6 x 10 -17 cm 2 /sec at 25 0 C was estimated from ESR data and alkyl radical migration as one-dimensional unsteady-state diffusion process. In irradiated PE, chlorination occurred mainly via chain reactions which were initiated by the irradiation-produced free radicals. Chlorine content values were determined by X-ray Energy Spectroscopy (XES). It was found that the magnitude of the chlorine uptake increased with increasing dose, and decreased with decreasing temperature at constant dose. Otherwise the observed PE chlorination phenomena was quite similar for all of the doses and temperatures studied here, consisting of a two step mechanism: a fast uptake which occurred between time tCl 2 = 0 - 5 minutes and a slower, approximately first-order rate of uptake which occurred between times tCl 2 = 5 - 120 minutes. Chlorination was essentially complete by time tCl 2 = 120 minutes. The rapid uptake probably occurred in the amorphous surface zones where Cl 2 is relatively high and the second, slower step was probably attributable to Cl 2 diffusion into the crystalline regions and subsequent chlorination there. Inasmuch as the PE density decreases with increasing dose (for 1-600 Mrad), Cl 2 diffusivity was enhanced, resulting in higher chlorine uptake values at higher doses

  14. Identification of chlorinated oligomers formed during anodic oxidation of phenol in the presence of chloride

    Chen, Linxi; Campo, Pablo; Kupferle, Margaret J.

    2015-01-01

    Graphical abstract: - Highlights: • By-products from anodic oxidation of phenol in the presence of chloride are investigated. • Chlorinated oligomer formation is demonstrated by LC-QTOF-MS. • They have structures similar to triclosan and polychlorinated dibenzo-p-dioxins. - Abstract: Chlorinated oligomer intermediates formed during the anodic electrochemical oxidation of phenol with a boron-doped diamond electrode were studied at two different concentrations of chloride (5 mM and 50 mM). Under the same ionic strength, with sodium sulfate being the make-up ion, a 10-fold increase in Cl − led to removal rates 10.8, 1.5, and 1.4 times higher for phenol, TOC, and COD, respectively. Mono-, di- and trichlorophenols resulting from electrophilic substitution were the identified by-products. Nevertheless, discrepancies between theoretical and measured TOC values along with gaps in the mass balance of chlorine-containing species indicated the formation of unaccounted-for chlorinated by-products. Accurate mass measurements by liquid chromatography quadrupole time-of-flight mass spectrometry and MS-MS fragmentation spectra showed that additional compounds formed were dimers and trimers of phenol with structures similar to triclosan and polychlorinated dibenzo-p-dioxins

  15. Identification of chlorinated oligomers formed during anodic oxidation of phenol in the presence of chloride

    Chen, Linxi; Campo, Pablo; Kupferle, Margaret J., E-mail: margaret.kupferle@uc.edu

    2015-02-11

    Graphical abstract: - Highlights: • By-products from anodic oxidation of phenol in the presence of chloride are investigated. • Chlorinated oligomer formation is demonstrated by LC-QTOF-MS. • They have structures similar to triclosan and polychlorinated dibenzo-p-dioxins. - Abstract: Chlorinated oligomer intermediates formed during the anodic electrochemical oxidation of phenol with a boron-doped diamond electrode were studied at two different concentrations of chloride (5 mM and 50 mM). Under the same ionic strength, with sodium sulfate being the make-up ion, a 10-fold increase in Cl{sup −} led to removal rates 10.8, 1.5, and 1.4 times higher for phenol, TOC, and COD, respectively. Mono-, di- and trichlorophenols resulting from electrophilic substitution were the identified by-products. Nevertheless, discrepancies between theoretical and measured TOC values along with gaps in the mass balance of chlorine-containing species indicated the formation of unaccounted-for chlorinated by-products. Accurate mass measurements by liquid chromatography quadrupole time-of-flight mass spectrometry and MS-MS fragmentation spectra showed that additional compounds formed were dimers and trimers of phenol with structures similar to triclosan and polychlorinated dibenzo-p-dioxins.

  16. Electrochemical performance and structure evolution of core-shell nano-ring α-Fe{sub 2}O{sub 3}@Carbon anodes for lithium-ion batteries

    Sun, Yan-Hui, E-mail: sunyanhui0102@163.com; Liu, Shan; Zhou, Feng-Chen; Nan, Jun-Min

    2016-12-30

    Core-shell nano-ring α-Fe{sub 2}O{sub 3}@Carbon (CSNR) composites with different carbon content (CSNR-5%C and CSNR-13%C) are synthesized using a hydrothermal method by controlling different amounts of glucose and α-Fe{sub 2}O{sub 3} nano-rings with further annealing. The CSNR electrodes exhibit much improved specific capacity, cycling stability and rate capability compared with that of bare nano-ring α-Fe{sub 2}O{sub 3} (BNR), which is attributed to the core-shell nano-ring structure of CSNR. The carbon shell in the inner and outer surface of CSNR composite can increase electron conductivity of the electrode and inhibit the volume change of α-Fe{sub 2}O{sub 3} during discharge/charge processes, and the nano-ring structure of CSNR can buffer the volume change too. The CSNR-5%C electrode shows super high initial discharge/charge capacities of 1570/1220 mAh g{sup −1} and retains 920/897 mAh g{sup −1} after 200 cycles at 500 mA g{sup −1} (0.5C). Even at 2000 mA g{sup −1} (2C), the electrode delivers the initial capacities of 1400/900 mAh g{sup −1}, and still maintains 630/610 mAh g{sup −1} after 200 cycles. The core-shell nano-rings opened during cycling and rebuilt a new flower-like structure consisting of α-Fe{sub 2}O{sub 3}@Carbon nano-sheets. The space among the nano-sheet networks can further buffer the volume expansion of α-Fe{sub 2}O{sub 3} and facilitate the transportation of electrons and Li{sup +} ions during the charge/discharge processes, which increases the capacity and rate capability of the electrode. It is the first time that the evolution of core-shell α-Fe{sub 2}O{sub 3}@Carbon changing to flower-like networks during lithiation/de-lithiation has been reported.

  17. Electrochemical performance and structure evolution of core-shell nano-ring α-Fe_2O_3@Carbon anodes for lithium-ion batteries

    Sun, Yan-Hui; Liu, Shan; Zhou, Feng-Chen; Nan, Jun-Min

    2016-01-01

    Core-shell nano-ring α-Fe_2O_3@Carbon (CSNR) composites with different carbon content (CSNR-5%C and CSNR-13%C) are synthesized using a hydrothermal method by controlling different amounts of glucose and α-Fe_2O_3 nano-rings with further annealing. The CSNR electrodes exhibit much improved specific capacity, cycling stability and rate capability compared with that of bare nano-ring α-Fe_2O_3 (BNR), which is attributed to the core-shell nano-ring structure of CSNR. The carbon shell in the inner and outer surface of CSNR composite can increase electron conductivity of the electrode and inhibit the volume change of α-Fe_2O_3 during discharge/charge processes, and the nano-ring structure of CSNR can buffer the volume change too. The CSNR-5%C electrode shows super high initial discharge/charge capacities of 1570/1220 mAh g"−"1 and retains 920/897 mAh g"−"1 after 200 cycles at 500 mA g"−"1 (0.5C). Even at 2000 mA g"−"1 (2C), the electrode delivers the initial capacities of 1400/900 mAh g"−"1, and still maintains 630/610 mAh g"−"1 after 200 cycles. The core-shell nano-rings opened during cycling and rebuilt a new flower-like structure consisting of α-Fe_2O_3@Carbon nano-sheets. The space among the nano-sheet networks can further buffer the volume expansion of α-Fe_2O_3 and facilitate the transportation of electrons and Li"+ ions during the charge/discharge processes, which increases the capacity and rate capability of the electrode. It is the first time that the evolution of core-shell α-Fe_2O_3@Carbon changing to flower-like networks during lithiation/de-lithiation has been reported.

  18. Electrochemical performance and structure evolution of core-shell nano-ring α-Fe2O3@Carbon anodes for lithium-ion batteries

    Sun, Yan-Hui; Liu, Shan; Zhou, Feng-Chen; Nan, Jun-Min

    2016-12-01

    Core-shell nano-ring α-Fe2O3@Carbon (CSNR) composites with different carbon content (CSNR-5%C and CSNR-13%C) are synthesized using a hydrothermal method by controlling different amounts of glucose and α-Fe2O3 nano-rings with further annealing. The CSNR electrodes exhibit much improved specific capacity, cycling stability and rate capability compared with that of bare nano-ring α-Fe2O3 (BNR), which is attributed to the core-shell nano-ring structure of CSNR. The carbon shell in the inner and outer surface of CSNR composite can increase electron conductivity of the electrode and inhibit the volume change of α-Fe2O3 during discharge/charge processes, and the nano-ring structure of CSNR can buffer the volume change too. The CSNR-5%C electrode shows super high initial discharge/charge capacities of 1570/1220 mAh g-1 and retains 920/897 mAh g-1 after 200 cycles at 500 mA g-1 (0.5C). Even at 2000 mA g-1 (2C), the electrode delivers the initial capacities of 1400/900 mAh g-1, and still maintains 630/610 mAh g-1 after 200 cycles. The core-shell nano-rings opened during cycling and rebuilt a new flower-like structure consisting of α-Fe2O3@Carbon nano-sheets. The space among the nano-sheet networks can further buffer the volume expansion of α-Fe2O3 and facilitate the transportation of electrons and Li+ ions during the charge/discharge processes, which increases the capacity and rate capability of the electrode. It is the first time that the evolution of core-shell α-Fe2O3@Carbon changing to flower-like networks during lithiation/de-lithiation has been reported.

  19. Synthesis of IV-VI Transition Metal Carbide and Nitride Nanoparticles Using a Reactive Mesoporous Template for Electrochemical Hydrogen Evolution Reaction

    Alhajri, Nawal Saad

    2016-01-01

    content rather than nitride. In addition, the reactivity of the transition metals of group IV-VI with the reactive template was investigated under a flow of N2 at different temperatures in the range of 1023 to 1573 K while keeping the weight ratio constant at 1:1. The results show that Ti, V, Nb, Ta, and Cr reacted with mpg-C3N4 at 1023 K to form nitride phase with face centered cubic structure. The nitride phase destabilized at higher temperature ≥1223 K through the reaction with the remaining carbon residue originated from the decomposition of the template to form carbonitride and carbide phases. Whereas, Mo and W produce a hexagonal structure of carbide irrespective of the applying reaction temperature. The tendency to form transition metal nitrides and carbides at 1023 K was strongly driven by the free energy of formation. The observed trend indicates that the free energy of formation of nitride is relatively lower for group IV and V transition metals, whereas the carbide phase is thermodynamically more favorable for group VI, in particular for Mo and W. The thermal stability of nitride decreases at high temperature due to the evolution of nitrogen gas. The electrocatalytic activities of the produced nanoparticles were tested for hydrogen evolution reaction in acid media and the results demonstrated that molybdenum carbide nanoparticles exhibited the highest HER current with over potential of 100 mV vs. RHE, among the samples prepared in this study. This result is attributed to the sufficiently small particle size (8 nm on average) and accordingly high surface area (308 m2 g-1). Also, the graphitized carbon layer with a thickness of 1 nm on its surface formed by this synthesis provides excellent electron pathway to the catalyst which will improve the rate of electron transfer reaction.

  20. In situ experimental study for the optimization of chlorine dosage in seawater cooling systems

    Nebot, E.; Casanueva, T.; Fernandez-Baston, M.M.; Sales, D. [Department of Chemical Engineering, Food Technology and Environmental Technologies, University of Cadiz (Spain); Casanueva, J.F. [Department of Thermal Engines, University of Cadiz (Spain)

    2006-11-15

    The paper details an in situ study for the evaluation of the evolution of fouling heat transfer resistance and to optimize the antifouling chlorine dosage at a 550MW power station. A portable pilot plant has been designed to simulate the steam surface condenser and used as an accurate fouling monitor that takes the seawater from the same intake point as the power station. This study includes fouling extraction and its characterization for different dosage patterns. The residual chlorine concentration at the cooling-water discharge from the power station is 0.2mg/l and has been considered appropriate for the prevention of the formation of fouling, because with this concentration approximately 90% reduction in the amount of fouling is obtained. Residual chlorine dosages lower than 0.2ppm could be effective in controlling fouling development if mechanical techniques of fouling control are also available. (author)

  1. Electrochemical combustion of indigo at ternary oxide coated titanium anodes

    María I. León

    2014-12-01

    Full Text Available The film of iridium and tin dioxides doped with antimony (IrO2-SnO2–Sb2O5 deposited on a Ti substrate (mesh obtained by Pechini method was used for the formation of ·OH radicals by water discharge. Detection of ·OH radicals was followed by the use of the N,N-dimethyl-p-nitrosoaniline (RNO as a spin trap. The electrode surface morphology and composition was characterized by SEM-EDS. The ternary oxide coating was used for the electrochemical combustion of indigo textile dye as a model organic compound in chloride medium. Bulk electrolyses were then carried out at different volumetric flow rates under galvanostatic conditions using a filter-press flow cell. The galvanostatic tests using RNO confirmed that Ti/IrO2-SnO2-Sb2O5 favor the hydroxyl radical formation at current densities between 5 and 7 mA cm-2, while at current density of 10 mA cm-2 the oxygen evolution reaction occurs. The indigo was totally decolorized and mineralized via reactive oxygen species, such as (·OH, H2O2, O3 and active chlorine formed in-situ at the Ti/IrO2-SnO2-Sb2O5 surface at volumetric flow rates between 0.1-0.4 L min-1 and at fixed current density of 7 mA cm-2. The mineralization of indigo carried out at 0.2 L min-1 achieved values of 100 %, with current efficiencies of 80 % and energy consumption of 1.78 KWh m-3.

  2. Electrochemical energy generation

    Kreysa, G.; Juettner, K.

    1993-01-01

    The proceedings encompass 40 conference papers belonging to the following subject areas: Baseline and review papers; electrochemical fuel cells; batteries: Primary and secondary cells; electrochemical, regenerative systems for energy conversion; electrochemical hydrogen generation; electrochemistry for nuclear power plant; electrochemistry for spent nuclear fuel reprocessing; energy efficiency in electrochemical processes. There is an annex listing the authors and titles of the poster session, and compacts of the posters can be obtained from the office of the Gesellschaft Deutscher Chemiker, Abteilung Tagungen. (MM) [de

  3. Quantifying Short-Chain Chlorinated Paraffin Congener Groups

    Yuan, Bo; Bogdal, Christian; Berger, Urs; MacLeod, Matthew; Gebbink, Wouter A.; Alsberg, Tomas; Wit, de Cynthia A.

    2017-01-01

    Accurate quantification of short-chain chlorinated paraffins (SCCPs) poses an exceptional challenge to analytical chemists. SCCPs are complex mixtures of chlorinated alkanes with variable chain length and chlorination level; congeners with a fixed chain length (n) and number of chlorines (m) are

  4. UV/chlorine treatment of carbamazepine: Transformation products and their formation kinetics.

    Pan, Yanheng; Cheng, ShuangShuang; Yang, Xin; Ren, Jingyue; Fang, Jingyun; Shang, Chii; Song, Weihua; Lian, Lushi; Zhang, Xinran

    2017-06-01

    Carbamazepine (CBZ) is one of the pharmaceuticals most frequently detected in the aqueous environment. This study investigated the transformation products when CBZ is degraded by chlorine under ultraviolet (UV) irradiation (the UV/chlorine process). Detailed pathways for the degradation of CBZ were elucidated using ultra-high performance liquid chromatography (UHPLC)-quadrupole time-of-flight mass spectrometry (QTOF-MS). CBZ is readily degraded by hydroxyl radicals (HO) and chlorine radicals (Cl) in the UV/chlorine process, and 24 transformation products were identified. The products indicate that the 10,11-double bond and aromatic ring in CBZ are the sites most susceptible to attack by HO and Cl. Subsequent reaction produces hydroxylated and chlorinated aromatic ring products. Four specific products were quantified and their evolution was related with the chlorine dose, pH, and natural organic matter concentration. Their yields showed an increase followed by a decreasing trend with prolonged reaction time. CBZ-10,11-epoxide (I), the main quantified transformation product from HO oxidation, was observed with a peak transformation yield of 3-32% depending on the conditions. The more toxic acridine (IV) was formed involving both HO and Cl with peak transformation yields of 0.4-1%. All four quantified products together amounted to a peak transformation yield of 34.5%. The potential toxicity of the transformation products was assayed by evaluating their inhibition of the bioluminescence of the bacterium Vibrio Fischeri. The inhibition increased at first and the decreased at longer reaction times, which was in parallel with the evolution of transformation products. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Mediated electrochemical hazardous waste destruction

    Hickman, R.G.; Farmer, J.C.; Wang, F.T.

    1991-08-01

    There are few permitted processes for mixed waste (radioactive plus chemically hazardous) treatment. We are developing electrochemical processes that convert the toxic organic components of mixed waste to water, carbon dioxide, an innocuous anions such as chloride. Aggressive oxidizer ions such as Ag 2+ or Ce +4 are produced at an anode. These can attack the organic molecules directly. They can also attack water which yields hydroxyl free radicals that in turn attack the organic molecules. The condensed (i.e., solid and/or liquid) effluent streams contain the inorganic radionuclide forms. These may be treated with existing technology and prepared for final disposal. Kinetics and the extent of destruction of some toxic organics have been measured. Depending on how the process is operated, coulombic efficiency can be nearly 100%. In addition, hazardous organic materials are becoming very expensive to dispose of and when they are combined with transuranic radioactive elements no processes are presently permitted. Mediated electrochemical oxidation is an ambient-temperature aqueous-phase process that can be used to oxidize organic components of mixed wastes. Problems associated with incineration, such as high-temperature volatilization of radionuclides, are avoided. Historically, Ag (2) has been used as a mediator in this process. Fe(6) and Co(3) are attractive alternatives to Ag(2) since they form soluble chlorides during the destruction of chlorinated solvents. Furthermore, silver itself is a toxic heavy metal. Quantitative data has been obtained for the complete oxidation of ethylene glycol by Fe(6) and Co(3). Though ethylene glycol is a nonhalogenated organic, this data has enabled us to make direct comparisons of activities of Fe(6) and Co(3) with Ag(2). Very good quantitative data for the oxidation of ethylene glycol by Ag(2) had already been collected. 4 refs., 6 figs

  6. Studies on chlorinated bromide salt for microfouling control

    Satpathy, K.K.; Rajmohan, R.; Rao, T.S.; Nair, K.V.K.; Mathur, P.K.

    1995-01-01

    The Fast Breeder Test reactor (FBTR) at Kalpakkam has been facing various problems in cooling water systems in spite of intermittent chlorination.Effects of chlorinated-bromide mixture was evaluated against heterotrophic bacteria (TVC) and iron oxidising bacteria (IOB) vis-a-vis chlorine. Results indicated that chlorinated-bromide mixture was far superior (2 orders of magnitude for TVC and 2 times for IOB) to chlorine in microfouling control. Results also showed that at bromide to chlorine ratio of one effectiveness of chlorinated-bromide was at its maximum. (author). 9 refs., 1 tab

  7. Chlorine isn't Just for Swimming Pools Anymore... Chlorination of Organic Compounds in the Arctic

    Han, A.; Raab, T. K.

    2013-12-01

    The cycling of chlorine between its organic and inorganic forms is known to occur in forest soils, but little is known about the generality of this mechanism, which soil components chlorine attaches to, and at what rate chlorination occurs. The study uses peat-rich tundra soils from Barrow, Alaska varying in age since formation of 50 yrs - 5500 yrs BP, and seeks to measure the rate at which organic molecules are chlorinated and to understand what changes those molecules undergo once chlorinated. Soil abundance of chlorine and bromine was estimated in soils of varying age using X-ray fluorescence, and org-Cl levels were measured using pyro-hydrolysis [Table 1]. We considered activity of the enzyme Chloroperoxidase, and data was gathered using absorbance scans of the organic molecule monochlorodimedone to determine whether it had been chlorinated and if so, at what rate. Additional information was gathered from the chlorination of small organic components of the macromolecule lignin, whose constituent molecules make up a large portion of humic materials critical to soil health, through emission scans and fluorescence scans. The results showed that the enzyme chloroperoxidase, which is found in nature and is associated with fungi or bacteria, attaches a chlorine atom to monochlorodimedone and that similar enzymes found in Arctic soils act on it, as well as the lignin model subunits cinnamaldehyde ((2E)-3-phenylprop-2-enal) and naringenin-7-rhamnoglucoside. The results may provide more information on chlorination rates in the Arctic and may contribute to an understanding of how and at what rate chlorine changes form in nature, and answer questions about ozone deterioration or anthropogenic chlorine impact(s) on the environment.Average Halogen Abundance in Arctic Soils xrf=Energy Dispersive X-Ray Fluorescencepyro= TOX Pyro-Hydrolysis

  8. Electrochemical capacity fading of polyaniline electrode in supercapacitor: An XPS analysis

    Jinxing Deng

    2017-04-01

    Full Text Available To understand the electrochemical capacity fading of the polyaniline (PANI electrodes in supercapacitors, for the first time, their chemical structure change during electrochemical cycles was traced with XPS analysis after the HCl doped PANI electrodes were subjected to the cyclic voltammetry test in 1.0 M H2SO4 electrolyte for different cycle numbers. The results showed that the chlorine disappeared in the electrode surface, while the surface element contents of sulfur and oxygen increased with the electrochemical cycles increased. It demonstrated that the hydrolytic degradation of the PANI chains and exchange of dopant occurred during the electrochemical cycling, causing the fading in the mechanical and electrochemical performance of the PANI electrodes. This understanding should lead to better design of the conductive polymer-based energy storage devices.

  9. Determination of chlorine in nuclear-grade uranium compounds

    Yang Chunqing; Liu Fuyun; Huang Dianfan

    1988-01-01

    The determination of chlorine in nuclear-grade uranium compounds is discribed. Chlorine is separated from uranium oxide pyrohydrolytically with stream of wet oxygen in a furnace at 800 ∼ 900 deg C. Chlorine is volatilized as hydrochloric acid, absorbed in a dilute alkaline solution and measured with chlorine-selective electrode. This method covers the concentration range of 10 ∼ 500 pm chlorine in uranium oxide. Precision of at least ± 10% and recovery of 85 ∼ 108% have been reported

  10. Microbial transformation of chlorinated aromatics in sediments

    Beurskens, J.E.M.

    1995-01-01

    Numerous contaminants like heavy metals, polycyclic aromatic hydrocarbons (PAHs), chlorinated benzenes (CBs), polychlorinated biphenyls (PCBs), polychlorinated dibenzo- p -dioxins (PCDDs) and polychlorinated furans (PCDFs) are detected in the major rivers in the

  11. Study for the chlorination of zirconium oxide

    Seo, E.S.M.; Takiishi, H.; Paschoal, J.O.A.; Andreoli, M.

    1990-12-01

    In the development of new ceramic and metallic materials the chlorination process constitutes step in the formation of several intermediate compounds, such as metallic chlorides, used for the production of high, purity raw materials. Chlorination studies with the aim of fabrication special zirconium-base alloys have been carried out at IPEN. Within this program the chlorination technique has been used for zirconium tetrachloride production from zirconium oxide. In this paper some relevant parameters such as: time and temperature of reaction, flow rate of chloride gas and percentage of the reducing agent which influence the efficiency of chlorination of zirconium oxide are evaluated. Thermodynamical aspects about the reactions involved in the process are also presented. (author)

  12. Hydrochloric acid recycling from chlorinated hydrocarbons

    Sowieja, D. [Sulzer Escher Wyss GmbH, Ravensburg (Germany); Schaub, M. [Sulzer Chemtech Ltd., Winterthur (Switzerland)

    1993-12-31

    Chlorinated hydrocarbons present a major ecological hazard since most of them are only poorly biodegradable. Incineration is an economical process for their destruction, however the usually recovered sodium or calcium chlorides do not present a value and their disposal may even be very costly. Recovery of hydrochloric acid may therefore present an economical solution, mainly were large quantities of highly chlorinated compounds can be processed (author) 6 refs., 4 figs., 1 tab.

  13. Dehalogenation of Chlorinated Hydroxybiphenyls by Fungal Laccase

    Schultz, Asgard; Jonas, Ulrike; Hammer, Elke; Schauer, Frieder

    2001-01-01

    We have investigated the transformation of chlorinated hydroxybiphenyls by laccase produced by Pycnoporus cinnabarinus. The compounds used were transformed to sparingly water-soluble colored precipitates which were identified by gas chromatography-mass spectrometry as oligomerization products of the chlorinated hydroxybiphenyls. During oligomerization of 2-hydroxy-5-chlorobiphenyl and 3-chloro-4-hydroxybiphenyl, dechlorinated C—C-linked dimers were formed, demonstrating the dehalogenation ability of laccase. In addition to these nonhalogenated dimers, both monohalogenated and dihalogenated dimers were identified. PMID:11526052

  14. Radiolytic removal of trihalomethane in chlorinated seawater

    Rajamohan, R.; Rajesh, Puspalata; Venugopalan, V.P.; Rangarajan, S.; Natesan, Usha

    2015-01-01

    Biofouling is one of the major operational problems in seawater cooling systems. It is controlled by application of chlorine based biocides in the range of 0.5-2.0 mg L -1 . The bromide in seawater reacts with the added chlorine and forms hypobromous acid. The brominated residual biocides react with natural organic matter present in the seawater, resulting in the formation of trihalomethanes (THM) such as bromoform (CHBr 3 ), dibromochloromethane (CHBr 2 Cl) bromodichloromethane (CHBrCl 2 ). Though THMs represent a small fraction of the added chlorine, they are relatively more persistent than residual chlorine, and hence pose a potential hazard to marine life because of their reported mutagenicity. There have been few reports on removal of THMs from chlorinated seawater. In this work, the efficacy of gamma irradiation technique for the removal of THMs from chlorine-dosed seawater was investigated. Experiments were carried out using seawater collected from Kalpakkam. Irradiation study was conducted in chlorinated (1, 3, and 5 mg L -1 of Cl 2 ) seawater by applying various dosages (0.4-5.0 kGy) of gamma radiation using a 60 Co Gamma Chamber 5000. Bromoform showed a faster rate of degradation as compared to other halocarbons like bromodichloromethane and dibromochloromethane. This shows the change in total THM concentration with variation in the radiation dose and initial Cl 2 dosing. When the percentage degradation of all the three trihalomethane species was compared with applied doses, it was found that the maximum reduction occurred at a dose of 2.5 kGy. The reduction was almost similar for all the three doses (1, 3, 5 ppm of Cl 2 ) used for chlorination. With a further increase in radiation dose to 5.0 kGy, a slight increase in reduction was observed

  15. Hydrochloric acid recycling from chlorinated hydrocarbons

    Sowieja, D [Sulzer Escher Wyss GmbH, Ravensburg (Germany); Schaub, M [Sulzer Chemtech Ltd., Winterthur (Switzerland)

    1994-12-31

    Chlorinated hydrocarbons present a major ecological hazard since most of them are only poorly biodegradable. Incineration is an economical process for their destruction, however the usually recovered sodium or calcium chlorides do not present a value and their disposal may even be very costly. Recovery of hydrochloric acid may therefore present an economical solution, mainly were large quantities of highly chlorinated compounds can be processed (author) 6 refs., 4 figs., 1 tab.

  16. Stratospheric chlorine: Blaming it on nature

    Taube, G.

    1993-01-01

    Much of the bitter public debate over ozone depletion has centered on the claim that chlorofluorocarbons (CFCs) pale into insignificance alongside natural sources of chlorine in the stratosphere. If so, goes the argument, chlorine could not be depleting ozone as atmospheric scientists claim, because the natural sources have been around since time immemorial, and the ozone layer is still there. The claim, put forward in a book by Rogelio Maduro and Ralf Schauerhammer, has since been touted by former Atomic Energy Commissioner Dixy Lee Ray and talk-show host Rush Limbaugh, and it forms the basis of much of the backlash now being felt by atmospheric scientists. The argument is simple: Maduro and Schauerhammer calculate that 600 million tons of chlorine enters the atmosphere annually from seawater, 36 million tons from volcanoes, 8.4 million tons from biomass burning, and 5 million tons from ocean biota. In contrast, CFCs account for a mere 750,000 tons of atmospheric chlorine a year. Besides disputing the numbers, scientists have both theoretical and observational bases for doubting that much of this chlorine is getting into the stratosphere, where it could affect the ozone layer. Linwood Callis of the National Aeronautics and Space Administration's (NASA) Langley Research Center points out one crucial problem with the argument: Chlorine from natural sources is soluble, and so it gets rained out of the lower atmosphere. CFCs, in contrast, are insoluble and inert and thus make it to the stratosphere to release their chlorine. What's more, observations of stratospheric chemistry don't support the idea that natural sources are contributing much to the chlorine there

  17. Chlorinated drinking water for lightweight laying hens

    A.F. Schneider

    Full Text Available ABSTRACT The study aimed to evaluate the effect of different levels of chlorine in drinking water of laying hens on zootechnical performance, eggs shell quality, hemogasometry levels and calcium content in tibia. 144 Hy-Line laying hens, 61 weeks old, were used distributed in 24 metabolism cages. They were subjected to water diets, for a period of 28 days, using sodium hypochlorite as a chlorine source in order to obtain the following concentrations: 5ppm (control, 20ppm, 50ppm, and 100ppm. Their performance was evaluated through water consumption, feed intake, egg production and weight, egg mass, feed conversion. Shell quality was measured by specific gravity. At the end of the experiment, arterial blood was collected for blood gas level assessment and a poultry of each replicate was sacrificed to obtain tibia and calcium content measurement. There was a water consumption reduction from 20ppm of chlorine and feed intake reduction in poultry receiving water with 100ppm of chlorine. The regression analysis showed that the higher the level of chlorine in water, the higher the reduction in consumption. There were no differences in egg production and weight, egg mass, feed conversion, specific gravity, tibia calcium content, and hemogasometry levels (hydrogenionic potential, carbon dioxide partial pressure, oxygen partial pressure, sodium, potassium, chloride, bicarbonate, carbon dioxide total concentration, anion gap and oxygen saturation. The use of levels above 5ppm of chlorine is not recommended in the water of lightweight laying hens.

  18. New model of chlorine-wall reaction for simulating chlorine concentration in drinking water distribution systems.

    Fisher, Ian; Kastl, George; Sathasivan, Arumugam

    2017-11-15

    Accurate modelling of chlorine concentrations throughout a drinking water system needs sound mathematical descriptions of decay mechanisms in bulk water and at pipe walls. Wall-reaction rates along pipelines in three different systems were calculated from differences between field chlorine profiles and accurately modelled bulk decay. Lined pipes with sufficiently large diameters (>500 mm) and higher chlorine concentrations (>0.5 mg/L) had negligible wall-decay rates, compared with bulk-decay rates. Further downstream, wall-reaction rate consistently increased (peaking around 0.15 mg/dm 2 /h) as chlorine concentration decreased, until mass-transport to the wall was controlling wall reaction. These results contradict wall-reaction models, including those incorporated in the EPANET software, which assume wall decay is of either zero-order (constant decay rate) or first-order (wall-decay rate reduces with chlorine concentration). Instead, results are consistent with facilitation of the wall reaction by biofilm activity, rather than surficial chemical reactions. A new model of wall reaction combines the effect of biofilm activity moderated by chlorine concentration and mass-transport limitation. This wall reaction model, with an accurate bulk chlorine decay model, is essential for sufficiently accurate prediction of chlorine residuals towards the end of distribution systems and therefore control of microbial contamination. Implementing this model in EPANET-MSX (or similar) software enables the accurate chlorine modelling required for improving disinfection strategies in drinking water networks. New insight into the effect of chlorine on biofilm can also assist in controlling biofilm to maintain chlorine residuals. Copyright © 2017 Elsevier Ltd. All rights reserved.

  19. Biomass derived porous nitrogen doped carbon for electrochemical devices

    Litao Yan

    2017-04-01

    Full Text Available Biomass derived porous nanostructured nitrogen doped carbon (PNC has been extensively investigated as the electrode material for electrochemical catalytic reactions and rechargeable batteries. Biomass with and without containing nitrogen could be designed and optimized to prepare PNC via hydrothermal carbonization, pyrolysis, and other methods. The presence of nitrogen in carbon can provide more active sites for ion absorption, improve the electronic conductivity, increase the bonding between carbon and sulfur, and enhance the electrochemical catalytic reaction. The synthetic methods of natural biomass derived PNC, heteroatomic co- or tri-doping into biomass derived carbon and the application of biomass derived PNC in rechargeable Li/Na batteries, high energy density Li–S batteries, supercapacitors, metal-air batteries and electrochemical catalytic reaction (oxygen reduction and evolution reactions, hydrogen evolution reaction are summarized and discussed in this review. Biomass derived PNCs deliver high performance electrochemical storage properties for rechargeable batteries/supercapacitors and superior electrochemical catalytic performance toward hydrogen evolution, oxygen reduction and evolution, as promising electrodes for electrochemical devices including battery technologies, fuel cell and electrolyzer. Keywords: Biomass, Nitrogen doped carbon, Batteries, Fuel cell, Electrolyzer

  20. Electrochemical characterisation of CaCl2 deficient LiCl-KCl-CaCl2 eutectic melt and electro-deoxidation of solid UO2

    Sri Maha Vishnu, D.; Sanil, N.; Mohandas, K. S.; Nagarajan, K.

    2016-03-01

    The CaCl2 deficient ternary eutectic melt LiCl-KCl-CaCl2 (50.5: 44.2: 5.3 mol %) was electrochemically characterised by cyclic voltammetry and polarization techniques in the context of its probable use as the electrolyte in the electrochemical reduction of solid UO2 to uranium metal. Tungsten (cathodic polarization) and graphite (anodic polarization) working electrodes were used in these studies carried out in the temperature range 623 K-923 K. The cathodic limit of the melt was observed to be set by the deposition of Ca2+ ions followed by Li+ ions on the tungsten electrode and the anodic limit by oxidation of chloride ions on the graphite electrode (chlorine evolution). The difference between the onset potential of deposition of Ca2+ and Li+ was found to be 0.241 V at a scan rate of 20 mV/s at 623 K and the difference decreased with increase in temperature and vanished at 923 K. Polarization measurements with stainless steel (SS) cathode and graphite anode at 673 K showed the possibility of low-energy reactions occurring on the UO2 electrode in the melt. UO2 pellets were cathodically polarized at 3.9 V for 25 h to test the feasibility of electro-reduction to uranium in the melt. The surface of the pellets was found reduced to U metal.

  1. A refined method for calculating equivalent effective stratospheric chlorine

    Engel, Andreas; Bönisch, Harald; Ostermöller, Jennifer; Chipperfield, Martyn P.; Dhomse, Sandip; Jöckel, Patrick

    2018-01-01

    Chlorine and bromine atoms lead to catalytic depletion of ozone in the stratosphere. Therefore the use and production of ozone-depleting substances (ODSs) containing chlorine and bromine is regulated by the Montreal Protocol to protect the ozone layer. Equivalent effective stratospheric chlorine (EESC) has been adopted as an appropriate metric to describe the combined effects of chlorine and bromine released from halocarbons on stratospheric ozone. Here we revisit the concept of calculating EESC. We derive a refined formulation of EESC based on an advanced concept of ODS propagation into the stratosphere and reactive halogen release. A new transit time distribution is introduced in which the age spectrum for an inert tracer is weighted with the release function for inorganic halogen from the source gases. This distribution is termed the release time distribution. We show that a much better agreement with inorganic halogen loading from the chemistry transport model TOMCAT is achieved compared with using the current formulation. The refined formulation shows EESC levels in the year 1980 for the mid-latitude lower stratosphere, which are significantly lower than previously calculated. The year 1980 is commonly used as a benchmark to which EESC must return in order to reach significant progress towards halogen and ozone recovery. Assuming that - under otherwise unchanged conditions - the EESC value must return to the same level in order for ozone to fully recover, we show that it will take more than 10 years longer than estimated in this region of the stratosphere with the current method for calculation of EESC. We also present a range of sensitivity studies to investigate the effect of changes and uncertainties in the fractional release factors and in the assumptions on the shape of the release time distributions. We further discuss the value of EESC as a proxy for future evolution of inorganic halogen loading under changing atmospheric dynamics using simulations from

  2. Effect of chlorination on the development of marine biofilms dominated by diatoms

    Patil, J.S.; Jagadeesan, V.

    , and Thalassionema did not increase in density after chlorine treatment. It was also demonstrated that diatoms can colonize, grow and photosynthesize on chlorine-treated surfaces. Under pulse chlorination (treatment every 6 h), irrespective of chlorine concentration...

  3. Chlorination of organophosphorus pesticides in natural waters

    Acero, Juan L. [Departamento de Ingenieria Quimica y Energetica, Universidad de Extremadura, 06071 Badajoz (Spain)], E-mail: jlacero@unex.es; Benitez, F. Javier; Real, Francisco J.; Gonzalez, Manuel [Departamento de Ingenieria Quimica y Energetica, Universidad de Extremadura, 06071 Badajoz (Spain)

    2008-05-01

    Unknown second-order rate constants for the reactions of three organophosphorus pesticides (chlorpyrifos, chlorfenvinfos and diazinon) with chlorine were determined in the present study, and the influence of pH and temperature was established. It was found that an increase in the pH provides a negative effect on the pesticides degradation rates. Apparent second-order rate constants at 20 {sup o}C and pH 7 were determined to be 110.9, 0.004 and 191.6 M{sup -1} s{sup -1} for chlorpyrifos, chlorfenvinfos and diazinon, respectively. A higher reactivity of chlorine with the phosphorothioate group (chlorpyrifos and diazinon) than with the phosphate moiety (chlorfenvinfos) could explain these results. Intrinsic rate constant for the elementary reactions of chlorine species with chlorpyrifos and diazinon were also calculated, leading to the conclusion that the reaction between hypochlorous acid and the pesticide is predominant at neutral pH. The elimination of these pesticides in surface waters was also investigated. A chlorine dose of 2.5 mg L{sup -1} was enough to oxidize chlorpyrifos and diazinon almost completely, with a formation of trihalomethanes below the EU standard for drinking water. However, the removal of chlorfenvinfos was not appreciable. Therefore, chlorination is a feasible option for the removal of organophosphorus pesticides with phosphorothioate group during oxidation and disinfection processes, but not for the elimination of pesticides with phosphate moiety.

  4. Chlorination of organophosphorus pesticides in natural waters

    Acero, Juan L.; Benitez, F. Javier; Real, Francisco J.; Gonzalez, Manuel

    2008-01-01

    Unknown second-order rate constants for the reactions of three organophosphorus pesticides (chlorpyrifos, chlorfenvinfos and diazinon) with chlorine were determined in the present study, and the influence of pH and temperature was established. It was found that an increase in the pH provides a negative effect on the pesticides degradation rates. Apparent second-order rate constants at 20 o C and pH 7 were determined to be 110.9, 0.004 and 191.6 M -1 s -1 for chlorpyrifos, chlorfenvinfos and diazinon, respectively. A higher reactivity of chlorine with the phosphorothioate group (chlorpyrifos and diazinon) than with the phosphate moiety (chlorfenvinfos) could explain these results. Intrinsic rate constant for the elementary reactions of chlorine species with chlorpyrifos and diazinon were also calculated, leading to the conclusion that the reaction between hypochlorous acid and the pesticide is predominant at neutral pH. The elimination of these pesticides in surface waters was also investigated. A chlorine dose of 2.5 mg L -1 was enough to oxidize chlorpyrifos and diazinon almost completely, with a formation of trihalomethanes below the EU standard for drinking water. However, the removal of chlorfenvinfos was not appreciable. Therefore, chlorination is a feasible option for the removal of organophosphorus pesticides with phosphorothioate group during oxidation and disinfection processes, but not for the elimination of pesticides with phosphate moiety

  5. Automatic analyzing device for chlorine ion

    Sugibayashi, Shinji; Morikawa, Yoshitake; Fukase, Kazuo; Kashima, Hiromasa.

    1997-01-01

    The present invention provides a device of automatically analyzing a trance amount of chlorine ions contained in feedwater, condensate and reactor water of a BWR type power plant. Namely, zero-adjustment or span calibration in this device is conducted as follows. (1) A standard chlorine ion liquid is supplied from a tank to a mixer by a constant volume pump, and the liquid is diluted and mixed with purified water to form a standard liquid. (2) The pH of the standard liquid is adjusted by a pH adjuster. (3) The standard liquid is supplied to an electrode cell to conduct zero adjustment or span calibration. Chlorine ions in a specimen are measured by the device of the present invention as follows. (1) The specimen is supplied to a head tank through a line filter. (2) The pH of the specimen is adjusted by a pH adjuster. (3) The specimen is supplied to an electrode cell to electrically measure the concentration of the chlorine ions in the specimen. The device of the present invention can automatically analyze trance amount of chlorine ions at a high accuracy, thereby capable of improving the sensitivity, reducing an operator's burden and radiation exposure. (I.S.)

  6. The study of chlorination of nickel oxide by chlorine and calcium chloride in the presence of active additives

    Ilic, Ilija; Krstev, Boris; Stopic, Srecko; Cerovic, K

    1997-01-01

    Chlorination of nickel oxide by chlorine and calcium chloride in the presence of C, BaS and S were studied, both experimentally and theoretically. Chlorination of nickel oxide by chlorine was carried out in the temperature range 573-873 K and by calcium chloride in the temperature range 1023-1223 K. The results obtained of the chlorination of nickel oxide by chlorine showed that C has the strongest and S the weakest effect on the process. Addition of BaS has a favorable effect on the chlorina...

  7. Solidification of metal chloride waste from pyrochemical process via dechlorination-chlorination reaction system

    Park, H.S.; Cho, I.H.; Lee, K.R.; Choi, J.H.; Eun, H.C.; Kim, I.T.; Park, G.I. [Korea Atomic Energy Research Inst., Deajeon (Korea, Republic of)

    2014-07-01

    The metal chloride wastes generated from the pyro-chemical process to recover uranium and TRUs has been considered as a problematic waste due to the high volatility and low compatibility with conventional silicate glass. Our research group has suggested the dechlorination approach for the solidification of this kind of waste by using a synthetic composite, SAP (SiO{sub 2}-Al{sub 2}O{sub 3}-P{sub 2}O{sub 5}). During the dechlorination, metal elements are chemically interacted with the inorganic composite, SAP, while chlorine is vaporized as gaseous chlorine. Metal elements in the salt were immobilized into phosphate and silicate glass which are uniformly distributed in tens of nm scale. During the dechlorination, gaseous chlorine is captured by Li{sub 2}O-Li{sub 2}O{sub 2} composite that can be converted into metal chloride (LiCl). About 98wt% of oxide composite was converted into LiCl that can be used as an electrolyte in the electrochemical process. The method suggested in this study can provide a chance to minimize the waste volume for the final disposal of salt wastes from a pyro-chemical process. (author)

  8. Ceramic carbon electrode-based anodes for use in the copper-chlorine thermochemical cycle

    Ranganathan, S.; Easton, E.B. [Univ. of Ontario Inst. of Technology, Oshawa, ON (Canada). Faculty of Science

    2009-07-01

    A thermochemical cycle is a process by which water is decomposed into hydrogen and oxygen through a series of chemical reactions. The chemicals that are used in these reactions are regenerated and recycled during the process. Sol-gel chemistry is becoming more common for the synthesis of electrode materials. The sol-gel reaction can be conducted in the presence of a carbon black to form a ceramic carbon electrode (CCE). The resultant CCE structure contains electronically conductive carbon particle pathways that are bound together through the ceramic binder, which can also promote ion transport. The CCE structure also has a high active surface area and is chemically and thermally robust. This paper presented an investigation of CCE materials prepared using 3-aminopropyl trimethoxysilane. Several electrochemical experiments including cyclic voltammetry and electrochemical impedance spectroscopy were performed to characterize their suitability as anode electrode materials for use in the electrochemical step of the copper-chlorine thermochemical cycle. Subsequent experiments included the manipulation of the relative ratio of organosilane carbon precursors to gauge its impact on electrode properties and performance. An overview of the materials characterization and electrochemical measurements were also presented. Specifically, the paper presented the experiment with particular reference to the CCE preparation; electrochemical experiments; thermal analysis; and scanning electron microscopy. Results were also provided. These included TGA analysis; scanning electron microscopy analysis; electrochemical characterization; and anodic polarization. Characterization of these CCE material demonstrated that they had good thermal stability, could be used at high temperatures, and were therefore, very promising anode materials. 15 refs., 7 figs.

  9. Separation of chlorinated diastereomers of decarboxy-betacyanins in myeloperoxidase catalyzed chlorinated Beta vulgaris L. extract.

    Wybraniec, Sławomir; Starzak, Karolina; Szneler, Edward; Pietrzkowski, Zbigniew

    2016-11-15

    A comparative chromatographic evaluation of chlorinated decarboxylated betanins and betanidins generated under activity of hypochlorous acid exerted upon these highly antioxidative potent decarboxylated pigments derived from natural sources was performed by LC-DAD-ESI-MS/MS. Comparison of the chromatographic profiles of the chlorinated pigments revealed two different directions of retention changes in relation to the corresponding substrates. Chlorination of all betacyanins that are decarboxylated at carbon C-17 results in an increase of their retention times. In contrast, all other pigments (the non-decarboxylated betacyanins as well as 2-decarboxy- and 15-decarboxy-derivatives) exhibit lower retention after chlorination. During further chromatographic experiments based upon chemical transformation of the related pigments (decarboxylation and deglucosylation), the compounds' structures were confirmed. The elaborated method for determination of chlorinated pigments enabled analysis of a chlorinated red beet root extract that was submitted to the MPO/H 2 O 2 /Cl - system acting under inflammation-like conditions (pH 5). This indicates a promising possibility for measurement of these chlorinated pigments as indicators of specific inflammatory states wherein betacyanins and decarboxylated betacyanins act as hypochlorite scavengers. Copyright © 2016 Elsevier B.V. All rights reserved.

  10. Effects of aging on chlorinated plasma polymers

    Turri, Rafael Gustavo; Amorim, Milena Kowalczuk Manosso; Hadich, Tayan Vieira; Fernandes, Isabela Cristina; Fernandes, Gabriel Ferreira; Rossi, Diego; Rangel, Elidiane Cipriano; Durrant, Steven Frederick, E-mail: steve@sorocaba.unesp.br [Universidade Estadual Paulista Julio de Mesquita Filho (UNESP), Sorocaba, SP (Brazil). Lab. de Plasmas Tecnologicos

    2017-07-15

    Thin films deposited from propanol-chloroform-argon mixtures by plasma enhanced chemical vapor deposition at different partial pressures of chloroform in the feed, C{sub Cl}, were characterized after two years of aging and their characteristics compared with their as-deposited properties. Film thickness decreased and surface roughness increased with aging. Surface contact angles also increased with aging for the chlorinated films. For the film deposited with 40% chloroform in the feed the contact angle increased about 14°. Transmission infrared and Energy dispersive X-ray spectroscopy revealed that the films gain carbonyl and hydroxyl groups and lose chlorine and hydrogen on aging. Chlorination appears to make the films more durable. Delamination was observed for the unchlorinated films. (author)

  11. Investigation of molybdenum pentachloride interaction with chlorine

    Salyulev, A.B.; Vovkotrub, Eh.G.; Strekalovskij, V.N.

    1993-01-01

    In Raman spectra of molybdenum pentachloride solutions in liquid chlorine lines were recorded in case of 397, 312, 410, 217 and 180 cm - 1 vibrations of ν 1 (A 1 '), ν 2 (A 1 '), ν 5 (E'), ν 6 (E') and ν 8 (E'') monomer (symmetry D 3h ) molecules of MoCl 5 . Interaction of molten molybdenum pentachloride with chlorine at increased (up to 6 MPa) pressures of Cl 2 was studied. In Raman spectra of its vapour distillation in liquid chlorine alongside with MoCl 5 lines appearance of new lines at 363 and 272 cm -1 , similar in their frequency to the ones calculated for the vibrations ν 1 (A 1g ) and ν 2 (E g ) of MoCl 6 molecules (symmetry O h ), was observed

  12. Electrochemical solar energy conversion

    Gerischer, H.

    1991-01-01

    The principles of solar energy conversion in photoelectrochemical cells are briefly reviewed. Cells for the generation of electric power and for energy storage in form of electrochemical energy are described. These systems are compared with solid state photovoltaic devices, and the inherent difficulties for the operation of the electrochemical systems are analyzed. (author). 28 refs, 10 figs

  13. The effects of low level chlorination and chlorine dioxide on biofouling control in a once-through service water system

    Garrett, W.E. Jr.; Laylor, M.M.

    1995-01-01

    Continuous chlorination has been successfully used for the control of Corbicula at a nuclear power plant located on the Chattahoochee River in southeastern Alabama, since 1986. The purpose of this study was to investigate further minimization of chlorine usage and determine if chlorine dioxide is a feasible alternative. Four continuous biocide treatments were evaluated for macro and microfouling control effectiveness, operational feasibility, and environmental acceptability. One semi-continuous chlorination treatment was also evaluated for macrofouling control effectiveness. Higher treatment residuals were possible with chlorine dioxide than with chlorination due to the river discharge limitations. At the levels tested, continuous chlorine dioxide was significantly more effective in providing both macro and microfouling control. Semi-continuous chlorination was just as effective as continuous chlorination for controlling macrofouling. The Corbicula treatment programs that were tested should all provide sufficient control for zebra mussels. Chlorine dioxide was not as cost effective as chlorination for providing macrofouling control. The semi-continuous treatment save 50% on chemical usage and will allow for the simultaneous treatment of two service water systems. Chlorite levels produced during the chlorine dioxide treatments were found to be environmentally acceptable. Levels of trihalomethanes in the chlorinated service water were less than the maximum levels allowed in drinking water

  14. Occupational exposure to chlorinated and petroleum solvents and mycosis fungoides

    Morales-Suárez-Varela, Maria M; Olsen, Jørn; Villeneuve, Sara

    2013-01-01

    To evaluate the potential association between occupational exposure to chlorinated and petroleum solvents and mycosis fungoides (MF).......To evaluate the potential association between occupational exposure to chlorinated and petroleum solvents and mycosis fungoides (MF)....

  15. Blends of caprolactam/caprolactone copolymers and chlorinated polymers

    Alberda van Ekenstein, G.O.R.; Deuring, H.; ten Brinke, G.; Ellis, T.S.

    The phase behaviour of blends of chlorinated polyethylene, polyvinyl chloride (PVC) and chlorinated PVC with random copolymers of caprolactone and caprolactam has been investigated and the results correlated with a binary interaction model. The known miscibility of polycaprolactone in the

  16. Chlorine isotopes potential as geo-chemical tracers

    Shirodkar, P.V.; Pradhan, U.K.; Banerjee, R.

    The potential of chlorine isotopes as tracers of geo-chemical processes of earth and the oceans is highlighted based on systematic studies carried out in understanding the chlorine isotope fractionation mechanism, its constancy in seawater and its...

  17. Electrochemical behaviour of rhenium-graphite electrode

    Varypaev, V.N.; Krasikov, V.L.

    1980-01-01

    Electrochemical behaviour of combination electrode from graphite with electrodeposited thin coating of electrolytic rhenium is studied. Solution of 0.5 m NaCl+0.04 m AlCl 3 served as an electrolite. Polarization galvanostatic curves of hydrogen evolution upon electrodes with conditional rhenium thickness of 3.5 and 0.35 μm, 35 and 3.5 nm are obtained. Possibility of preparation of rhenium-graphite cathode with extremely low rhenium consume, electro-chemical properties of which are simu-lar to purely rhenium cathode is shown. Such electrode is characterized with stable in time low cathode potential of hydrogen evolution in chloride electrolyte and during cathode polarization it is not affected by corrosion

  18. Electrochemical thermodynamic measurement system

    Reynier, Yvan [Meylan, FR; Yazami, Rachid [Los Angeles, CA; Fultz, Brent T [Pasadena, CA

    2009-09-29

    The present invention provides systems and methods for accurately characterizing thermodynamic and materials properties of electrodes and electrochemical energy storage and conversion systems. Systems and methods of the present invention are configured for simultaneously collecting a suite of measurements characterizing a plurality of interconnected electrochemical and thermodynamic parameters relating to the electrode reaction state of advancement, voltage and temperature. Enhanced sensitivity provided by the present methods and systems combined with measurement conditions that reflect thermodynamically stabilized electrode conditions allow very accurate measurement of thermodynamic parameters, including state functions such as the Gibbs free energy, enthalpy and entropy of electrode/electrochemical cell reactions, that enable prediction of important performance attributes of electrode materials and electrochemical systems, such as the energy, power density, current rate and the cycle life of an electrochemical cell.

  19. Chlorin derivatives for potential use in BNCT

    Osterloh, J.; Neumann, M.; Ruf, S.; Gabel, D.

    2000-01-01

    A series of BSH containing alkyl ether homologues of pytropheophorbide a has been prepared. Cellular uptake studies show that is possible to accumulate 2.2 mg of the heptyl ether after 2 h of incubation with a 0.04 mM solution. That means a boron amount of 330 μg per gram cell mass. Cytotoxicity studies allow radiobiological experiments. The patterns of subcellular localisation visualised by fluorescence microscopy and CLSM show that much of the chlorins is located close to the nucleus and in the nucleus membrane. However, no chlorin was found in the nucleus. (author)

  20. Chlorinated tyrosine derivatives in insect cuticle

    Andersen, Svend Olav

    2004-01-01

    A method for quantitative measurement of 3-monochlorotyrosine and 3,5-dichlorotyrosine in insect cuticles is described, and it is used for determination of their distribution in various cuticular regions in nymphs and adults of the desert locust, Schistocerca gregaria. The two chlorinated tyrosine......, not-yet sclerotized cuticle of adult femur and tibia, the amounts increased rapidly during the first 24 h after ecdysis and more slowly during the next two weeks. Control analyses using stable isotope dilution mass spectrometry have confirmed that the chlorinated tyrosines are not artifacts formed...

  1. Determination of carbon chlorine and fluorine in uranium dioxide

    Kijko, N.I.; Timofeev, G.A.

    1983-01-01

    Techniques of chlorine and fluorine determination and simultaneous determination of carbon and chlorine in electrolytic uranium dioxide are described. The method of chlorine and fluorine determination is based on their separation during oxide pyrohydrolysis with subsequent spectrophotometric analysis of condensate. Lower determination limits constitute 1 μg for chlorine, 0.5 μg for fluorine. Relative standard deviation when the content of impurities analyzed is 10 -3 % constitutes 0.05-0.07

  2. Anaerobic electrochemical membrane bioreactor and process for wastewater treatment

    Amy, Gary

    2015-07-09

    An anaerobic electrochemical membrane bioreactor (AnEMBR) can include a vessel into which wastewater can be introduced, an anode electrode in the vessel suitable for supporting electrochemically active microorganisms (EAB, also can be referred to as anode reducing bacteria, exoelectrogens, or electricigens) that oxidize organic compounds in the wastewater, and a cathode membrane electrode in the vessel, which is configured to pass a treated liquid through the membrane while retaining the electrochemically active microorganisms and the hydrogenotrophic methanogens (for example, the key functional microbial communities, including EAB, methanogens and possible synergistic fermenters) in the vessel. The cathode membrane electrode can be suitable for catalyzing the hydrogen evolution reaction to generate hydro en.

  3. 21 CFR 177.2430 - Polyether resins, chlorinated.

    2010-04-01

    ... 21 Food and Drugs 3 2010-04-01 2009-04-01 true Polyether resins, chlorinated. 177.2430 Section 177... Components of Articles Intended for Repeated Use § 177.2430 Polyether resins, chlorinated. Chlorinated polyether resins may be safely used as articles or components of articles intended for repeated use in...

  4. Electrochemical gating in scanning electrochemical microscopy

    Ahonen, P.; Ruiz, V.; Kontturi, K.; Liljeroth, P.; Quinn, B.M.

    2008-01-01

    We demonstrate that scanning electrochemical microscopy (SECM) can be used to determine the conductivity of nanoparticle assemblies as a function of assembly potential. In contrast to conventional electron transport measurements, this method is unique in that electrical connection to the film is not

  5. 21 CFR 177.1610 - Polyethylene, chlorinated.

    2010-04-01

    ... Chlorine in Vinyl Chloride Polymers and Copolymers,” which is incorporated by reference (Copies may be..., Philadelphia, PA 19428-2959, or may be examined at the National Archives and Records Administration (NARA). For... percent in plastic articles prepared from polyvinyl chloride and/or from vinyl chloride copolymers...

  6. 46 CFR 151.50-31 - Chlorine.

    2010-10-01

    ... inside diameter manhole, fitted with a cover located above the maximum liquid level and as close as... accessary equipment shall be of a type suitable for use with chlorine and shall be made of metal, corrosion... shutoff valves and with safety relief valves. All valves shall be bolted to the cover or covers specified...

  7. Thermodynamic consideration on chlorination of uraniferous phosphorite

    Itagaki, Kimio; Tozawa, Kazuteru; Taki, Tomihiro; Hirono, Shuichiro.

    1989-01-01

    The uranium ore of low grade which has apatite as a main mineral, but is different from the phosphorite used as the raw material for phosphoric acid production, exists in large amount in South America and Africa continents, and the importance of its effective utilization as future uranium resources is recognized. The Power Reactor and Nuclear Fuel Development Corp. took up the establishment of the treatment techniques to make this ore into resources as the subject of a project, and proposed the process of volatilizing the uranium in the ore as the chloride and recovering it, and at present, it attempts the experiment on the chlorination treatment. In this paper, the thermodynamic examination on the feasibility of this process, the optimum condition for leaving calcium existing in a large amount in the ore as the phosphate without chlorination and recovering only uranium by chlorination and volatilization, the phase reaction equilibrium chart and the calculation method according to thermodynamics concerning the behavior of chlorination of accompanying elements such as iron, silicon and aluminum and the effect of moisture in the ore are reported. (K.I.)

  8. Nucleic Acids and Enzymes at Electrodes: Electrochemical Nanomedical Biosensors and Biofuel Cell Development

    Ferapontova, Elena

    Starting from the development of the first electrochemical biosensor for glucose, as far as in 1962, the electrochemical biosensor research area underwent a dramatic evolution both in scientific and commercial directions. At present, electrochemical biosensors are widely used in medical practice,...... perspectives of the biosensor research and such biotechnological applications as enzyme electrodes for sustainable energy production (6) will be discussed.......Starting from the development of the first electrochemical biosensor for glucose, as far as in 1962, the electrochemical biosensor research area underwent a dramatic evolution both in scientific and commercial directions. At present, electrochemical biosensors are widely used in medical practice......, by offering extremely sensitive and accurate yet simple, rapid, and inexpensive biosensing platforms (1). In this talk, I will discuss the developed at iNANO reagentless enzymatic biosensors, in which the enzyme is directly electronically coupled to the electrode (1-3), and advanced genosensor platforms...

  9. Electrochemical force microscopy

    Kalinin, Sergei V.; Jesse, Stephen; Collins, Liam F.; Rodriguez, Brian J.

    2017-01-10

    A system and method for electrochemical force microscopy are provided. The system and method are based on a multidimensional detection scheme that is sensitive to forces experienced by a biased electrode in a solution. The multidimensional approach allows separation of fast processes, such as double layer charging, and charge relaxation, and slow processes, such as diffusion and faradaic reactions, as well as capturing the bias dependence of the response. The time-resolved and bias measurements can also allow probing both linear (small bias range) and non-linear (large bias range) electrochemical regimes and potentially the de-convolution of charge dynamics and diffusion processes from steric effects and electrochemical reactivity.

  10. Turbidity and chlorine demand reduction using alum and moringa flocculation before household chlorination in developing countries.

    Preston, Kelsey; Lantagne, Daniele; Kotlarz, Nadine; Jellison, Kristen

    2010-03-01

    Over 1.1 billion people in the world lack access to improved drinking water. Diarrhoeal and other waterborne diseases cause an estimated 1.87 million deaths per year. The Safe Water System (SWS) is a household water treatment intervention that reduces diarrhoeal disease incidence among users in developing countries. Turbid waters pose a particular challenge to implementation of SWS programmes; although research shows that a 3.75 mg l(-1) sodium hypochlorite dose effectively treats turbid waters, users sometimes object to the strong chlorine taste and prefer to drink water that is more aesthetically pleasing. This study investigated the efficacy of two locally available chemical water treatments-alum and Moringa oleifera flocculation-to reduce turbidity and chlorine demand at turbidities of 10, 30, 70, 100 and 300 NTU. Both treatments effectively reduced turbidity (alum flocculation 23.0-91.4%; moringa flocculation 14.2-96.2%). Alum flocculation effectively reduced chlorine demand compared with controls at 30, 70, 100 and 300 NTU (p=0.01-0.06). Moringa flocculation increased chlorine demand to the point where adequate free chlorine residual was not maintained for 24 hours after treatment. Alum pretreatment is recommended in waters>or=30 NTU for optimum water disinfection. Moringa flocculation is not recommended before chlorination.

  11. A study on chlorination of uranium metal using ammonium chloride

    Eun, H.C.; Kim, T.J.; Jang, J.H.; Kim, G.Y.; Lee, S.J.; Hur, J.M.

    2017-01-01

    In this study, the chlorination of uranium metal using ammonium chloride (NH 4 Cl) was conducted to derive an easy and simple uranium chloride production method without impurities. In thermodynamic equilibrium calculations, it was predicted that only uranium chlorides can be produced by the reactions between uranium metal and NH 4 Cl. Experimental conditions for the chlorination of uranium metal were determined using a chlorination test of cerium metal using NH 4 Cl. It was confirmed that UCl 3 and UCl 4 in the form of particles as uranium chlorination products can be obtained from the chlorination method using NH 4 Cl. (author)

  12. Development of a Chlorine Dosing Strategy for Fresh Produce Washing Process to Maintain Microbial Food Safety and Minimize Residual Chlorine.

    Chen, Xi; Hung, Yen-Con

    2018-05-22

    The residual free chlorine level in fresh produce wash solution is closely correlated to the chemical and microbial safety of produce. Excess amount of free chlorine can quickly react with organic matters to form hazardous disinfection by-products (DBPs) above EPA-permitted levels, whereas deficiency of residual chlorine in produce wash solution may result in incompletely removing pathogens on produce. The purpose of this study was to develop a chlorine dosing strategy to optimize the chlorine dosage during produce washing process without impacting the microbial safety of fresh produce. Prediction equations were developed to estimate free chlorine needed to reach targeted residual chlorine at various sanitizer pH and organic loads, and then validated using fresh-cut iceberg lettuce and whole strawberries in an automated produce washer. Validation results showed that equations successfully predicted the initial chlorine concentration needed to achieve residual chlorine at 10, 30, 60, and 90 mg/L for both lettuce and strawberry washing processes, with the root mean squared error at 4.45 mg/L. The Escherichia coli O157:H7 reductions only slightly increased on iceberg lettuce and strawberries with residual chlorine increasing from 10 to 90 mg/L, indicating that lowering residual chlorine to 10 mg/L would not compromise the antimicrobial efficacy of chlorine-based sanitizer. Based on the prediction equations and E. coli O157:H7 reduction results, a chlorine dosing strategy was developed to help the produce industry to maintain microbial inactivation efficacy without adding excess amount of free chlorine. The chlorine dosing strategy can be used for fresh produce washing process to enhance the microbial food safety and minimize the DBPs formation potential. © 2018 Institute of Food Technologists®.

  13. Toxic effects of chlorinated cake flour in rats.

    Cunningham, H M; Lawrence, G A; Tryphonas, L

    1977-05-01

    Four experiments were conducted using weanling Wistar rats to determine whether chlorinated cake flour or its constituents were toxic. Levels of 0.2 and 1.0% chlorine added to unbleached cake flour significantly (p less than 0.01) reduced growth rate by 20.7 and 85.2% and increased liver weight relative to body weight by 16.7 and 25.3%, respectively. Lipids extracted from flour chlorinated at the same levels had similar effects. Rat chow diets containing 0.2 and 0.6% chlorine in the form of chlorinated wheat gluten reduced growth rate and increased liver weight as a percentage of body weight. A rat chow diet containing 0.2% chlorine as chlorinated flour lipids increased absolute liver weight by 40%, kidney by 20%, and heart by 10% compared to pair-fed controls.

  14. Reaction of uranium oxides with chlorine and carbon or carbon monoxide to prepare uranium chlorides

    Haas, P.A.; Lee, D.D.; Mailen, J.C.

    1991-11-01

    The preferred preparation concept of uranium metal for feed to an AVLIS uranium enrichment process requires preparation of uranium tetrachloride (UCI{sub 4}) by reacting uranium oxides (UO{sub 2}/UO{sub 3}) and chlorine (Cl{sub 2}) in a molten chloride salt medium. UO{sub 2} is a very stable metal oxide; thus, the chemical conversion requires both a chlorinating agent and a reducing agent that gives an oxide product which is much more stable than the corresponding chloride. Experimental studies in a quartz reactor of 4-cm ID have demonstrated the practically of some chemical flow sheets. Experimentation has illustrated a sequence of results concerning the chemical flow sheets. Tests with a graphite block at 850{degrees}C demonstrated rapid reactions of Cl{sub 2} and evolution of carbon dioxide (CO{sub 2}) as a product. Use of carbon monoxide (CO) as the reducing agent also gave rapid reactions of Cl{sub 2} and formation of CO{sub 2} at lower temperatures, but the reduction reactions were slower than the chlorinations. Carbon powder in the molten salt melt gave higher rates of reduction and better steady state utilization of Cl{sub 2}. Addition of UO{sub 2} feed while chlorination was in progress greatly improved the operation by avoiding the plugging effects from high UO{sub 2} concentrations and the poor Cl{sub 2} utilizations from low UO{sub 2} concentrations. An UO{sub 3} feed gave undesirable effects while a feed of UO{sub 2}-C spheres was excellent. The UO{sub 2}-C spheres also gave good rates of reaction as a fixed bed without any molten chloride salt. Results with a larger reactor and a bottom condenser for volatilized uranium show collection of condensed uranium chlorides as a loose powder and chlorine utilizations of 95--98% at high feed rates. 14 refs., 7 figs., 14 tabs.

  15. Electrochemical characterisation of CaCl2 deficient LiCl–KCl–CaCl2 eutectic melt and electro-deoxidation of solid UO2

    Sri Maha Vishnu, D.; Sanil, N.; Mohandas, K.S.; Nagarajan, K.

    2016-01-01

    The CaCl 2 deficient ternary eutectic melt LiCl–KCl–CaCl 2 (50.5: 44.2: 5.3 mol %) was electrochemically characterised by cyclic voltammetry and polarization techniques in the context of its probable use as the electrolyte in the electrochemical reduction of solid UO 2 to uranium metal. Tungsten (cathodic polarization) and graphite (anodic polarization) working electrodes were used in these studies carried out in the temperature range 623 K–923 K. The cathodic limit of the melt was observed to be set by the deposition of Ca 2+ ions followed by Li + ions on the tungsten electrode and the anodic limit by oxidation of chloride ions on the graphite electrode (chlorine evolution). The difference between the onset potential of deposition of Ca 2+ and Li + was found to be 0.241 V at a scan rate of 20 mV/s at 623 K and the difference decreased with increase in temperature and vanished at 923 K. Polarization measurements with stainless steel (SS) cathode and graphite anode at 673 K showed the possibility of low–energy reactions occurring on the UO 2 electrode in the melt. UO 2 pellets were cathodically polarized at 3.9 V for 25 h to test the feasibility of electro-reduction to uranium in the melt. The surface of the pellets was found reduced to U metal. - Highlights: • Electrochemically characterized LiCl–KCl–CaCl 2 (50.5: 44.2: 5.3 mol %) melt by CV, LSV and polarization techniques. • Ca 2+ deposits first on tungsten working electrode followed by Li + . Cl − discharges on graphite to liberate chlorine gas. • Surface of UO 2 pellet reduced to U in the melt with low carbon contamination of melt. • Slow reduction of UO 2 due to slow kinetics and low solubility of oxide ions in the low temperature melt.

  16. Fundamentals of electrochemical science

    Oldham, Keith

    1993-01-01

    Key Features* Deals comprehensively with the basic science of electrochemistry* Treats electrochemistry as a discipline in its own right and not as a branch of physical or analytical chemistry* Provides a thorough and quantitative description of electrochemical fundamentals

  17. Electrochemical Analysis of Neurotransmitters

    Bucher, Elizabeth S.; Wightman, R. Mark

    2015-07-01

    Chemical signaling through the release of neurotransmitters into the extracellular space is the primary means of communication between neurons. More than four decades ago, Ralph Adams and his colleagues realized the utility of electrochemical methods for the study of easily oxidizable neurotransmitters, such as dopamine, norepinephrine, and serotonin and their metabolites. Today, electrochemical techniques are frequently coupled to microelectrodes to enable spatially resolved recordings of rapid neurotransmitter dynamics in a variety of biological preparations spanning from single cells to the intact brain of behaving animals. In this review, we provide a basic overview of the principles underlying constant-potential amperometry and fast-scan cyclic voltammetry, the most commonly employed electrochemical techniques, and the general application of these methods to the study of neurotransmission. We thereafter discuss several recent developments in sensor design and experimental methodology that are challenging the current limitations defining the application of electrochemical methods to neurotransmitter measurements.

  18. Organic electrochemical transistors

    Rivnay, Jonathan; Inal, Sahika; Salleo, Alberto; Owens, Ró isí n M.; Berggren, Magnus; Malliaras, George G.

    2018-01-01

    Organic electrochemical transistors (OECTs) make effective use of ion injection from an electrolyte to modulate the bulk conductivity of an organic semiconductor channel. The coupling between ionic and electronic charges within the entire volume

  19. Electrochemical polymer electrolyte membranes

    Fang, Jianhua; Wilkinson, David P

    2015-01-01

    Electrochemical Polymer Electrolyte Membranes covers PEMs from fundamentals to applications, describing their structure, properties, characterization, synthesis, and use in electrochemical energy storage and solar energy conversion technologies. Featuring chapters authored by leading experts from academia and industry, this authoritative text: Discusses cutting-edge methodologies in PEM material selection and fabricationPoints out important challenges in developing PEMs and recommends mitigation strategies to improve PEM performanceAnalyzes the cur

  20. Relation between chlorine with the quality of crude water

    Lim, Fang Yee; Mohd Pauzi Abdullah

    2008-01-01

    Chlorine as disinfection agent in drinking water was used widely since it was successfully been practiced in drinking water in Jersey City, 1908. Mostly, water treatment plants in Malaysia were using chlorine as disinfection agent to kill pathogen and contaminated materials that can be dangerous to consumer. Because of chlorine was a strongly disinfection agent, it also can react with another chemical components such as manganese, hydrogen, sulfides, ammonia and phenol in water. These reactions happen very fast, and chlorine will not react as disinfection agent unless all the organic and inorganic substitution presented in water reacts with chlorine. These reactions between components will increase demand of chlorine in water. The demand of chlorine in water must be filled before the free radical chlorine occurred. These free radical chlorine will decay into hypochlorous acid and hypochlorite ion that so important in disinfection process to kill pathogens and pollutants in water. Most of water treatment plant to maintain free chlorine up to 0.2 mg/ L in distribution system to consumer. These researches involved determination of parameters that can be trusted to react with the chlorine in nine sampling station along Semenyih River and four stations in water treatment plants. These parameters were determined from ammonia, cyanides, sulfides, phenol, phosphorus, nitrite, manganese, iron and sum of organic carbons. Overall, these researches concluded that ammonia and sum of organic carbons were the most compounds that react with the chlorine to produce tryhalometane and chloramines. Besides that, the concentration of cyanides compounds, sulfide, phenol, phosphorus, nitrite, manganese and iron also decrease after the chlorination process. Results can used to evaluate demanding levels of chlorine in Semenyih River. (author)

  1. DFT based study of transition metal nano-clusters for electrochemical NH3 production

    Howalt, Jakob Geelmuyden; Bligaard, Thomas; Rossmeisl, Jan

    2013-01-01

    Theoretical studies of the possibility of producing ammonia electrochemically at ambient temperature and pressure without direct N2 dissociation are presented. Density functional theory calculations were used in combination with the computational standard hydrogen electrode to calculate the free...... for electrochemical ammonia production. The competing hydrogen evolution reaction has also been analyzed for comparison....

  2. Oxidative elimination of cyanotoxins: comparison of ozone, chlorine, chlorine dioxide and permanganate.

    Rodríguez, Eva; Onstad, Gretchen D; Kull, Tomas P J; Metcalf, James S; Acero, Juan L; von Gunten, Urs

    2007-08-01

    As the World Health Organization (WHO) progresses with provisional Drinking Water Guidelines of 1 microg/L for microcystin-LR and a proposed Guideline of 1 microg/L for cylindrospermopsin, efficient treatment strategies are needed to prevent cyanotoxins such as these from reaching consumers. A kinetic database has been compiled for the oxidative treatment of three cyanotoxins: microcystin-LR (MC-LR), cylindrospermopsin (CYN), and anatoxin-a (ANTX) with ozone, chlorine, chlorine dioxide and permanganate. This kinetic database contains rate constants not previously reported and determined in the present work (e.g. for permanganate oxidation of ANTX and chlorine dioxide oxidation of CYN and ANTX), together with previously published rate constants for the remaining oxidation processes. Second-order rate constants measured in pure aqueous solutions of these toxins could be used in a kinetic model to predict the toxin oxidation efficiency of ozone, chlorine, chlorine dioxide and permanganate when applied to natural waters. Oxidants were applied to water from a eutrophic Swiss lake (Lake Greifensee) in static-dose testing and dynamic time-resolved experiments to confirm predictions from the kinetic database, and to investigate the effects of a natural matrix on toxin oxidation and by-product formation. Overall, permanganate can effectively oxidize ANTX and MC-LR, while chlorine will oxidize CYN and MC-LR and ozone is capable of oxidizing all three toxins with the highest rate. The formation of trihalomethanes (THMs) in the treated water may be a restriction to the application of sufficiently high-chlorine doses.

  3. Transformation mechanism of benzophenone-4 in free chlorine promoted chlorination disinfection.

    Xiao, Ming; Wei, Dongbin; Yin, Junxia; Wei, Guohua; Du, Yuguo

    2013-10-15

    The UV-filter BP-4 (2-hydroxy-4-methoxybenzophenone-5-sulfonic acid) has been frequently observed in the environment, showing high potentials to invade drinking water, swimming water, or wastewater reclamation treatment systems. With the help of high performance liquid chromatography-high resolution mass spectrometry and nuclear magnetic resonance spectroscopy, 10 new products from free chlorine-promoted BP-4 disinfection have been disclosed and their possible transformation routes have been investigated. The first route is chlorine substitution of BP-4 and its transformation products, forming mono-, di-, and tri-chlorinated BP-4 analogs. The second is Baeyer-Villiger-Type oxidation, converting diphenyl ketone to phenyl ester derivatives. The third is ester hydrolysis, generating corresponding phenolic and benzoic products. The fourth is decarboxylation, replacing the carboxyl group by chloride in the benzoic-type intermediate. The fifth is desulfonation, degrading the sulfonic group through an alternative chlorine substitution on the benzene ring. Orthogonal experiments have been established to investigate the species transformed from BP-4 at different pH values and free available chlorine (FAC) dosages. The reaction pathways are strongly dependent on pH conditions, while an excessive amount of FAC eliminates BP-4 to the smaller molecules. The initial transformation of BP-4 in chlorination system follows pseudo-first-order kinetics, and its half-lives ranged from 7.48 s to 1.26 × 10(2) s. More importantly, we have observed that the FAC-treated BP-4 aqueous solution might increase the genotoxic potentials due to the generation of chlorinated disinfection by-products. Copyright © 2013 Elsevier Ltd. All rights reserved.

  4. Antiradiation effectiveness of the chlorine C

    Bubnova, O.M.; Grechka, I.I.; Znamensky, V.V.

    1996-01-01

    At present ever more attention of the experimenters in the field of search of high-effective antiray means - is directed to development of preparations from bio-active substances of a natural origin. In this connection all greater interest is caused by researches of antiray activity of these compounds, distinguished, as a rule, from known preparations of synthetic manufacture of low toxicity, absence of expressed collateral effects and possibility of course application. It has biological (antiray) activity in dozes 5-10 mg/kg and chlorine C which is derivative of chlorophil A. At present it passes tests in oncology. Porphyrines (synthetic and natural) are recently subjected to wide study as potential medicinal means, due to their ability to be accumulated in bodies of the reticulo-endothelial system and proliferous tissues, as well as their physical-chemical characteristics (fluorescence, photosensitizing action, colouring). All this testifies for the benefit of perspective use of porphyrin for treatment and diagnostics of tumors. According to the above described properties of porphyrines there is that fact, that for some of them radioprotective properties are revealed during the injections as well as before and after radiation treatment. The above said has formed the basis for study of antiray properties of the chlorine C during the experiments on small-sized laboratory animals. Antiradiation effectivity of chlorine C was studied on the mice (CBA x C57 B1) F1. Chlorine C was applied in a wide range of dozes with its' use in 3 variants: before radiation treatment, after radiation treatment, combined (before and after radiation treatment). Radioprotective activity of chlorine C reduces at an increase of a time of the injection before radiation treatment and at other ways of injection (intramuscularly, subcutaneously, per os). Studies of medical activity of chlorine C in experiments on mice have shown, that the compound does not possess medical activity. The death of

  5. As(III) oxidation by active chlorine and subsequent removal of As(V) by Al13 polymer coagulation using a novel dual function reagent.

    Hu, Chengzhi; Liu, Huijuan; Chen, Guixia; Jefferson, William A; Qu, Jiuhui

    2012-06-19

    An electrochemically prepared water treatment reagent containing a high concentration of Al(13) polymer and active chlorine (PACC) showed promising potential for the removal of As(III) due to the combined function of oxidation and coagulation. The results indicated that PACC was effective for As(III) removal through oxidation by the active chlorine and subsequent removal of As(V) by coagulation with the Al(13) polymer. The As(III) was oxidized to As(V) by active chlorine in PACC, with a stoichiometric rate of 0.99 mg Cl(2)/mg As(III). The Al(13) polymer was the most active Al species responsible for As(V) removal in PACC. To meet As drinking water standards the stoichiometric weight ratio of Cl(2)/Al within PACC was 0.09 for the treatment of As(III). Considering the process of As(III) oxidation and As(V) coagulation together, the optimal pH conditions for the removal of As by PACC was within the neutral range, which facilitated the reaction of As(III) with active chlorine and favored the formation of Al hydroxide flocs. The presence of humic acid reduced the As(III) removal efficiency of PACC due to its negative influence on subsequent As(V) coagulation, and disinfection byproduct yields were very low in the presence of insufficient or stoichiometric active chlorine.

  6. Dispersion of chlorine at seven southern California coastal generating stations

    Grove, R.S.

    1983-01-01

    The objectives of this study were to (1) determine chlorine concentrations and exposure time gradients of chlorine through seven coastal generating stations and (2) assess the dispersion characteristics of chlorine in the receiving waters. Remarkable variability in chlorine injection concentrations, condenser outlet concentrations, outfall concentrations, and dissipation rates between generating stations and, to a lesser extent, between surveys at the same generating station was found in this chlorine monitoring study. Other than quite consistent low injection and correspondingly low outfall concentrations at San Onofre (a generating station that had one of the more rigorous chlorine control and minimization programs in effect at the time), no recognizable patterns of chlorination could be discerned in the data. Over half of the outfall chlorine surveys had chlorine concentrations below 0.08 mg/L, which is the accepted level of detection for the titrator being used in the surveys. The post-outfall dilution calculations further showed that the chlorine that does enter the receiving water is initially diluted with entrained ambient water at a ratio of 5.2:19.0

  7. Spectrographic determination of chlorine and fluorine

    Contamin, G.

    1965-04-01

    Experimental conditions have been investigated in order to obtain the highest sensitivity in spectrographic determination of chlorine and fluorine using the Fassel method of excitation in an inert atmosphere. The influence of the nature of the atmosphere, of the discharge conditions and of the matrix material has been investigated. The following results have been established: 1. chlorine determination is definitely possible: a working curve has been drawn between 10 μg and 100 μg, the detection limit being around 5 μg; 2. fluorine determination is not satisfactory: the detection limit is still of the order of 80 μg. The best operating conditions have been defined for both elements. (author) [fr

  8. Chlorine-36 dating of continental evaporites

    Huang Qi

    1990-01-01

    Teh chloring-36 production, principle and experimental method of 36 Cl dating are briefly described. The ages calculated from the 36 Cl/Cl ratios are generally concordant with those obtained by using 14 C, 230 Th and magnetostratigraphic techniques. It confirms the constancy of the chlorine input ratio over the last million years and implys that 36 Cl can provide accurate dates on continental saline sediments

  9. Microbial transformation of chlorinated aromatics in sediments

    Beurskens, J.E.M.

    1995-01-01

    Numerous contaminants like heavy metals, polycyclic aromatic hydrocarbons (PAHs), chlorinated benzenes (CBs), polychlorinated biphenyls (PCBs), polychlorinated dibenzo- p -dioxins (PCDDs) and polychlorinated furans (PCDFs) are detected in the major rivers in the Netherlands. These contaminants have relatively low aqueous solubilities and bind substantially to the suspended solids in river water. Due to decreasing stream velocities in the downstream stretches of a...

  10. Thermal diffusion of chlorine in uranium dioxide

    Pipon, Y.; Toulhoat, N.; Moncoffre, N.; Jaffrezic, H.; Gavarini, S.; Martin, P.; Raimbault, L.; Scheidegger, A.M.

    2006-01-01

    In a nuclear reactor, isotopes such as 35 Cl present as impurities in the nuclear fuel are activated by thermal neutron capture. During interim storage or geological disposal of nuclear fuel, the activation products such as 36 Cl may be released from the fuel to the geo/biosphere and contribute to the ''instant release fraction'' as they are likely to migrate in defects and grain boundaries. In order to differentiate diffusion mechanisms due to ''athermal'' processes during irradiation from thermally activated diffusion, both irradiation and thermal effects must be assessed. This work concerns the measurement of the thermal diffusion coefficient of chlorine in UO 2 . 37 Cl was implanted at a 10 13 at/cm 2 fluence in depleted UO 2 samples which were then annealed in the 900-1200 C temperature range and finally analyzed by secondary ion mass spectrometry (SIMS) to obtain 37 Cl depth profiles. The migration process appears to be rather complex, involving mechanisms such as atomic, grain boundary, directed diffusion along preferential patterns as well as trapping into sinks before successive effusion. However, using a diffusion model based on general equation of transport, apparent diffusion coefficients could be calculated for 1000 and 1100 C and a mean activation energy of 4.3 eV is proposed. This value is one of the lowest values compared to those found in literature for other radionuclides pointing out a great ability of chlorine to migrate in UO 2 at relatively low temperatures. In order to unequivocally determine the diffusion behaviour of both implanted and pristine chlorine before and after thermal annealing, the structural environment of chlorine in UO 2 was examined using micro X-ray fluorescence (micro-XRF) and micro X-ray absorption spectroscopy (micro-XAS). (orig.)

  11. Accumulation of chlorinated benzenes in earthworms

    Beyer, W.N.

    1996-01-01

    Chlorinated benzenes are widespread in the environment. Hexachlorobenzene, pentachlorobenzene and all isomers of dichlorobenzenes, trichlorobenzenes, and tetrachlorobenzenes, have been detected in fish, water, and sediments from the Great Lakes. This paper describes a long-term (26 week) experiment relating the concentrations of chlorinated benzenes in earthworms to 1) the length of exposure, and it describes three 8-week experiments relating concentrations of chlorinated benzenes in earthworms to 2) their concentration in soil 3) the soil organic matter content and, 4) the degree of chlorination. In the 26-week experiment, the concentration of 1,2,4 - trichlorobenzene in earthworms fluctuated only slightly about a mean of 0.63 ppm (Fig. 1). Although a statistically significant decrease can be demonstrated over the test (Pearson correlation coefficient, r = -0.62 p earthworms showed a cyclical trend that coincided with replacement of the media, and a slight but statistically significant tendency to increase from about 2 to 3 ppm over the 26 weeks (r = 0.55, p earthworms increased as the concentrations in the soil increased (Fig. 2), but leveled off at the highest soil concentrations. The most surprising result of this study was the relatively low concentrations in earthworms compared to those in soils. The average concentration of each of the six isomers of trichlorobenzene and tetrachlorobenzene in earthworms was only about 1 ppm (Table 2); the isomeric structure did not affect accumulation. The concentration of organic matter in soil had a prominent effect on hexachlorobenzene concentrations in earthworms (Fig. 3). Hexachlorobenzene concentrations decreased steadily from 9.3 ppm in earthworms kept in soil without any peat moss added to about 1 ppm in soil containing 16 or 32% organic matter.

  12. Chlorination and Carbochlorination of Cerium Oxide

    Esquivel, Marcelo; Bohe, Ana; Pasquevich, Daniel

    2000-01-01

    The chlorination and carbochlorination of cerium oxide were studied by thermogravimetry under controlled atmosphere (TG) in the 700 0 C 950 0 C temperature range.Both reactants and products were analyzed by X-ray diffraction (RX), scanning electronic microscopy (SEM) and energy dispersive spectroscopy (EDS). Thermodynamic calculations were performed by computer assisted software.The chlorination starts at a temperature close to 800 0 C.This reaction involves the simultaneous formation and evaporation of CeCl3.Both processes control the reaction rate and their kinetic may not be easily separated.The apparent chlorination activation energy in the 850 0 C-950 0 C temperature range is 172 to 5 kJ/ mole.Carbon transforms the CeO2-Cl2 into a more reactive system: CeO2-C-Cl2, where the effects of the carbon content, total flow rate and temperature were analyzed.The carbochlorination starting temperature is 700 0 C.This reaction is completed in one step controlled by mass transfer with an apparent activation energy of 56 to 5 kJ/mole in the 850 0 C-950 0 C temperature range

  13. Radiolytic degradation of chlorinated hydrocarbons in water

    Wu, Xing-Zheng; Yamamoto, Takeshi [Fukui Univ., Faculty of Engineering, Dept. of Materials Science and Engineering, Fukui (Japan); Hatashita, Masanori [The Wakasa Wan Energy Research Center, Research Dept., Tsuruga, Fukui (Japan)

    2002-11-01

    Radiolytic degradation of chlorinated hydrocarbons (chloroform, trichloroethylene, and tetrachloroethylene) in water was carried out. Water solutions of the chlorinated hydrocarbons with different concentrations were irradiated with {gamma} rays. Concentrations of methane, ethane, CO, CO{sub 2}, H{sub 2}, and O{sub 2} after the irradiation were determined by gas chromatography. Concentration of chloride ion in the irradiated sample was determined by ion chromatography. Experimental results show that radiolytic degradation of the chlorinated hydrocarbon increased with the radiation dose. Methane, ethane, CO{sub 2}, H{sub 2}, and Cl{sup -} concentrations increased with the radiation dose and the sample concentration. On the other hand, O{sub 2} concentration decreased with the radiation dose and the sample concentration. When sample concentration was high, dissolved oxygen might be not enough for converting most of the C atoms in the sample into CO{sub 2}. This resulted in a low decomposition ratio. Addition of H{sub 2}O{sub 2} as an oxygen resource could increase the decomposition ratio greatly. Furthermore, gas chromatography-mass spectroscopy was applied to identify some intermediates of the radiolytic dehalogenation. Radiolytic degradation mechanisms are also discussed. (author)

  14. Radioimmunoassay for chlorinated dibenzo-p-dioxins

    Albro, P.W.; Chae, K.; Luster, M.I.; Mckinney, J.D.

    1980-01-01

    The invention provides a double-antibody radioimmunoassay method for the determination of chlorinated dibenzo-p-dioxins, particularly, 2,3,7,8-tetrachlorodibenzo-p-dioxin, in environmental samples including animal tissues such as monkey liver and adipose tissues. The limit of detection is approximately 25 picograms for 2,3,7,8-tetrachlorodibenzo-pdioxin. Assuming an appropriate cleanup procedure is used, chlorinated dibenzofurans are the only likely interferences, and these can be distinguished through the use of two antisers of different dibenzo-furan/dibenzodioxin selectivities. The invention includes the preparation of a reproducible antigen, an appropriate radiolabeled hapten, and effective sample extracts. A feature of the assay method is the use of a nonionic detergent (e.g., ''cutscum'' or ''triton x-305'') to solubilize the extremely hydrophobic dibenzo-p-dioxins in a manner permitting their binding by antibodies. The immunoassay is applicable to screening samples in order to minimize the demand for mass spectrometric screening, and to routine monitoring for exposure to known chlorinated dibenzo-p-dioxins in potentially contaminated environments

  15. Materials for electrochemical capacitors

    Simon, Patrice; Gogotsi, Yury

    2008-11-01

    Electrochemical capacitors, also called supercapacitors, store energy using either ion adsorption (electrochemical double layer capacitors) or fast surface redox reactions (pseudo-capacitors). They can complement or replace batteries in electrical energy storage and harvesting applications, when high power delivery or uptake is needed. A notable improvement in performance has been achieved through recent advances in understanding charge storage mechanisms and the development of advanced nanostructured materials. The discovery that ion desolvation occurs in pores smaller than the solvated ions has led to higher capacitance for electrochemical double layer capacitors using carbon electrodes with subnanometre pores, and opened the door to designing high-energy density devices using a variety of electrolytes. Combination of pseudo-capacitive nanomaterials, including oxides, nitrides and polymers, with the latest generation of nanostructured lithium electrodes has brought the energy density of electrochemical capacitors closer to that of batteries. The use of carbon nanotubes has further advanced micro-electrochemical capacitors, enabling flexible and adaptable devices to be made. Mathematical modelling and simulation will be the key to success in designing tomorrow's high-energy and high-power devices.

  16. Electrochemical reduction of NOx

    Traulsen, Marie Lund

    NO and NO2 (collectively referred to as NOx) are air pollutants, and the largest single contributor to NOx pollution is automotive exhaust. This study investigates electrochemical deNOx, a technology which aims to remove NOx from automotive diesel exhaust by electrochemical reduction of NOx to N2...... and O2. The focus in this study is on improving the activity and selectivity of solid oxide electrodes for electrochemical deNOx by addition of NOx storage compounds to the electrodes. Two different composite electrodes, La0.85Sr0.15MnO3-δ-Ce0.9Gd0.1O1.95 (LSM15-CGO10) and La0.85Sr0.15FeO3-δ-Ce0.9Gd0.1O......1.95 (LSF15-CGO10), have been investigated in combination with three different NOx storage compounds: BaO, K2O and MnOx. The main focus in the investigation has been on conversion measurements and electrochemical characterization, the latter by means of electrochemical impedance spectroscopy...

  17. Identification of intermediates leading to chloroform and C-4 diacids in the chlorination of humic acid

    Sinninghe Damsté, J.S.; Leer, E.W.B. de; Erkelens, Corrie; Galan, L.

    1985-01-01

    The chlorination of terrestrial humic acid was studied at pH 7. 2 with varying chlorine to carbon ratios. The principal products are chloroform, di- and trichloroacetic acid, and chlorinated C-4 diacids. At a high chlorine dose many new chlorination products were detected, among them

  18. Electrochemical measurements in PWR steam generators to follow crevice chemistry

    Feron, D.

    1991-01-01

    In PWR steam generator crevices, the evolution of chemistry is important for the understanding of corrosion phenomena. Electrochemical measurements have been performed in high temperature simulated crevice environments in order to follow hideout processes and remedial actions (on-line addition of boric acid). Reported tests have been conducted with model boilers of AJAX facilities. Eccentric and concentric tube support plate crevices have been instrumented with platinum electrodes. Electrochemical measurements have been collected when model boiler was under nominal conditions (primary temperature: 335 deg C, secondary temperature: 280 deg C). They include Electrochemical Impedance Spectroscopy (EIS) and potential measurements: with EIS, sodium and boric acid hideouts have been detected and followed. Potential measurements have been performed in an attempt to measure crevice PH evolution

  19. Features of copper etching in chlorine-argon plasma

    Efremov, A.M.; Svettsov, V.I.

    1995-01-01

    Chlorine mixtures with inert gases including argon exhibit promise as plasma feed gases for etching metals and semiconductors in the microelectronics industry. It was shown that even strong dilution of reactive gas with an inert gas (up to 80-90% of the latter) has virtually no effect in decreasing the rate of plasma etching of materials such as silicon and gallium arsenide, compared to etching in pure chlorine. The principal reactive species responsible for etching these substrates are chlorine atoms therefore, a possible explanation of the effect is an increase in the rate of bulk generation of chlorine atoms in the presence of argon. In this work the authors studied the influence of argon on the rate of copper etching in chlorine, because copper, unlike the above substrates, reacts effectively not only with the atoms but with the ground-state molecules of chlorine

  20. Kinetic modelling of chlorination of nitrided ilmenite using MATLAB

    Ramakrishnan, Sivakumar, E-mail: srsivakumar@usm.my; Kwok, Teong Chen, E-mail: ctck@live.com; Hamid, Sheikh Abdul Rezan Sheikh Abdul, E-mail: rezanshk@gmail.com [School of Materials and Mineral Resources Engineering, Universiti Sains Malaysia, 14300, Nibong Tebal, Penang (Malaysia)

    2016-07-19

    In the present study, chlorination of nitride ilmenite using 2{sup k} factorial design was investigated. The reduction experiments were carried out in a temperature range of 400°C to 500°C, chlorination duration from 1 hour to 3 hours and using different type of carbon reactant. Phases of raw materials and reduced samples were analyzed by X-ray diffraction (XRD). Ilmenite was reduced to TiO{sub x}C{sub y}N{sub z} through carbothermal and nitridation for further chlorination into titanium tetrachloride. The Design of Experiment analysis suggested that the types of carbon reactant contribute most influence to the extent of chlorination of nitride ilmenite. The extent of chlorination was highest at 500°C with 3 hours chlorination time and carbon nanotube as carbon reactant.

  1. Quantifying Chemical and Electrochemical Reactions in Liquids by in situ Electron Microscopy

    Canepa, Silvia

    and developing a robust imaging analysis method for quantitatively understand chemical and electrochemical process during in situ liquid electron microscopy. By using two custom-made liquid cells (an electrochemical scanning electron microscopy (EC-SEM) platform and Liquid Flow S/TEM holder) beam...... of electrochemical deposition of copper (Cu) by electrochemical liquid scanning electron microscopy (EC-SEM) was done in order to direct observe the formation of dendritic structures. Finally the shape evolution from solid to hollow structures through galvanic replacement reactions were observed for different silver...

  2. Regiospecific synthesis of polychlorinated dibenzofurans with chlorine-37 excess

    Yoonseok Chang; Deinzer, M.L.; Oregon State Univ., Corvallis, OR

    1991-01-01

    The synthesis of regiospecifically chlorine-37 labeled di-and trichlorodibenzofurans is described. The strategy for introducing a chlorine-37 label regiospecifically has been to reduce the nitro derivative to the corresponding amine. The amine is converted to the diazonium salt with t-butyl nitrite, and this product is converted to the final product via the Sandmeyer reaction with chlorine-37 labeled cuprous chloride. (author)

  3. The removal of phenols from oily wastewater by chlorine dioxide

    Hsu, Chung-Jung

    1988-01-01

    Treatability studies were performed on oily wastewaters produced by petroleum and canning industries. Chlorine dioxide was used for the removal of phenolic compounds from these oily wastewaters. Most of phenolic compounds can be destroyed by chlorine dioxide within 15 minutes if CI02-to-phenol ratios of higher than 5.0 are provided. Factors such as pH, temperature, and COD have little effect on phenol removal. The effectiveness of chlorine dioxide treatment depends critic...

  4. Chlorine gas processing of oxide nuclear fuel particles containing thorium

    Knotik, K.; Bildstein, H.; Falta, G.; Wagner, H.

    Experimental studies on the chloride extraction and separation of U and Th from coated Th--U oxide particles are reported. After a description of the chlorination equipment and the experimental procedures, the results are discussed. The yield of U is determined as a function of the reaction temperature. The results of a thermogravimetric analysis of the chlorination of uranium carbide and thorium carbides are reported and used to establish the reaction mechanism for the chlorination

  5. Electrochemical energy storage

    Tarascon, Jean-Marie

    2015-01-01

    The electrochemical storage of energy has become essential in assisting the development of electrical transport and use of renewable energies. French researchers have played a key role in this domain but Asia is currently the market leader. Not wanting to see history repeat itself, France created the research network on electrochemical energy storage (RS2E) in 2011. This book discusses the launch of RS2E, its stakeholders, objectives, and integrated structure that assures a continuum between basic research, technological research and industries. Here, the authors will cover the technological

  6. A new kind of Molotov? Gasoline-pool chlorinator mixtures.

    Hutches, Katherine; Lord, James

    2012-07-01

    This paper investigates the reaction between pool chlorinators and gasoline. In particular, the propensity for self-ignition and the resulting chemical products were studied. An organic pool chlorinator was combined with gasoline in varying proportions in an attempt to form a hypergolic mixture. None of the combinations resulted in self-ignition, but larger quantities of chlorinator produced vigorous light-colored smoke and a solid mass containing isocyanuric acid and copper chloride. Additionally, the chlorinating abilities of different commercially available pool chlorinators were explored. When Ca(ClO)(2) and sodium dichloro-s-triazinetrione-based chlorinators were used, the presence of gasoline was still visible after 10 days, despite limited chlorination. The trichloro-s-triazinetrione-based chlorinator, however, caused efficient chlorination of the C(2)- and C(3)-alkylbenzenes, making gasoline no longer identifiable. 2012 American Academy of Forensic Sciences. Published 2012. This article is a U.S. Government work and is in the public domain in the U.S.A.

  7. Inactivation of viruses in municipal effluent by chlorine.

    Hajenian, H. G.; Butler, M.

    1980-01-01

    The influence of pH and temperature on the efficiency of chlorine inactivation of two unrelated picornaviruses in a typical urban wastewater effluent was examined. Temperature, unlike pH, had relatively little effect on the rate of inactivation. The pH effect was complex and the two viruses differed. The f2 coliphage was more sensitive to chlorine at low pH, but at all values there was a threshold above which additional chlorine resulted in very rapid inactivation. The amount of chlorine requ...

  8. Characterization of a stirred tank electrochemical cell for water disinfection processes

    Polcaro, A.M.; Vacca, A.; Mascia, M.; Palmas, S.; Pompei, R.; Laconi, S.

    2007-01-01

    Laboratory experiments were performed to characterize the behaviour of an electrochemical cell equipped with boron-doped diamond anodes and to verify its effectiveness in water disinfection. The hydrodynamic regime was determined when the cell worked either in batch or in continuous mode. Galvanostatic electrolyses of aqueous 1 mM Na 2 SO 4 solutions were performed to investigate on the oxidant production in different experimental conditions. The same solutions contaminated by E. coli, enterococci and coliforms were used as test media to verify the effectiveness of the system in the disinfection process. Experimental results indicated that the major inactivation mechanism of bacteria in the electrochemical cell is a disinfection by electrochemically generated oxidants, however a cooperative effect of superficial reaction has to be taken into account. The great capability of BDD anode to produce reactive oxygen species (ROS) and other oxidizing species during the electrolysis allows to establish a chlorine-free disinfection process

  9. Evidence for Perchlorates and the Origin of Chlorinated Hydrocarbons Detected by SAM at the Rocknest Aeolian Deposit in Gale Crater

    Glavin, Daniel P.; Freissinet, Caroline; Miller, Kristen E.; Eigenbrode, Jennifer L.; Brunner, Anna E.; Buch, Arnaud; Sutter, Brad; Archer, P. Douglas, Jr.; Atreya, Sushil K.; Brinckerhoff, William B.; hide

    2013-01-01

    A single scoop of the Rocknest aeolian deposit was sieved (less than 150 micrometers), and four separate sample portions, each with a mass of approximately 50 mg, were delivered to individual cups inside the Sample Analysis at Mars (SAM) instrument by the Mars Science Laboratory rover's sample acquisition system. The samples were analyzed separately by the SAM pyrolysis evolved gas and gas chromatograph mass spectrometer analysis modes. Several chlorinated hydrocarbons including chloromethane, dichloromethane, trichloromethane, a chloromethylpropene, and chlorobenzene were identified by SAM above background levels with abundances of approximately 0.01 to 2.3 nmol. The evolution of the chloromethanes observed during pyrolysis is coincident with the increase in O2 released from the Rocknest sample and the decomposition of a product of N-methyl-N-(tert-butyldimethylsilyl)-trifluoroacetamide (MTBSTFA), a chemical whose vapors were released from a derivatization cup inside SAM. The best candidate for the oxychlorine compounds in Rocknest is a hydrated calcium perchlorate (Ca(ClO4)2·nH2O), based on the temperature release of O2 that correlates with the release of the chlorinated hydrocarbons measured by SAM, although other chlorine-bearing phases are being considered. Laboratory analog experiments suggest that the reaction of Martian chlorine from perchlorate decomposition with terrestrial organic carbon from MTBSTFA during pyrolysis can explain the presence of three chloromethanes and a chloromethylpropene detected by SAM. Chlorobenzene may be attributed to reactions of Martian chlorine released during pyrolysis with terrestrial benzene or toluene derived from 2,6-diphenylphenylene oxide (Tenax) on the SAM hydrocarbon trap. At this time we do not have definitive evidence to support a nonterrestrial carbon source for these chlorinated hydrocarbons, nor do we exclude the possibility that future SAM analyses will reveal the presence of organic compounds native to the

  10. DBP formation from degradation of DEET and ibuprofen by UV/chlorine process and subsequent post-chlorination.

    Aghdam, Ehsan; Xiang, Yingying; Sun, Jianliang; Shang, Chii; Yang, Xin; Fang, Jingyun

    2017-08-01

    The formation of disinfection by-products (DBPs) from the degradation of N,N-diethyl-3-methyl benzoyl amide (DEET) and ibuprofen (IBP) by the ultraviolet irradiation (UV)/chlorine process and subsequent post-chlorination was investigated and compared with the UV/H 2 O 2 process. The pseudo first-order rate constants of the degradation of DEET and IBP by the UV/chlorine process were 2 and 3.1 times higher than those by the UV/H 2 O 2 process, respectively, under the tested conditions. This was due to the significant contributions of both reactive chlorine species (RCS) and hydroxyl radicals (HO) in the UV/chlorine process. Trichloromethane, 1,1,1-trichloro-2-propanone and dichloroacetic acid were the major known DBPs formed after 90% of both DEET and IBP that were degraded by the UV/chlorine process. Their yields increased by over 50% after subsequent 1-day post-chlorination. The detected DBPs after the degradation of DEET and IBP comprised 13.5% and 19.8% of total organic chlorine (TOCl), respectively, and the proportions increased to 19.8% and 33.9% after subsequent chlorination, respectively. In comparison to the UV/H 2 O 2 process accompanied with post-chlorination, the formation of DBPs and TOCl in the UV/chlorine process together with post-chlorination was 5%-63% higher, likely due to the generation of more DBP precursors from the attack of RCS, in addition to HO. Copyright © 2017. Published by Elsevier B.V.

  11. Pulse radiolysis investigations on the oxidation of bilirubin by chlorinated peroxyl radicals (Preprint No. RC.18)

    Mohan, Hari; Gopinathan, C.

    1989-01-01

    Chlorinated peroxyl radicals were observed to oxidize bilirubin. The rate constants, estimated from the formation kinetics of bilirubin cation, were observed to decrease with decrease in the chlorine substitution of various chlorinated peroxyl radicals. (author)

  12. Reductive cleavage of chlorine from 6-chloronicotinic acid on mercury electrodes

    Ruiz Montoya, M.; Pintado, S.; Rodriguez Mellado, J.M.

    2011-01-01

    Highlights: → Dissociation constants (as pK) of 6 chloronicotinic acid (6CNA) obtained by UV-vis spectroscopy: -0.80 ± 0.05 (-COOH group) and 3.2 ± 0.1 (pyridinic nitrogen). → Electrolysis of 6CNA evidenced the reductive cleavage of chlorine from the molecule. → Kinetic parameters (Tafel slopes and reaction orders) determined at the foot of the waves. → Reduction pathways have been proposed. - Abstract: This paper presents polarographic (direct current, dc, and differential pulse, DP) and voltammetric (linear-sweep cyclic voltammetry) studies on the electroreduction of 6-chloronicotinic acid (6CNA) on mercury electrodes. In order to obtain the dissociation constants of 6CNA, UV-vis spectra were recorded as a function of pH. pK values of -0.80 ± 0.05 (-COOH group) and 3.2 ± 0.1 (pyridinic nitrogen) were obtained. The electrochemical studies were performed in the acidity range 6 M H 2 SO 4 to pH 8. Above the last pH value no signals were obtained. Electrolysis made at potentials corresponding to the limiting current of the first wave indicates that there is a reductive cleavage of chlorine from the molecule. This was confirmed by dc and DP polarografic results and also by voltammetric results. Kinetic parameters such as Tafel slopes and electrochemical reaction orders have been determined at potentials corresponding to the foot of the waves. From these results, together with those obtained by cyclic voltammetry, a reaction pathway is proposed, in which the rate-determining step of the process is the release of a chloride ion from the radical formed after the uptake of a H + ion and an electron.

  13. Reductive cleavage of chlorine from 6-chloronicotinic acid on mercury electrodes

    Ruiz Montoya, M., E-mail: mmontoya@uhu.e [Departamento de Ingenieria Quimica, Quimica Fisica y Quimica Organica, Universidad de Huelva, Campus El Carmen, Facultad de Ciencias Experimentales, E-21071 Huelva (Spain); Pintado, S., E-mail: q02pibes@uco.e [Departamento de Quimica Fisica y Termodinamica Aplicada, Universidad de Cordoba, Campus Universitario de Rabanales, edificio ' Marie Curie' ., E-14014 Cordoba (Spain); Rodriguez Mellado, J.M., E-mail: jmrodriguez@uco.e [Departamento de Quimica Fisica y Termodinamica Aplicada, Universidad de Cordoba, Campus Universitario de Rabanales, edificio ' Marie Curie' ., E-14014 Cordoba (Spain)

    2011-04-30

    Highlights: Dissociation constants (as pK) of 6 chloronicotinic acid (6CNA) obtained by UV-vis spectroscopy: -0.80 {+-} 0.05 (-COOH group) and 3.2 {+-} 0.1 (pyridinic nitrogen). Electrolysis of 6CNA evidenced the reductive cleavage of chlorine from the molecule. Kinetic parameters (Tafel slopes and reaction orders) determined at the foot of the waves. Reduction pathways have been proposed. - Abstract: This paper presents polarographic (direct current, dc, and differential pulse, DP) and voltammetric (linear-sweep cyclic voltammetry) studies on the electroreduction of 6-chloronicotinic acid (6CNA) on mercury electrodes. In order to obtain the dissociation constants of 6CNA, UV-vis spectra were recorded as a function of pH. pK values of -0.80 {+-} 0.05 (-COOH group) and 3.2 {+-} 0.1 (pyridinic nitrogen) were obtained. The electrochemical studies were performed in the acidity range 6 M H{sub 2}SO{sub 4} to pH 8. Above the last pH value no signals were obtained. Electrolysis made at potentials corresponding to the limiting current of the first wave indicates that there is a reductive cleavage of chlorine from the molecule. This was confirmed by dc and DP polarografic results and also by voltammetric results. Kinetic parameters such as Tafel slopes and electrochemical reaction orders have been determined at potentials corresponding to the foot of the waves. From these results, together with those obtained by cyclic voltammetry, a reaction pathway is proposed, in which the rate-determining step of the process is the release of a chloride ion from the radical formed after the uptake of a H{sup +} ion and an electron.

  14. Electrochemical Power Sources

    Home; Journals; Resonance – Journal of Science Education; Volume 6; Issue 7. Electrochemical Power Sources - Rechargeable Batteries. A K Shukla S K Martha. General Article Volume 6 Issue 7 July 2001 pp 52-63. Fulltext. Click here to view fulltext PDF. Permanent link:

  15. Electro-chemical grinding

    Feagans, P. L.

    1972-01-01

    Electro-chemical grinding technique has rotation speed control, constant feed rates, and contour control. Hypersonic engine parts of nickel alloys can be almost 100% machined, keeping tool pressure at virtual zero. Technique eliminates galling and permits constant surface finish and burr-free interrupted cutting.

  16. Skeletal and chlorine effects on 13C-NMR chemical shifts of chlorinated polycyclic systems

    Costa V.E.U.

    1999-01-01

    Full Text Available In order to establish a comparative analysis of chemical shifts caused by ring compression effects or by the presence of a chlorine atom on strained chlorinated carbons, a series of the chlorinated and dechlorinated polycyclic structures derived from "aldrin" (5 and "isodrin" (14 was studied. Compounds were classified in four different groups, according to their conformation and number of ring such as: endo-exo and endo-endo tetracyclics, pentacyclics and hexacyclics. The 13C chemical shift comparison between the chlorinated and dechlorinated compounds showed that when C-9 and C-10 are olefinic carbons, it occurs a shielding of 0.5-2.4 ppm for endo-endo tetracyclics and of 4.7-7.6 ppm for endo-exo tetracyclic. The chemical shift variation for C-11 reaches 49-53 ppm for endo-exo and endo-endo tetracyclics, 54 ppm for pentacyclic and 56-59 ppm for hexacyclic compounds. From these data, it was possible to observe the influence of ring compression on the chemical shifts.

  17. Layering and Ordering in Electrochemical Double Layers

    Liu, Yihua [Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, United States; Kawaguchi, Tomoya [Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, United States; Pierce, Michael S. [Rochester Institute of Technology, School of Physics and Astronomy, Rochester, New York 14623, United States; Komanicky, Vladimir [Faculty of Science, Safarik University, 041 54 Kosice, Slovakia; You, Hoydoo [Materials Science Division, Argonne National Laboratory, Argonne, Illinois 60439, United States

    2018-02-26

    Electrochemical double layers (EDL) form at electrified interfaces. While Gouy-Chapman model describes moderately charged EDL, formation of Stern layers was predicted for highly charged EDL. Our results provide structural evidence for a Stern layer of cations, at potentials close to hydrogen evolution in alkali fluoride and chloride electrolytes. Layering was observed by x-ray crystal truncation rods and atomic-scale recoil responses of Pt(111) surface layers. Ordering in the layer is confirmed by glancing-incidence in-plane diffraction measurements.

  18. Scenarios Evaluation Tool for Chlorinated Solvent MNA

    Vangelas, Karen; Michael J. Truex; Charles J. Newell; Brian Looney

    2007-02-28

    Over the past three decades, much progress has been made in the remediation of chlorinated solvents from the subsurface. Yet these pervasive contaminants continue to present a significant challenge to the U.S. Department of Energy (DOE), other federal agencies, and other public and private organizations. The physical and chemical properties of chlorinated solvents make it difficult to rapidly reach the low concentrations typically set as regulatory limits. These technical challenges often result in high costs and long remediation time frames. In 2003, the DOE through the Office of Environmental Management funded a science-based technical project that uses the U.S. Environmental Protection Agency's technical protocol (EPA, 1998) and directives (EPA, 1999) on Monitored Natural Attenuation (MNA) as the foundation on which to introduce supporting concepts and new scientific developments that will support remediation of chlorinated solvents based on natural attenuation processes. This project supports the direction in which many site owners want to move to complete the remediation of their site(s), that being to complete the active treatment portion of the remedial effort and transition into MNA. The overarching objective of the effort was to examine environmental remedies that are based on natural processes--remedies such as Monitored Natural Attenuation (MNA) or Enhanced Attenuation (EA). The research program did identify several specific opportunities for advances based on: (1) mass balance as the central framework for attenuation based remedies, (2) scientific advancements and achievements during the past ten years, (3) regulatory and policy development and real-world experience using MNA, and (4) exploration of various ideas for integrating attenuation remedies into a systematic set of ''combined remedies'' for contaminated sites. These opportunities are summarized herein and are addressed in more detail in referenced project documents and

  19. A current driven capacitively coupled chlorine discharge

    Huang, Shuo; Gudmundsson, J T

    2014-01-01

    The effect of driving current, driving frequency and secondary electrons on capacitively coupled chlorine discharge is systematically investigated using a hybrid approach consisting of a particle-in-cell/Monte Carlo simulation and a volume-averaged global model. The driving current is varied from 20 to 80 A m −2 , the driving frequency is varied from 13.56 to 60 MHz and the secondary electron emission coefficient is varied from 0.0 to 0.4. Key plasma parameters including electron energy probability function, electron heating rate, ion energy and angular distributions are explored and their variations with control parameters are analyzed and compared with other discharges. Furthermore, we extend our study to dual-frequency (DF) capacitively coupled chlorine discharge by adding a low-frequency current source and explore the effect of the low-frequency source on the discharge. The low-frequency current density is increased from 0 to 4 A m −2 . The flux of Cl 2 + ions to the surface increases only slightly while the average energy of Cl 2 + ions to the surface increases almost linearly with increasing low-frequency current, which shows possible independent control of the flux and energy of Cl 2 + ions by varying the low-frequency current in a DF capacitively coupled chlorine discharge. However, the increase in the flux of Cl + ions with increasing low-frequency current, which is mainly due to the increased dissociation fraction of the background gas caused by extra power supplied by the low-frequency source, is undesirable. (paper)

  20. Sonolysis of chlorinated compounds in aqueous solution.

    Lim, Myung Hee; Kim, Seung Hyun; Kim, Young Uk; Khim, Jeehyeong

    2007-02-01

    To examine the reaction rates of sonochemical degradation of aqueous phase carbon tetrachloride, trichloroethylene and 1,2,3-trichloropropane at various temperatures, power intensities, and saturating gases, the batch tests were carried out. The degradations of chlorinated hydrocarbons were analyzed as pseudo first order reactions and their reaction rate constants were in the range of 10(-1)-10(-3)/min. The reaction was fast at the low temperature with higher power intensity. Also, the reaction went fast with the saturating gas with high specific heat ratio, high solubility and low thermal conductivity. The main mechanism of destruction of chemicals was believed the thermal combustion in the bubble.

  1. Chlorine and bromine solar neutrino experiments

    Davis, R. Jr.; Cleveland, B.T.; Rowley, J.K.

    1985-01-01

    The solar neutrino experiment based upon the neutrino capture reaction 37 Cl (ν, e - ) 37 Ar has been in operation in the Homestake Gold Mine at Lead, South Dakota since 1967. The results of this experiment are well known, and have been reported most recently to the solar neutrino conference at Lead in 1984. We report here the latest results from this experiment. A radiochemical neutrino detector based upon the neutrino capture reaction 81 Br (ν, e - ) 81 Kr* → 81 Kr has recently been shown to be feasible. Our plans for performing a full scale test of the method using the Homestake chlorine detector are discussed briefly. 8 refs

  2. Biological Chlorine Cycling in Arctic Peat Soils

    Zlamal, J. E.; Raab, T. K.; Lipson, D.

    2014-12-01

    Soils of the Arctic tundra near Barrow, Alaska are waterlogged and anoxic throughout most of the profile due to underlying permafrost. Microbial communities in these soils are adapted for the dominant anaerobic conditions and are capable of a surprising diversity of metabolic pathways. Anaerobic respiration in this environment warrants further study, particularly in the realm of electron cycling involving chlorine, which preliminary data suggest may play an important role in arctic anaerobic soil respiration. For decades, Cl was rarely studied outside of the context of solvent-contaminated sites due to the widely held belief that it is an inert element. However, Cl has increasingly become recognized as a metabolic player in microbial communities and soil cycling processes. Organic chlorinated compounds (Clorg) can be made by various organisms and used metabolically by others, such as serving as electron acceptors for microbes performing organohalide respiration. Sequencing our arctic soil samples has uncovered multiple genera of microorganisms capable of participating in many Cl-cycling processes including organohalide respiration, chlorinated hydrocarbon degradation, and perchlorate reduction. Metagenomic analysis of these soils has revealed genes for key enzymes of Cl-related metabolic processes such as dehalogenases and haloperoxidases, and close matches to genomes of known organohalide respiring microorganisms from the Dehalococcoides, Dechloromonas, Carboxydothermus, and Anaeromyxobacter genera. A TOX-100 Chlorine Analyzer was used to quantify total Cl in arctic soils, and these data were examined further to separate levels of inorganic Cl compounds and Clorg. Levels of Clorg increased with soil organic matter content, although total Cl levels lack this trend. X-ray Absorption Near Edge Structure (XANES) was used to provide information on the structure of Clorg in arctic soils, showing great diversity with Cl bound to both aromatic and alkyl groups

  3. Effects of conventional ozonation and electro-peroxone pretreatment of surface water on disinfection by-product formation during subsequent chlorination.

    Mao, Yuqin; Guo, Di; Yao, Weikun; Wang, Xiaomao; Yang, Hongwei; Xie, Yuefeng F; Komarneni, Sridhar; Yu, Gang; Wang, Yujue

    2018-03-01

    The electro-peroxone (E-peroxone) process is an emerging ozone-based electrochemical advanced oxidation process that combines conventional ozonation with in-situ cathodic hydrogen peroxide (H 2 O 2 ) production for oxidative water treatment. In this study, the effects of the E-peroxone pretreatment on disinfection by-product (DBP) formation from chlorination of a synthetic surface water were investigated and compared to conventional ozonation. Results show that due to the enhanced transformation of ozone (O 3 ) to hydroxyl radicals (OH) by electro-generated H 2 O 2 , the E-peroxone process considerably enhanced dissolved organic carbon (DOC) abatement and significantly reduced bromate (BrO 3 - ) formation compared to conventional ozonation. However, natural organic matter (NOM) with high UV 254 absorbance, which is the major precursors of chlorination DBPs, was less efficiently abated during the E-peroxone process than conventional ozonation. Consequently, while both conventional ozonation and the E-peroxone process substantially reduced the formation of DBPs (trihalomethanes and haloacetic acids) during post-chlorination, higher DBP concentrations were generally observed during chlorination of the E-peroxone pretreated waters than conventional ozonation treated. In addition, because of conventional ozonation or the E-peroxone treatment, DBPs formed during post-chlorination shifted to more brominated species. The overall yields of brominated DBPs exhibited strong correlations with the bromide concentrations in water. Therefore, while the E-peroxone process can effectively suppress bromide transformation to bromate, it may lead to higher formation of brominated DBPs during post-chlorination compared to conventional ozonation. These results suggest that the E-peroxone process can lead to different DBP formation and speciation during water treatment trains compared to conventional ozonation. Copyright © 2017 Elsevier Ltd. All rights reserved.

  4. Bacterial oxidation of low-chlorinated compounds under anoxic conditions

    Dijk, J.A.

    2005-01-01

    Chlorinated hydrocarbons belong to the most frequently encountered contaminants in soil and groundwater. Many of them were found to be toxic and recalcitrant, which causes a potential threat to the environment. Therefore, it is of great importance that sites contaminated with chlorinated

  5. 78 FR 66767 - Chlorinated Isocyanurates From China and Japan

    2013-11-06

    ...)] Chlorinated Isocyanurates From China and Japan Determinations On the basis of the record \\1\\ developed in the... reason of imports from China and Japan of chlorinated isocyanurates, provided for in subheadings 2933.69... (LTFV) from Japan and subsidized by the Government of China.\\2\\ \\1\\ The record is defined in sec. 207.2...

  6. Chlorine-containing natural compounds in higher plants

    Engvild, Kjeld Christensen

    1986-01-01

    More than 130 chlorine-containing compounds have been isolated from higher plants and ferns; about half are polyacetylenes, thiophenes and sesquiterpene lactones from the Asteraceae. A chlorinated chlorophyll may be an important part of photosystem 1. High biological activity is found in 4...

  7. Dense chlorinated solvents and other DNAPLs in groundwater

    Broholm, K.

    1996-01-01

    Anmeldelse af Pankow,J.F. & Cherry,J.A.: Dense chlorinated solvents and other DNAPLs in groundwater. Waterloo Press, Portland, Oregon, USA, 1996......Anmeldelse af Pankow,J.F. & Cherry,J.A.: Dense chlorinated solvents and other DNAPLs in groundwater. Waterloo Press, Portland, Oregon, USA, 1996...

  8. UASB reactor effluent disinfection by ozone and chlorine

    Ribeiro da Silvia, G.H.; Bruning, H.; Gerrity, D.; Daniel, L.A.

    2015-01-01

    This research studied the sequential ozone and chlorine process with respect to, the inactivation of indicator bacteria and the formation of ozone disinfection byproducts in sanitary wastewater effluent. The applied ozone doses were 5, 8 and 10 mg.O3.L-1, followed by chlorine doses of 10, 20 and 30

  9. Inhibition of lipopolysaccharide induced acute inflammation in lung by chlorination

    Zhang, Jinshan; Xue, Jinling; Xu, Bi; Xie, Jiani [Environmental Simulation and Pollution Control State Key Joint Laboratory, School of Environment, Tsinghua University, Beijing 100084 (China); Qiao, Juan, E-mail: qjuan@tsinghua.edu.cn [Department of Chemistry, Tsinghua University, Beijing 100084 (China); Lu, Yun, E-mail: luyun@tsinghua.edu.cn [Environmental Simulation and Pollution Control State Key Joint Laboratory, School of Environment, Tsinghua University, Beijing 100084 (China)

    2016-02-13

    Highlights: • Chlorination is effective to reduce the inflammation inducing capacity of LPS in lung. • LAL-detected endotoxin activity is not correlated to the potency of inflammation induction. • Alkyl chain of LPS was chlorinated in chlorination process. • LPS aggregate size decreases after chlorination. - Abstract: Lipopolysaccharide (LPS, also called endotoxin) is a pro-inflammatory constituent of gram negative bacteria and cyanobacteria, which causes a potential health risk in the process of routine urban application of reclaimed water, such as car wash, irrigation, scenic water refilling, etc. Previous studies indicated that the common disinfection treatment, chlorination, has little effect on endotoxin activity removal measured by Limulus amebocyte lysate (LAL) assay. However, in this study, significant decrease of acute inflammatory effects was observed in mouse lung, while LAL assay still presented a moderate increase of endotoxin activity. To explore the possible mechanisms, the nuclear magnetic resonance (NMR) results showed the chlorination happened in alkyl chain of LPS molecules, which could affect the interaction between LPS and LPS-binding protein. Also the size of LPS aggregates was found to drop significantly after treatment, which could be another results of chlorination caused polarity change. In conclusion, our observation demonstrated that chlorination is effective to reduce the LPS induced inflammation in lung, and it is recommended to use health effect-based methods to assess risk removal of water treatment technologies.

  10. Inhibition of lipopolysaccharide induced acute inflammation in lung by chlorination

    Zhang, Jinshan; Xue, Jinling; Xu, Bi; Xie, Jiani; Qiao, Juan; Lu, Yun

    2016-01-01

    Highlights: • Chlorination is effective to reduce the inflammation inducing capacity of LPS in lung. • LAL-detected endotoxin activity is not correlated to the potency of inflammation induction. • Alkyl chain of LPS was chlorinated in chlorination process. • LPS aggregate size decreases after chlorination. - Abstract: Lipopolysaccharide (LPS, also called endotoxin) is a pro-inflammatory constituent of gram negative bacteria and cyanobacteria, which causes a potential health risk in the process of routine urban application of reclaimed water, such as car wash, irrigation, scenic water refilling, etc. Previous studies indicated that the common disinfection treatment, chlorination, has little effect on endotoxin activity removal measured by Limulus amebocyte lysate (LAL) assay. However, in this study, significant decrease of acute inflammatory effects was observed in mouse lung, while LAL assay still presented a moderate increase of endotoxin activity. To explore the possible mechanisms, the nuclear magnetic resonance (NMR) results showed the chlorination happened in alkyl chain of LPS molecules, which could affect the interaction between LPS and LPS-binding protein. Also the size of LPS aggregates was found to drop significantly after treatment, which could be another results of chlorination caused polarity change. In conclusion, our observation demonstrated that chlorination is effective to reduce the LPS induced inflammation in lung, and it is recommended to use health effect-based methods to assess risk removal of water treatment technologies.

  11. Experimental and Theoretical Studies of Atmosphereic Inorganic Chlorine Chemistry

    Sander, Stanley P.; Friedl, Randall R.

    1993-01-01

    Over the last five years substantial progress has been made in defining the realm of new chlorine chemistry in the polar stratosphere. Application of existing experimental techniques to potentially important chlorine-containing compounds has yielded quantitative kinetic and spectroscopic data as well as qualitative mechanistic insights into the relevant reactions.

  12. Selective Electrochemical Generation of Hydrogen Peroxide from Water Oxidation

    Viswanathan, Venkatasubramanian; Hansen, Heine Anton; Nørskov, Jens K.

    2015-01-01

    evolution and form hydrogen peroxide. Using density functional theory calculations, we show that the free energy of adsorbed OH* can be used to determine selectivity trends between the 2e(-) water oxidation to H2O2 and the 4e(-) oxidation to O2. We show that materials which bind oxygen intermediates...... sufficiently weakly, such as SnO2, can activate hydrogen peroxide evolution. We present a rational design principle for the selectivity in electrochemical water oxidation and identify new material candidates that could perform H2O2 evolution selectively....

  13. Electrochemical behavior of synthesized Al{sub x}Sn{sub y} with mechanical grinding in hydrogen evolution reaction (HER); Comportamiento electroquimico del Al{sub x}Sn{sub y} sintetizado por molienda mecanica en la REH (Reaccion de Evolucion de Hidrogeno)

    Olvera Vazquez, S. L.; Arce Estrada, E. M. [Instituto Politecnico Nacional, Mexico, D.F. (Mexico )]. E-mail: seydyliz@hotmail.com

    2009-09-15

    Currently, the best catalyst for HER is Pt, nevertheless because of its high costs, many studies have been performed with a variety of materials, including AI, which is a promising source of hydrogen. Therefore, this work studied the effect of tin on Al{sub x}Sn{sub y} alloys obtained by mechanical grinding. The materials obtained were characterized with electron sweep microscopy, x-ray diffraction and electrochemical techniques. It was determined that the synthesized materials have a micrometer size and present at least two phases. The electrochemical characterization for use as electrocatalysts for the hydrogen evolution reaction (HER) was performed in an NaCl 2 M solution using potentiodynamic polarization and chronoamperometry techniques, showing that the materials with low tin contents have better electrocatalytic activity for HER. [Spanish] Actualmente el mejor catalizador para la REH es el Pt, sin embargo debido a sus altos costos se han realizado numerosos estudios con diversos materiales entre los cuales se encuentra el Al, que es una promisoria fuente de hidrogeno. Por tal motivo en este trabajo se realizaron estudios del efecto que presenta el contenido de estano en aleaciones Al{sub x}Sn{sub y} obtenidas por molienda mecanica. Los materiales obtenidos se caracterizaron por microscopia electronica de barrido, difraccion de rayos X y tecnicas electroquimicas. Se determino que los materiales sintetizados son de tamano micrometrico y que al menos presentan dos fases. La caracterizacion electroquimica para su uso como electrocatalizadores para la reaccion de evolucion de hidrogeno, REH, se llevo a cabo en una solucion de NaCl 2 M, empleando las tecnicas de polarizacion potenciodinamica y cronoamperometria, observandose que los materiales con contenidos bajos de estano presentan una mejor actividad electrocatalitica para la REH.

  14. Local coordination and medium range order in molten trivalent metal chlorides: The role of screening by the chlorine component

    Pastore, G.; Tosi, M.P.

    1995-11-01

    Earlier work has identified the metal ion size R M as a relevant parameter in determining the evolution of the liquid structure of trivalent metal chlorides across the series from LaCl 3 (R M approx. 1.4 A) to AlCl 3 (R M approx. 0.8 A). Here we highlight the structural role of the chlorines by contrasting the structure of fully equilibrated melts with that of disordered systems obtained by quenching the chlorine component. Main attention is given to how the suppression of screening of the polyvalent ions by the chlorines changes trends in the local liquid structure (first neighbour coordination and partial radial distribution functions) and in the intermediate range order (first sharp diffraction peak in the partial structure factors). The main microscopic consequences of structural quenching of the chlorine component are a reduction in short range order and an enhancement of intermediate range order in the metal ion component, as well as the suppression of a tendency to molecular-type states at the lower end of the range of R M . (author). 23 refs, 6 figs

  15. Preliminary GRS Measurement of Chlorine Distribution on Surface of Mars

    Keller, J. M.; Boynton, W. V.; Taylor, G. J.; Hamara, D.; Janes, D. M.; Kerry, K.

    2003-12-01

    Ongoing measurements with the Gamma Ray Spectrometer (GRS) aboard Mars Odyssey provide preliminary detection of chlorine at the surface of Mars. Summing all data since boom deployment and using a forward calculation model, we estimate values for chlorine concentration at 5° resolution. Rebinning this data and smoothing with a 15-degree-radius boxcar filter reveal regions of noticeable chlorine enrichment at scales larger than the original 5° resolution and allow for preliminary comparison with previous Mars datasets. Analyzing chlorine concentrations within 30 degrees of the equator, we find a negative correlation with thermal inertia (R2=0.55) and positive correlation with albedo (R2=0.52), indicating that chlorine is associated with fine, non-rock surface materials. Although possibly a smoothing artifact, the spatial correlation is more noticeable in the region covering Tharsis and Amazonis than around Arabia and Elysium. Additionally, a noticeable region of chlorine enrichment appears west of Tharsis Montes ( ˜0 to 20N, ˜110 to 150W) and chlorine concentration is estimated to vary in the equatorial region by over a factor of two. A simplified two-component model involving chlorine-poor rocks and a homogenous chlorine-rich fine material requires rock abundance to vary from zero to over 50%, a result inconsistent with previous measurements and models. In addition to variations in rock composition and distribution, substantial variations in chlorine content of various types of fine materials including dust, sand, and duricrust appear important in explaining this preliminary observation. Surprisingly, visual comparison of surface units mapped by Christensen and Moore (1992) does not show enrichment in chlorine associated with regions of indurated surfaces, where cementation has been proposed. Rather, Tharsis, a region of active deposition with proposed mantling of 0.1 to 2 meters of recent dust (Christensen 1986), shows the greatest chlorine signal. In light of

  16. Effects of short-chain chlorinated paraffins on soil organisms.

    Bezchlebová, Jitka; Cernohlávková, Jitka; Kobeticová, Klára; Lána, Jan; Sochová, Ivana; Hofman, Jakub

    2007-06-01

    Despite the fact that chlorinated paraffins have been produced in relatively large amounts, and high concentrations have been found in sewage sludge applied to soils, there is little information on their concentrations in soils and the effect on soil organisms. The aim of this study was to investigate the toxicity of chlorinated paraffins in soils. The effects of short-chain chlorinated paraffins (64% chlorine content) on invertebrates (Eisenia fetida, Folsomia candida, Enchytraeus albidus, Enchytraeus crypticus, Caenorhabditis elegans) and substrate-induced respiration of indigenous microorganisms were studied. Differences were found in the sensitivity of the tested organisms to short-chain chlorinated paraffins. F. candida was identified as the most sensitive organism with LC(50) and EC(50) values of 5733 and 1230 mg/kg, respectively. Toxicity results were compared with available studies and the predicted no effect concentration (PNEC) of 5.28 mg/kg was estimated for the soil environment, based on our data.

  17. Release of chlorine from biomass at gasification conditions

    Bjoerkman, E.; Stroemberg, B. [TPS Termiska Processer AB, Nykoeping (Sweden)

    1997-05-01

    The objective of the project was to investigate the influence of different gasifying atmospheres on the release of chlorine from biomass during gasification conditions. Furthermore, the purpose was also to try and identify the formed chloro compounds. The results showed that O{sub 2}, H{sub 2}O and CO{sub 2} had negligible effect on the chlorine release at temperatures under 700 deg C. At temperatures above 800 deg C the reactivity towards CO{sub 2} increased and could be seen as higher chlorine release and less solid residue. No chloro organic compounds (aliphatic one to six carbons or aromatic one to two rings) could be detected in the tar or the fuel gas produced during pyrolysis/gasifying. On the other hand, comparable amounts of chlorinated benzenes were found in the cooling section during combustion of lucerne and of synthetic waste, indicating that oxygen is essential for chlorination reactions. 11 refs, 4 figs, 1 tab

  18. Release of chlorine from biomass at gasification conditions

    Bjoerkman, E.; Stroemberg, B.

    1997-05-01

    The objective of the project was to investigate the influence of different gasifying atmospheres on the release of chlorine from biomass during gasification conditions. Furthermore, the purpose was also to try and identify the formed chloro compounds. The results showed that O 2 , H 2 O and CO 2 had negligible effect on the chlorine release at temperatures under 700 deg C. At temperatures above 800 deg C the reactivity towards CO 2 increased and could be seen as higher chlorine release and less solid residue. No chloro organic compounds (aliphatic one to six carbons or aromatic one to two rings) could be detected in the tar or the fuel gas produced during pyrolysis/gasifying. On the other hand, comparable amounts of chlorinated benzenes were found in the cooling section during combustion of lucerne and of synthetic waste, indicating that oxygen is essential for chlorination reactions. 11 refs, 4 figs, 1 tab

  19. Detecting chlorinated hydrocarbon residues: Rachel Carson's villains.

    Travis, Anthony S

    2012-07-01

    In 1962, Rachel Carson's Silent Spring drew the public's attention to the deleterious effects of chlorinated hydrocarbons employed as economic poisons in agriculture. However, she did not discuss how their residues could be routinely identified and quantified. In part, this was because the introduction of instruments for use in environmental analysis had only just begun, and she was probably unaware of their existence. The development of the instrumental methods began in industry, particularly at Dow and Shell, in the mid-1950s. Dow scientists, by combining mass spectrometry with gas chromatography, developed the most powerful technique, then and now, for the separation, quantitation and identification of chlorinated hydrocarbons. Shell scientists were no less innovative, particularly with the application of highly sensitive gas chromatography detectors to trace analysis. The first of these detectors, the electron capture detector, was invented by James Lovelock at the National Institute of Medical Research, North London, at the end of the 1950s. Around the same time, Dale Coulson in the USA developed his microcoulometric detector.

  20. Chlorinated hydrocarbons in a pelagic community

    Elder, D.; Fowler, S.W.

    1976-01-01

    For several years data have been accruing on the distribution of chlorinated hydrocarbon pollutants in marine ecosystems. An overall picture of ambient levels in biota, water and sediments is now emerging however, despite the vast amount of data collected to date, questions still arise as to whether certain pollutants such as chlorinated hydrocarbons are indeed magnified through the marine food web. Evidence both for and against trophic concentration of PCB and DDT compounds has been cited. The answer to this question remains unclear due to lack of adequate knowledge on the relative importance of food and water in the uptake of these compounds as well as the fact that conclusions are often confounded by comparing pollutant concentrations in successive links in the food chain sampled at different geographical locations and/or at different points in time. The situation is further complicated by complex prey-predator relationships that exist in many marine communities. In the present study we have tried to eliminate some of these problems by examining PCB and DOT concentrations in species belonging to a relatively well-defined pelagic food chain sampled at one point in space and time

  1. Bioremediation of chlorinated solvents and diesel soils

    Huismann, S.S.; Peterson, M.A.; Jardine, R.J.

    1995-01-01

    The US Army, in a cooperative effort with the Tennessee Valley Authority (TVA) and its cooperator, ENSR, performed an innovative enhanced bioremediation project at Fort Gillem in Atlanta, Georgia. The objective of the project was to remediate six hundred cubic yards of soil affected by a mixture of chlorinated compounds and petroleum hydrocarbons which posed a threat to uppermost groundwater and private drinking water wells. ENSR completed a demonstration project to measure the effects of bioremediation on both chlorinated compounds (primarily TCE) and petroleum hydrocarbons (number-sign 2 diesel). Contaminated soil was placed on top of a bermed polyethylene liner to construct an ex-situ biovault. Nutrients were added to the soil as it was loaded onto the liner. Contaminated soil was also used to construct a control vault. A methane barrier cover was placed over both piles. The cover was designed to prevent short circuiting of induced airflow in and around the enhanced pile, and to prevent the release of fugitive emissions from either pile

  2. Atomic scale insights into electrochemical versus gas phase oxidation of HCl over RuO2-based catalysts: A comparative review

    Over, Herbert

    2013-01-01

    In this article our current understanding of the electro-catalyzed chlorine evolution reaction (CER) in comparison with that of the heterogeneously-catalyzed gas phase oxidation of HCl (Deacon process: heterogeneous catalysis) over RuO 2 -based catalysts will be reviewed. Both types of harsh reactions are chemically similar: The main concern is catalyst stability, and in both cases the best catalyst contains RuO 2 as the catalytically active component so that a critical comparison may provide new insights into the underlying physicochemical processes. It is the primary scope of this review addresses atomic scale information on the RuO 2 -catalyzed HCl oxidation reaction either in electrochemical or in gas phase environment. In particular, the involved reaction mechanisms and the reason for the extraordinary stability of RuO 2 under such harsh reaction conditions will be discussed, emphasizing similarities and differences in the Deacon process and the CER and what can be learnt from this comparison. The distinct properties of RuO 2 , which are responsible for its extraordinary catalytic performance in both the CER and the Deacon process, are highlighted

  3. Electrochemical characterisation of CaCl{sub 2} deficient LiCl–KCl–CaCl{sub 2} eutectic melt and electro-deoxidation of solid UO{sub 2}

    Sri Maha Vishnu, D., E-mail: smvd2@cam.ac.uk; Sanil, N.; Mohandas, K.S.; Nagarajan, K.

    2016-03-15

    The CaCl{sub 2} deficient ternary eutectic melt LiCl–KCl–CaCl{sub 2} (50.5: 44.2: 5.3 mol %) was electrochemically characterised by cyclic voltammetry and polarization techniques in the context of its probable use as the electrolyte in the electrochemical reduction of solid UO{sub 2} to uranium metal. Tungsten (cathodic polarization) and graphite (anodic polarization) working electrodes were used in these studies carried out in the temperature range 623 K–923 K. The cathodic limit of the melt was observed to be set by the deposition of Ca{sup 2+} ions followed by Li{sup +} ions on the tungsten electrode and the anodic limit by oxidation of chloride ions on the graphite electrode (chlorine evolution). The difference between the onset potential of deposition of Ca{sup 2+} and Li{sup +} was found to be 0.241 V at a scan rate of 20 mV/s at 623 K and the difference decreased with increase in temperature and vanished at 923 K. Polarization measurements with stainless steel (SS) cathode and graphite anode at 673 K showed the possibility of low–energy reactions occurring on the UO{sub 2} electrode in the melt. UO{sub 2} pellets were cathodically polarized at 3.9 V for 25 h to test the feasibility of electro-reduction to uranium in the melt. The surface of the pellets was found reduced to U metal. - Highlights: • Electrochemically characterized LiCl–KCl–CaCl{sub 2} (50.5: 44.2: 5.3 mol %) melt by CV, LSV and polarization techniques. • Ca{sup 2+} deposits first on tungsten working electrode followed by Li{sup +}. Cl{sup −} discharges on graphite to liberate chlorine gas. • Surface of UO{sub 2} pellet reduced to U in the melt with low carbon contamination of melt. • Slow reduction of UO{sub 2} due to slow kinetics and low solubility of oxide ions in the low temperature melt.

  4. Chlorine inactivation of Tubifex tubifex in drinking water and the synergistic effect of sequential inactivation with UV irradiation and chlorine.

    Nie, Xiao-Bao; Li, Zhi-Hong; Long, Yuan-Nan; He, Pan-Pan; Xu, Chao

    2017-06-01

    The inactivation of Tubifex tubifex is important to prevent contamination of drinking water. Chlorine is a widely-used disinfectant and the key factor in the inactivation of T. tubifex. This study investigated the inactivation kinetics of chlorine on T. tubifex and the synergistic effect of the sequential use of chlorine and UV irradiation. The experimental results indicated that the Ct (concentration × time reaction ) concept could be used to evaluate the inactivation kinetics of T. tubifex with chlorine, thus allowing for the use of a simpler Ct approach for the assessment of T. tubifex chlorine inactivation requirements. The inactivation kinetics of T. tubifex by chlorine was found to be well-fitted to a delayed pseudo first-order Chick-Watson expression. Sequential experiments revealed that UV irradiation and chlorine worked synergistically to effectively inactivate T. tubifex as a result of the decreased activation energy, E a , induced by primary UV irradiation. Furthermore, the inactivation effectiveness of T. tubifex by chlorine was found to be affected by several drinking water quality parameters including pH, turbidity, and chemical oxygen demand with potassium permanganate (COD Mn ) concentration. High pH exhibited pronounced inactivation effectiveness and the decrease in turbidity and COD Mn concentrations contributed to the inactivation of T. tubifex. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Formation of assimilable organic carbon during oxidation of natural waters with ozone, chlorine dioxide, chlorine, permanganate, and ferrate.

    Ramseier, Maaike K; Peter, Andreas; Traber, Jacqueline; von Gunten, Urs

    2011-02-01

    Five oxidants, ozone, chlorine dioxide, chlorine, permanganate, and ferrate were studied with regard to the formation of assimilable organic carbon (AOC) and oxalate in absence and presence of cyanobacteria in lake water matrices. Ozone and ferrate formed significant amounts of AOC, i.e. more than 100 μg/L AOC were formed with 4.6 mg/L ozone and ferrate in water with 3.8 mg/L dissolved organic carbon. In the same water samples chlorine dioxide, chlorine, and permanganate produced no or only limited AOC. When cyanobacterial cells (Aphanizomenon gracile) were added to the water, an AOC increase was detected with ozone, permanganate, and ferrate, probably due to cell lysis. This was confirmed by the increase of extracellular geosmin, a substance found in the selected cyanobacterial cells. AOC formation by chlorine and chlorine dioxide was not affected by the presence of the cells. The formation of oxalate upon oxidation was found to be a linear function of the oxidant consumption for all five oxidants. The following molar yields were measured in three different water matrices based on oxidant consumed: 2.4-4.4% for ozone, 1.0-2.8% for chlorine dioxide and chlorine, 1.1-1.2% for ferrate, and 11-16% for permanganate. Furthermore, oxalate was formed in similar concentrations as trihalomethanes during chlorination (yield ∼ 1% based on chlorine consumed). Oxalate formation kinetics and stoichiometry did not correspond to the AOC formation. Therefore, oxalate cannot be used as a surrogate for AOC formation during oxidative water treatment. Copyright © 2010 Elsevier Ltd. All rights reserved.

  6. Electrochemical Oxidation of PAHs in Water from Harbor Sediment Purification

    Muff, Jens; Søgaard, Erik Gydesen

    2010-01-01

    generated oxidant solution with a free chlorine concentration of 2 gL-1. Both strategies resulted in a successful degradation of 5 PAHs to fulfil the discharge limit on 0.010 µgL-1. The intermixing-with-oxidant approach can also be applied as a method to address the actual sediment matrix....... of the discharge water addressing primarily polycyclic aromatic hydrocarbons (PAHs). PAHs are by-products of incomplete combustion of organic materials with recalcitrant and strong mutagenic/carcinogenic properties, due to their benzene analogue structures. PAHs are hydrophobic compounds and their persistence...... evidence for the importance of the indirect oxidation mechanism in the degradation of the PAHs. The proof-of-concept study was conducted both by a direct treatment approach and an intermixing-with-oxidant approach, where the contaminated water was intermixed in different ratios with an electrochemically...

  7. Survey of electrochemical production of inorganic compounds. Final report

    1980-10-01

    The electrochemical generation of inorganic compounds, excluding chlorine/caustic, has been critically reviewed. About 60 x 10/sup 12/ Btu/y fossil fuel equivalent will be used in the year 2000 for the electrosynthesis of inorganic compounds. Significant energy savings in chlorate production can result from the development of suitable electrocatalysts for lowering the cathodic overpotential. Perchlorates, electrolytic hypochlorite, electrolytic manganese dioxide, fluorine and other miscellaneous compounds use relatively small amounts of electrical energy. Implementation of caustic scrubber technology for stack gas cleanup would result in appreciable amounts of sodium sulfate which could be electrolyzed to regenerate caustic. Hydrogen peroxide, now produced by the alkyl anthraquinone process, could be made electrolytically by a new process coupling anodic oxidation of sulfate with cathodic reduction of oxygen in alkaline solution. Ozone is currently manufactured using energy-inefficient silent discharge equipment. A novel energy-efficient approach which uses an oxygen-enhanced anodic reaction is examined.

  8. Electrochemical Approaches to Renewable Energy

    Lobaccaro, Peter

    Renewable energy is becoming an increasingly important component of the world's energy supply as the threat of global warming continues to rise. There is a need to reduce the cost of this renewable energy and a future challenge to deal with the strain intermittent power sources like renewables place on the power grid. In this dissertation, electrochemistry is harnessed to address possible solutions to both of these issues. First, it is used to develop a low cost alternative photovoltaic material. Then, it is used to investigate the production of chemical fuel stocks which can be used for energy storage. In chapter 2, advances are made in the electrochemical deposition of indium (In) on molybdenum foil which enables the deposition of electronic-grade purity, continuous films with thicknesses in the micron range. As an example application, the electrodeposited In films are phosphorized via the thin-film vapor-liquid-solid growth method. The resulting poly-crystalline InP films display excellent optoelectronic quality, comparable to films grown from more standard vacuum deposition techniques. This demonstrates the versatility of the developed electrochemical deposition procedure. In the remaining chapters, renewable fuel production is investigated. First in chapter 3, molybdenum disulfide (MoS2) is examined as a catalyst for the hydrogen evolution reaction (HER). Typically, high-cost synthesized MoS2 is used as the catalyst because the pristine MoS 2 mineral is known to be a poor catalyst. The fundamental challenge with pristine MoS2 is the inert HER activity of the predominant (0001) basal surface plane. Here, we report a general thermal process in which the basal plane is texturized to increase the density of HER-active edge sites. The process generates high HER catalytic performance in pristine MoS 2 across various morphologies such as the bulk mineral, films composed of micron-scale flakes, and even films of a commercially-available spray of nanoflake MoS2. In

  9. Does Chlorination of Seawater Reverse Osmosis Membranes Control Biofouling?

    Khan, Muhammad Tariq; Hong, Pei-Ying; Nada, Nabil; Croue, Jean Philippe

    2015-01-01

    Biofouling is the major problem of reverse osmosis (RO) membranes used for desalting seawater (SW). The use of chlorine is a conventional and common practice to control/prevent biofouling. Unlike polyamide RO membranes, cellulose triacetate (CTA) RO membranes display a high chlorine tolerance. Due to this characteristic, CTA membranes are used in most of the RO plants located in the Middle East region where the elevated seawater temperature and water quality promote the risk of membrane biofouling. However, there is no detailed study on the investigation/characterization of CTA-RO membrane fouling. In this investigation, the fouling profile of a full–scale SWRO desalination plant operating with not only continuous chlorination of raw seawater but also intermittent chlorination of CTA-RO membranes was studied. Detailed water quality and membrane fouling analyses were conducted. Profiles of microbiological, inorganic, and organic constituents of analysed fouling layers were extensively discussed. Our results clearly identified biofilm development on these membranes. The incapability of chlorination on preventing biofilm formation on SWRO membranes could be assigned to its failure in effectively reaching throughout the different regions of the permeators. This failure could have occurred due to three main factors: plugging of membrane fibers, chlorine consumption by organics accumulated on the front side fibers, or chlorine adaptation of certain bacterial populations.

  10. Radiation-Initiated Chlorination of 1, 2-Dichloroethane

    Danno, A.; Abe, T.; Washino, M.; Souda, T.; Shimada, K. [Takasaki Radiation Chemistry Research Establishment, Japan Atomic Energy Research Institute, Watanuki-machi, Takasaki-shi, Gunma-ken (Japan)

    1969-12-15

    Radiation-initiated chlorination of 1,2-dichloroethane was carried out with a batch system to study the chlorination reaction in the laboratory and also with a flow system to obtain information on its scale-up. It was found that the direct chlorination of 1,2-dichloroethane in the presence of gamma radiation takes place by a free-radical chain reaction with a high G-value of the order of 10{sup 5}. Successive chlorination of 1,2-dichloroethane gives 1,1, 2-trichloroethane, 1,1,1, 2- and 1,1, 2, 2-tetrachloroethane, pentachloroethane and hexachloroethane. No products other than these polychloro ethanes were detected. The composition of the reaction products depends on the degree of chlorination; it is independent of the dose rate and the chlorine feed rate. A promising application of this process is to produce trichloroethylene and perchloroethylene by thermal dehydrochlorination of a mixture of tetrachloroethane and pentachloroethane. The optimum conditions of producing these compounds with high yields depend on the feed rate of 1, 2-dichloroethane and chlorine gas, the dose rate and the reaction temperature. A pilot experimental facility with a 2-litre reaction vessel has been completed and is now in operation. (author)

  11. Does Chlorination of Seawater Reverse Osmosis Membranes Control Biofouling?

    Khan, Muhammad Tariq

    2015-04-01

    Biofouling is the major problem of reverse osmosis (RO) membranes used for desalting seawater (SW). The use of chlorine is a conventional and common practice to control/prevent biofouling. Unlike polyamide RO membranes, cellulose triacetate (CTA) RO membranes display a high chlorine tolerance. Due to this characteristic, CTA membranes are used in most of the RO plants located in the Middle East region where the elevated seawater temperature and water quality promote the risk of membrane biofouling. However, there is no detailed study on the investigation/characterization of CTA-RO membrane fouling. In this investigation, the fouling profile of a full–scale SWRO desalination plant operating with not only continuous chlorination of raw seawater but also intermittent chlorination of CTA-RO membranes was studied. Detailed water quality and membrane fouling analyses were conducted. Profiles of microbiological, inorganic, and organic constituents of analysed fouling layers were extensively discussed. Our results clearly identified biofilm development on these membranes. The incapability of chlorination on preventing biofilm formation on SWRO membranes could be assigned to its failure in effectively reaching throughout the different regions of the permeators. This failure could have occurred due to three main factors: plugging of membrane fibers, chlorine consumption by organics accumulated on the front side fibers, or chlorine adaptation of certain bacterial populations.

  12. [Toxicity and influencing factors of liquid chlorine on chironomid larvae].

    Sun, Xing-Bin; Cui, Fu-Yi; Zhang, Jin-Song; Guo, Zhao-Hai; Xu, Feng; Liu, Li-Jun

    2005-09-01

    The excessive propagation of Chironomid larvae (red worm) in the sedimentation tanks is a difficult problem for the normal function of waterworks. The toxic effect of liquid chlorine on the different instar larvae of Chironomid was studied using distilled water as test sample. Furthermore, the effect of pH value, organic matter content, ammonia nitrogen, and algae content on toxicity of liquid chlorine was observed. The results show that the tolerance of Chironomid larvae to liquid chlorine is strengthened with the increase in instar. The 24h semi-lethal concentration (LC50) of liquid chlorine to the 4th instar larvae of Chironomid is 3.39 mg/L. Low pH value and high algae content are helpful to improve the toxic effect of liquid chlorine to Chironomid larvae. In neutral water body, the increase in organic matter content results in the decrease in the death rate of Chironomid larvae. The toxicity of liquid chlorine differs greatly in different concentrations of ammonia nitrogen. The death rate of the 4th instar larvae of Chironomid in raw water is higher by contrast with that in sedimentation tanks water for 24h disposal with various amount of liquid chlorine.

  13. Chlorine diffusion in uranium dioxide under heavy ion irradiation

    Pipon, Y.; Bererd, N.; Moncoffre, N.; Peaucelle, C.; Toulhoat, N.; Jaffrezic, H.; Raimbault, L.; Sainsot, P.; Carlot, G.

    2007-01-01

    The radiation enhanced diffusion of chlorine in UO 2 during heavy ion irradiation is studied. In order to simulate the behaviour of 36 Cl, present as an impurity in UO 2 , 37 Cl has been implanted into the samples (projected range 200 nm). The samples were then irradiated with 63.5 MeV 127 I at two fluxes and two temperatures and the chlorine distribution was analyzed by SIMS. The results show that, during irradiation, the diffusion of the implanted chlorine is enhanced and slightly athermal with respect to pure thermal diffusion. A chlorine gain of 10% accumulating near the surface has been observed at 510 K. This corresponds to the displacement of pristine chlorine from a region of maximum defect concentration. This behaviour and the mean value of the apparent diffusion coefficient found for the implanted chlorine, around 2.5 x 10 -14 cm 2 s -1 , reflect the high mobility of chlorine in UO 2 during irradiation with fission products

  14. Chlorine diffusion in uranium dioxide under heavy ion irradiation

    Pipon, Y.; Bérerd, N.; Moncoffre, N.; Peaucelle, C.; Toulhoat, N.; Jaffrézic, H.; Raimbault, L.; Sainsot, P.; Carlot, G.

    2007-04-01

    The radiation enhanced diffusion of chlorine in UO2 during heavy ion irradiation is studied. In order to simulate the behaviour of 36Cl, present as an impurity in UO2, 37Cl has been implanted into the samples (projected range 200 nm). The samples were then irradiated with 63.5 MeV 127I at two fluxes and two temperatures and the chlorine distribution was analyzed by SIMS. The results show that, during irradiation, the diffusion of the implanted chlorine is enhanced and slightly athermal with respect to pure thermal diffusion. A chlorine gain of 10% accumulating near the surface has been observed at 510 K. This corresponds to the displacement of pristine chlorine from a region of maximum defect concentration. This behaviour and the mean value of the apparent diffusion coefficient found for the implanted chlorine, around 2.5 × 10-14 cm2 s-1, reflect the high mobility of chlorine in UO2 during irradiation with fission products.

  15. Toxic Byproduct Formation during Electrochemical Treatment of Latrine Wastewater.

    Jasper, Justin T; Yang, Yang; Hoffmann, Michael R

    2017-06-20

    Electrochemical systems are an attractive option for onsite latrine wastewater treatment due to their high efficiency and small footprint. While concerns remain over formation of toxic byproducts during treatment, rigorous studies examining byproduct formation are lacking. Experiments treating authentic latrine wastewater over variable treatment times, current densities, chloride concentrations, and anode materials were conducted to characterize byproducts and identify conditions that minimize their formation. Production of inorganic byproducts (chlorate and perchlorate) and indicator organic byproducts (haloacetic acids and trihalomethanes) during electrolysis dramatically exceeded recommendations for drinking water after one treatment cycle (∼10-30 000 times), raising concerns for contamination of downstream water supplies. Stopping the reaction after ammonium was removed (i.e., the chlorination breakpoint) was a promising method to minimize byproduct formation without compromising disinfection and nutrient removal. Though treatment was accelerated at increased chloride concentrations and current densities, byproduct concentrations remained similar near the breakpoint. On TiO 2 /IrO 2 anodes, haloacetic acids (up to ∼50 μM) and chlorate (up to ∼2 μM) were of most concern. Although boron-doped diamond anodes mineralized haloacetic acids after formation, high production rates of chlorate and perchlorate (up to ∼4 and 25 μM) made them inferior to TiO 2 /IrO 2 anodes in terms of toxic byproduct formation. Organic byproduct formation was similar during chemical chlorination and electrolysis of wastewater, suggesting that organic byproducts are formed by similar pathways in both cases (i.e., reactions with chloramines and free chlorine).

  16. Experimental lifetimes for Mg-like chlorine

    Engstroem, L.; Bengtsson, P.; Jupen, C.; Livingston, A.E.; Martinson, I.

    1995-01-01

    The results of beam-foil measurements of lifetimes for low-lying singlet levels in Mg-like chlorine, Cl VI, are presented. The decay curves were analyzed by means of the arbitrarily normalized decay curve method, combined with the recently developed CANYL code, which facilitates studies of decay chains. Cascade corrected data are presented for the levels 3s3p 1 P, 3p 2 1 S, 3p 2 1 D, and 3s3d 1 D, whereas less rigorous lifetime values, based on curve fits, were obtained for the 3p3d 1 D, 3p3d 1 F, and 3s4f 1 F levels. The data are in excellent agreement with recent theoretical values, and previous discrepancies between experiment and theory for short-lived states have been removed

  17. Electrobiorefineries: Unlocking the Synergy of Electrochemical and Microbial Conversions.

    Harnisch, Falk; Urban, Carolin

    2017-12-13

    An integrated biobased economy urges an alliance of the two realms of "chemical production" and "electric power". The concept of electrobiorefineries provides a blueprint for such an alliance. Joining the forces of microbial and electrochemical conversions in electrobiorefineries allows interfacing the production, storage, and exploitation of electricity as well as biobased chemicals. Electrobiorefineries are a technological evolution of biorefineries by the addition of (bio)electrochemical transformations. This interfacing of microbial and electrochemical conversions will result in synergies affecting the entire process line, like enlarging the product portfolio, increasing the productivity, or exploiting new feedstock. A special emphasis is given to the utilization of oxidative and reductive electroorganic reactions of microbially produced intermediates that may serve as privileged building blocks. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Electrochemical Sensors for Clinic Analysis

    Guang Li

    2008-03-01

    Full Text Available Demanded by modern medical diagnosis, advances in microfabrication technology have led to the development of fast, sensitive and selective electrochemical sensors for clinic analysis. This review addresses the principles behind electrochemical sensor design and fabrication, and introduces recent progress in the application of electrochemical sensors to analysis of clinical chemicals such as blood gases, electrolytes, metabolites, DNA and antibodies, including basic and applied research. Miniaturized commercial electrochemical biosensors will form the basis of inexpensive and easy to use devices for acquiring chemical information to bring sophisticated analytical capabilities to the non-specialist and general public alike in the future.

  19. Preparation of 1,1,2,2-tetrachloroethane and trichloroethylene labelled with radioactive chlorine

    Smirnova, G.E.; Shalygin, V.A.; Zel'venskij, Ya.D.; Prosyanov, N.N.

    1980-01-01

    The chemical synthesis of 1,1,2,2-tetrachloroethane is carried out. 1,2,2,2-tetrachloroethane is labelled with radioactive chlorine by chlorinating the mixture of cis-, transisomeres of dichlorethylene with elementary chlorine. Trichloroethylene labelled with radioactive chlorine is prepared by the effect of alkali alcohol solution on radioactive 1,1,2,2-tetrachloroethane

  20. Corrosion of copper by chlorine trifluoride

    Vincent, L.

    1966-01-01

    The research described called for a considerable amount of preliminary development of the test methods and equipment in order that the various measurements and observations could be carried out without contaminating either the samples or this highly reactive gas. The chlorine trifluoride was highly purified before use, its purity being checked by gas-phase chromatography, micro-sublimation and infrared spectrography. The tests were carried out on copper samples of various purities, in particular a 99.999 per cent copper in the form of mono-crystals. They involved kinetic measurements and the characterization of corrosion products under different temperature and pressure conditions. The kinetics showed reactions of the same order of magnitude as those obtained with elementary fluorine. At atmospheric pressure there occurs formation of cupric fluoride and cuprous chloride. The presence of this latter product shows that it is not possible to consider ClF 3 simply as a fluorinating agent. At low pressures an unknown product has been characterized. There are strong grounds for believing that it is the unstable cuprous fluoride which it has not yet been possible to isolate. A germination phenomenon has been shown to exist indicating an analogy between the initial phases of fluorination and those of oxidation. Important effects resulting from the dissociation of the copper fluorides and the solubility of chlorine in this metal have been demonstrated. Finally, tests have shown the considerable influence of the purity of the gas phase and of the nature of the reaction vessel walls on the rates of corrosion which can in certain cases be increased by a factor of several powers of ten. (author) [fr

  1. Chlorination of niobium oxide in the presence of carbon monoxide

    Freitas, L.R. de

    1984-01-01

    The chlorination kinetics of niobium pentoxide in the presence of carbon monoxide between 500-800 0 C of temperature is studied. The following variable that influences on the reaction rate are analysed: gas flow, geometry and volume of the Nb 2 O 5 samples, reaction temperature and composition of the chlorinated mixture. At the same time, two other materials were studied: the CaO.Nb 2 O 5 (synthetized in laboratory) and pyrochlorine concentrates. The three materials are compared for the chlorination method used. (M.A.C.) [pt

  2. Release of Chlorine and Sulfur during Biomass Torrefaction and Pyrolysis

    Saleh, Suriyati Binti; Flensborg, Julie Pauline; Shoulaifar, Tooran Khazraie

    2014-01-01

    The release of chlorine (Cl) and sulfur (S) during biomass torrefaction and pyrolysis has been investigated via experiments in two laboratory-scale reactors: a rotating reactor and a fixed bed reactor. Six biomasses with different chemical compositions covering a wide range of ash content and ash...... reporting that biomasses with a lower chlorine content release a higher fraction of chlorine during the pyrolysis process. A significant sulfur release (about 60%) was observed from the six biomasses investigated at 350 degrees C. The initial sulfur content in the biomass did not influence the fraction...

  3. Chlorine and bromine contents in tobacco and tobacco smoke

    Haesaenen, E.; Manninen, P.K.G.; Himberg, K.; Vaeaetaeinen, V.

    1990-01-01

    The chlorine and bromine contents in tobacco and tobacco smoke in both the particulate and gaseous phases were studied by neutron activation analysis. Eleven popular brands of western filter cigarettes were tested. Methyl chloride and methyl bromide concentrations were measured in the gaseous phase in two leading brands in Finland. The results suggest that the mainstream smoke from one cigarette conveys into the lungs about 150 μg chlorine and about 5 μg bromine. Probably most of the chlorine and bromine is in the form of organic compounds and the main components are methyl chloride and methyl bromide. (author) 14 refs.; 1 tab

  4. Effect of Chlorine on Giardia lamblia Cyst Viability

    Jarroll, Edward L.; Bingham, Alan K.; Meyer, Ernest A.

    1981-01-01

    The effect of chlorine concentration on Giardia lamblia cyst viability was tested under a variety of conditions. The ability of Giardia cysts to undergo excystation was used as the criterion of viability. The experimental variables employed included temperature (25, 15, and 5°C), pH (6, 7, and 8), chlorine-cyst contact time (10, 30, and 60 min), and chlorine concentration (1 to 8 mg/liter). In the pH range studied, cyst survival generally was observed to increase as buffer pH increased. Water...

  5. Nonaqueous chlorination of uranium metal in tributyl phosphate

    Buchikhin, E.P.; Kuznetsov, A.Yu.; Shatalov, V.V.; Vidanov, V.L.; Chekmarev, A.M.

    2005-01-01

    Low-temperature (30-50 deg C) chlorination of uranium metal in the TBP-TCE-Cl 2 system (TCE = tetrachloroethylene) was studied. Dissolution of uranium in the dipolar aprotic solvent proceeds with formation of U(IV) compounds. The activation energy of this process is 31.24 kJ mol -1 , and relative reaction order with respect to Cl 2 is 2. The effect of TBP concentration on chlorination was examined. The chlorination rate sharply increases at a water content in the TBP-TCE system of 0.2- 0.6 vol % [ru

  6. Analysis of temporal evolution of quantum dot surface chemistry by surface-enhanced Raman scattering.

    Doğan, İlker; Gresback, Ryan; Nozaki, Tomohiro; van de Sanden, Mauritius C M

    2016-07-08

    Temporal evolution of surface chemistry during oxidation of silicon quantum dot (Si-QD) surfaces were probed using surface-enhanced Raman scattering (SERS). A monolayer of hydrogen and chlorine terminated plasma-synthesized Si-QDs were spin-coated on silver oxide thin films. A clearly enhanced signal of surface modes, including Si-Clx and Si-Hx modes were observed from as-synthesized Si-QDs as a result of the plasmonic enhancement of the Raman signal at Si-QD/silver oxide interface. Upon oxidation, a gradual decrease of Si-Clx and Si-Hx modes, and an emergence of Si-Ox and Si-O-Hx modes have been observed. In addition, first, second and third transverse optical modes of Si-QDs were also observed in the SERS spectra, revealing information on the crystalline morphology of Si-QDs. An absence of any of the abovementioned spectral features, but only the first transverse optical mode of Si-QDs from thick Si-QD films validated that the spectral features observed from Si-QDs on silver oxide thin films are originated from the SERS effect. These results indicate that real-time SERS is a powerful diagnostic tool and a novel approach to probe the dynamic surface/interface chemistry of quantum dots, especially when they involve in oxidative, catalytic, and electrochemical surface/interface reactions.

  7. Structural study of chlorine tri-fluoride and bromine penta-fluoride in liquid and solid phase

    Rousson, R.

    1973-01-01

    This research thesis reports the structural study of chlorine tri-fluoride and bromine penta-fluoride between 20 C and about -265 C. After some generalities on these compounds and a presentation of the experimental technique, the author reports and discusses results obtained with these both compounds: Raman spectrum for the liquid and for the solid phase, infrared spectrum for the solid phase, calorimetric measurements. In the case of chlorine tri-fluoride, the author studies the evolution of the liquid spectrum with temperature, shows the existence of an intermediate solid phase, and compares results obtained by Raman spectroscopy and nuclear magnetic resonance. He also applies to bromine penta-fluoride an analysis of normal coordinates of a XF 5 molecule: relationship between force constants and vibration frequencies, application of Wilson method, resolution of the molecular equation, determination of normal vibration modes [fr

  8. Electrochemical destruction of nitrosamines

    Lejen, T; Volchek, K; Ladanowski, C; Velicogna, D; Whittaker, H [Environment Canada, Ottawa, ON (Canada). Emergencies Engineering Div.

    1996-09-01

    Treatment conditions for the electrolytic destruction of nitrosamines were studied. The joint investigation between Canada and the Ukraine was part of an assessment of hazardous contaminants at former Soviet ICBM missile sites. The electrochemical destruction of N-dimethylnitrosamines (NDMA) on carbon/platinum electrodes was studied under basic and acidic conditions by UV spectroscopy, gas chromatography, mass spectroscopy, and colorimetry. Experiments with a 100 ppm NDMA solution showed that electrolytic-reduction was pH sensitive within a range of pH 0.5 to 4.0. Electrolysis was effective for the reduction of NDMA in strong acidic conditions. 30 refs., 1 tab., 4 figs.

  9. Electrochemical Science and Technology

    Oldham, Keith; Bond, Alan

    2011-01-01

    The book addresses the scientific principles underlying electrochemistry. Starting with the basic concepts of electricity, the early chapters discuss the physics and chemistry of the materials from which electrochemical cells are constructed and the properties that make these materials appropriate as cell components. Much of the importance of electrochemistry lies in the conversion of electrical energy into chemical energy and vice versa; the thermodynamics of these processes is described, in the context of a wide range of applications of these interconversions. An electrode is a surface at wh

  10. Aqueous chemistry of chlorine: chemistry, analysis, and environmental fate of reactive oxidant species

    Jolley, R.L.; Carpenter, J.H.

    1982-01-01

    This report reviews (1) the chemistry of chlorine relative to its reactions in fresh, estuarine, and marine waters and the formation of reactive oxidant species; (2) the current status of chemical analysis of reactive chlorine species and chlorine-produced oxidant species relative to analysis of low concentrations (microgram-per-liter range) and determination of accuracy and precision of methods; and (3) the environmental fate of chlorine and chlorine-produced oxidant species.

  11. Assessing the Impact of Chlorinated-Solvent Sites on Metropolitan Groundwater Resources

    Brusseau, Mark L.; Narter, Matthew

    2013-01-01

    Chlorinated-solvent compounds are among the most common groundwater contaminants in the U.S.A. The majority of the many sites contaminated by chlorinated-solvent compounds are located in metropolitan areas, and most such areas have one or more chlorinated-solvent contaminated sites. Thus, contamination of groundwater by chlorinated-solvent compounds may pose a potential risk to the sustainability of potable water supplies for many metropolitan areas. The impact of chlorinated-solvent sites on...

  12. Chemical and Electrochemical Properties of La0.58Sr0.4Fe0.8Co0.2O3-δ (LSCF) Thin Films upon Oxygen Reduction and Evolution Reactions

    Pitscheider, Simon; Machala, Michael; Guan, Zixuan

    2017-01-01

    The Oxygen Evolution and Oxygen Reduction Reactions (OER/ORR), occurring at the oxygen electrode of Solid Oxide Cells (SOCs) in the two possible ways of operation, require substantial overpotentials, therefore lowering the operating efficiency of the cells. The reaction mechanisms occurring...... at these electrodes are still not completely understood due to their complexity and localized character at the interfaces between different materials or between the gas atmosphere and the electrocatalyst, and need in situ techniques with very high chemical sensitivity, with the additional difficulty of probing...... the materials as close as possible to their realistic operating conditions. In addition, the properties of LSCF are, despite numerous studies, still unclear in many aspects, despite LSCF being one of the state-of-the-art electrocatalysts used for SOCs. It is understood that the surface chemical composition...

  13. MICROEMULSION OF MIXED CHLORINATED SOLVENTS USING FOOD GRADE (EDIBLE) SURFACTANTS

    Ground water contamination frequently consists of mixed chlorinated solvents [e.g., tetrachloroethylene (PCE), trichloroethylene (TCE), and trans-1,2- dichloroethylene (DCE)]. In this research, mixtures of the food grade (edible) surfactants bis(2-ethylhexyl) sodium sulfosuccinat...

  14. Chlorine inactivation of fungal spores on cereal grains.

    Andrews, S; Pardoel, D; Harun, A; Treloar, T

    1997-04-01

    Although 0.4% chlorine for 2 min has been recommended for surface disinfection of food samples before direct plating for fungal enumeration, this procedure may not be adequate for highly contaminated products. The effectiveness of a range of chlorine solutions was investigated using barley samples artificially contaminated with four different concentrations of Aspergillus flavus. A. niger, A. ochraceus, Eurotium repens, Penicillium brevicompactum P. chrysogenum and Cladosporium cladosporioides. At initial contamination levels greater than 10(4)/g, 0.4% chlorine did not inactivate sufficient spores to produce less than 20% contamination. Of the test fungi, ascospores of E. repens were the most resistant to chlorine inactivation, whereas the conidia of C. cladosporioides were the most sensitive. Rinsing the samples with 70% ethanol improved the effectiveness of the recommended surface disinfection procedure. However, some ethanol appears to permeate into the grains and may inactivate sensitive internal fungi, although a minimal effect only was observed on wheat infected with Alternaria.

  15. CHLORINE INACTIVATION OF CATEGORY "A" BIO-TERRORISM AGENTS

    This poster presents information on the inactivation of select bioterrorist agents. Information will be presented on chlorine disinfection of vegetative cells of Brucella suis, Brucella melitensis, Burkholderia mallei, Burkholderia pseudomallei, Francisella tularensis and endos...

  16. In situ bioremediation of chlorinated solvent with natural gas

    Rabold, D.E.

    1996-01-01

    A bioremediation system for the removal of chlorinated solvents from ground water and sediments is described. The system involves the the in-situ injection of natural gas (as a microbial nutrient) through an innovative configuration of horizontal wells

  17. Determination of chlorine in graphite by combustion-ion chromatography

    Chen Lianzhong; Watanabe, Kazuo; Itoh, Mitsuo.

    1995-09-01

    A combustion/ion chromatographic method has been studied for the sensitive determination of chlorine in graphite. A graphite sample was burnt at 900degC in a silica reaction tube at an oxygen flow rate of 200 ml/min. Chlorine evolved was absorbed in 20 ml of a 0.1 mM sodium carbonate solution. The solution was evaporated to dryness. The residue was dissolved with a small volume of water. Chlorine in the solution was determined using ion chromatography. The method was applied to JAERI graphite certified reference materials and practical graphite materials. The detection limit was about 0.8 μgCl/g for a 2.0 g sample. The precision was about 2.5% (relative standard deviation) for samples with chlorine content of 70 μg/g level. The method is also usable for coal samples. (author)

  18. The chlorination kinetics of zirconium dioxide mixed with carbon black

    Movahedian, A.; Raygan, Sh.; Pourabdoli, M.

    2011-01-01

    In this research, the effects of chlorine gas at different chlorine partial pressures and carbon concentrations on the carbochlorination of zirconia were studied. It was found that in briquettes containing 18.7 %wt carbon, in a chlorine partial pressure range of 0.25-0.75 atm and for a reacted fraction of less than 0.7, the chemical reaction model was dominant for the carbochlorination process of zirconia. The order of reaction into chlorine gas (n) in this situation was 0.57. Moreover, the best weight ratio of carbon to zirconia was 40/60. In this case, the activation energy of the reaction was 209.9 kJ mol -1 in a temperature range of 1023-1223 K, and the dominant model was the chemical reaction model.

  19. Chlorination of zirconium (0001) surface: A first-principles study.

    Kim, Eunja [Univ. of Nevada, Las Vegas, NV (United States). Dept. of Physics and Astronomy; Weck, Philippe F [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Borjas, Rosendo [Univ. of Nevada, Las Vegas, NV (United States). Dept. of Chemistry; Poineau, Frederic [Univ. of Nevada, Las Vegas, NV (United States). Dept. of Chemistry

    2017-01-01

    Here, the mechanisms and energetics of Zr(0001) surface chlorination by dissociative adsorption of gaseous Cl2, and associated speciation and surface degradation processes, have been investigated within the framework of density functional theory. Chlorination of Zr(0001) is predicted to be exothermic by ~3 eV/Cl for dissociative adsorption of a single Cl2 molecule, followed by exothermic chlorination to 1ML and 2 ML under Cl-rich conditions, with respective energy gains of 1.93 and 2.79 eV/Cl. Calculations also show that exfoliation of the top Cl-Zr-Cl sandwich layers is exothermic and most energetically favorable, and can thus be considered as a leading mechanism for Zr(0001) surface dissolution. Consistent with experimental findings, formation of ZrCl4 molecular products is also found to be dominant during Zr(0001) chlorination.

  20. Chlorination of zirconium (0001) surface: A first-principles study

    Kim, E. [Univ. of Nevada, Las Vegas, NV (United States). Department of Physics and Astronomy; Weck, Philippe F [Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Poineau, F. [Univ. of Nevada, Las Vegas, NV (United States). Department of Chemistry; Paviet, P. [Dept. of Energy (DOE), Washington DC (United States)

    2016-12-13

    The mechanisms and energetics of Zr(0001) surface chlorination by dissociative adsorption of gaseous Cl2, and associated speciation and surface degradation processes, have been investigated within the framework of density functional theory. Chlorination of Zr(0001) is predicted to be exothermic by 3 eV/Cl for dissociative adsorption of a single Cl2 molecule, followed by exothermic chlorination to 1ML and 2 ML under Cl-rich conditions, with respective energy gains of 1.93 and 2.79 eV/Cl. Calculations also show that exfoliation of the top Cl-Zr-Cl sandwich layers is exothermic and most energetically favorable, and can thus be considered as a leading mechanism for Zr(0001) surface dissolution. Finally, consistent with experimental findings, formation of ZrCl4 molecular products is also found to be dominant during Zr(0001) chlorination.

  1. Submarine Biofouling Control- Chlorination DATS Study at Pearl Harbor

    Wegand, John

    2001-01-01

    The intent of this document is to sumarize the chlorination studies performed at Naval Station, Pearl Harbor in support of biofouling control initiatives for the submarine community, as requested by NAVSEA 92T...

  2. Chlorinated rubbers with advanced properties for tire industry

    Mikhaylov, I. A.; Sukhareva, K. V.; Andriasyan, Yu. O.; Popov, A. A.

    2017-12-01

    The paper investigates the production and processing of halide-modified chlorinated rubbers, such as isobutylene isoprene rubber and ethylene-propylene-diene-monomer rubber (IIR and EPDM), which are perspective in terms of application in rubber industry. Prospects for their production and application are determined by the specific properties of these rubbers (low gas permeability of IIR, high heat and ozone resistance of EPDM). These properties are governed by the structure of both initial IIR and EPDM and chlorinated rubbers (ChIIR and ChEPDM). A new alternative technology of obtaining chlorinated elastomers based on solid-phase mechanochemical halide modification is proposed. Novel chlorinated polyolefin rubbers obtained by the developed technology show good technological properties under industrial production conditions due to enhanced covulcanization.

  3. Characters of chlorine isotopic composition in ocean water

    Xiao, Y.; Zhou, Y.; Liu, W.G.; Hong, A.; Wang, Q.; Wang, Y.; Wei, H.; Shirodkar, P.V.

    The chlorine isotopic composition of ocean water was determined using thermal ionization mass spectrometry based on the measurement of Cs sub(2) Cl sup(+) ion. The results show that the sup(37) Cl/ sup(35) Cl ratios are basically homogeneous...

  4. Bioremediation of chlorinated ethenes in aquifer thermal energy storage

    Ni, Z.

    2015-01-01

    Subjects: bioremediation; biodegradation; environmental biotechnology, subsurface and groundwater contamination; biological processes; geochemistry; microbiology

    The combination of enhanced natural attenuation (ENA) of chlorinated volatile organic compounds

  5. Electrochemical photovoltaic cells and electrodes

    Skotheim, Terje A.

    1984-01-01

    Improved electrochemical photovoltaic cells and electrodes for use therein, particularly electrodes employing amorphous silicon or polyacetylene coating are produced by a process which includes filling pinholes or porous openings in the coatings by electrochemical oxidation of selected monomers to deposit insulating polymer in the openings.

  6. Thermodynamics of irreversible electrochemical phenomena

    Groot, S.R. de; Mazur, P.; Tolhoek, H.A.

    1953-01-01

    A discussion from first principles is given of the energy and entropy laws in electrochemical systems. It is found that it is possible to clarify such controversial concepts as the form of the second law and the role of the electrochemical potential in the systems concerned.

  7. Fate of free chlorine in drinking water during distribution in premise plumbing.

    Zheng, Muzi; He, Chunguang; He, Qiang

    2015-12-01

    Free chlorine is a potent oxidizing agent and has been used extensively as a disinfectant in processes including water treatment. The presence of free chlorine residual is essential for the prevention of microbial regrowth in water distribution systems. However, excessive levels of free chlorine can cause adverse health effects. It is a major challenge to maintain appropriate levels of free chlorine residual in premise plumbing. As the first effort to assessing the fate of chlorine in premise plumbing using actual premise plumbing pipe sections, three piping materials frequently used in premise plumbing, i.e. copper, galvanized iron, and polyvinyl chloride (PVC), were investigated for their performance in maintaining free chlorine residual. Free chlorine decay was shown to follow first-order kinetics for all three pipe materials tested. The most rapid chlorine decay was observed in copper pipes, suggesting the need for higher chlorine dosage to maintain appropriate levels of free chlorine residual if copper piping is used. PVC pipes exhibited the least reactivity with free chlorine, indicative of the advantage of PVC as a premise plumbing material for maintaining free chlorine residual. The reactivity of copper piping with free chlorine was significantly hindered by the accumulation of pipe deposits. In contrast, the impact on chlorine decay by pipe deposits was not significant in galvanized iron and PVC pipes. Findings in this study are of great importance for the development of effective strategies for the control of free chlorine residual and prevention of microbiological contamination in premise plumbing.

  8. Electrochemical impedance study of copper in phosphate buffered solution

    Salimon, J.; Mohamad, M.; Yamin, B.M.; Kalaji, M.

    2003-01-01

    The processes occurring on the copper electrode surface in phosphate buffered solution were investigated using the Electrochemical Impedance Spectroscopy. The electrochemical behaviors of copper through their charge transfer resistance and double-layer capacitance at the onset of the hydrogen evolution region and the anodic passivation layer formation and diffusion of copper species at anodic potential regions are discussed. The specific adsorption of anions (hydroxide and/or H/sub 2/PO/sub 4/) occurred at potential less negative than -0.9V. Adsorbed hydrogen appeared at hydrogen evolution region at potential range of -1.5 to -1.0 V. The deposition of insoluble copper species occurred at anodic potential regions. (author)

  9. Bio-remediation of aquifers polluted by chlorinated solvents

    Fayolle, F.

    1996-01-01

    Numerous cases of contamination of aquifers by chlorinated aliphatic solvents, largely utilized during the last decades, constitute a public health problem, because of the toxic effect of such compounds. Different types of aerobic or anaerobic bacteria are able to degrade these molecules. Processes of bio remediation are now experimented in order to restore polluted aquifers. We present here the microorganisms and the enzymatic reactions involved in the biodegradation of chlorinated solvents, and different examples of in situ bio remediation operations are described. (author)

  10. The chlorine-36 dating program at the Australian National University

    Fifield, L.F.; Ophel, T.R.; Bird, J.R.; Calf, G.E.; Allison, G.B.; Chivas, A.R.

    1987-05-01

    A chlorine-36 dating capability based on the 14UD pelletron accelerator was developed at the Australian National University during 1986 and is now entering the routine measurement phase. It involves a collaboration between the Department of Nuclear Physics, the Australian Atomic Energy Commission and CSIRO Division of Soils. The chlorine-36 dating system is described and some early results are presented for samples of chloride from salt lakes in Western Australia and soil profiles in South Australia

  11. Decomposition of dilute residual active chlorine in sea-water

    Yoshinaga, Tetsutaro; Kawano, Kentaro; Yanagase, Kenjiro; Shiga, Akira

    1985-01-01

    Coastal industries such as power stations require enormous quantities of sea-water for cooling, but the marine organisms in it often result in fouling and/or blockade of the circulating water condenser and pipeworks. To prevent this, chlorine, or hypochlorite by the direct electrolysis of sea-water have been added. Environmental concerns, however, dictate that the residual chlorine concentration at the outlet should be less than the regulated value (0.02 ppm). Methods for decomposing dilute residual chlorine solutions were therefore studied. It was found that: 1) The addition of (raw) sea-water to the sea-water which passed through the condenser lowered the residual chlorine concentration to an greater extent than could be expected by dilution only. 2) Ozonation of the residual chlorine solution led to degradation of OCl - , but in solutions with a residual chlorine concentrations of less than 3 -- 4 ppm, ozonation had no effect. 3) Irradiation with ultra violet light (254 nm) decomposed the residual chlorine. Under the present work conditions (25 0 C: pH 8; depth 10 mm), nearly first order kinetics were to hold [da/dt = ksub((1)) (1-a)sup(n)]. There is a proportional relationship between the kinetic constant (k) and illuminous intensity (L), i.e., ksub((1))[C 0 sup(Cl 2 ): 10 ppm] = 6.56 x 10 -5 L (L = 0 -- 1000 lx). Thus, the use of both sea-water addition and UV irradiation provides a probable method for decomposing a residual chlorine to the expected concentration. (author)

  12. Degradation of Nicotine in Chlorinated Water: Pathways and ...

    Report The objective of the study is to illustrate how drinking water would affect alkaloid pesticides, and to address the issue by (a) investigating the fate of nicotine in chlorinated drinking water and deionized water, (b) determining the reaction rate and pathway of the reaction between nicotine and aqueous chlorine, (c) identifying nicotine’s degradation products, and (d) providing data that can be used to assess the potential threat from nicotine in drinking water.

  13. Epidemiological evidence of carcinogenicity of chlorinated organics in drinking water.

    Cantor, K P

    1982-01-01

    Concern has recently been voiced over possible chronic toxicity associated with chlorination of public drinking water supplies in the United States. This paper reviews the available evidence and the studies underway to further evaluate hypothesized associations between cancer risk and byproducts of chlorination. Preliminary data from measures of halogenated volatiles and personal exposure histories from respondents in a large epidemiologic study of bladder cancer are presented. These data sup...

  14. Electrochemical biosensors for hormone analyses.

    Bahadır, Elif Burcu; Sezgintürk, Mustafa Kemal

    2015-06-15

    Electrochemical biosensors have a unique place in determination of hormones due to simplicity, sensitivity, portability and ease of operation. Unlike chromatographic techniques, electrochemical techniques used do not require pre-treatment. Electrochemical biosensors are based on amperometric, potentiometric, impedimetric, and conductometric principle. Amperometric technique is a commonly used one. Although electrochemical biosensors offer a great selectivity and sensitivity for early clinical analysis, the poor reproducible results, difficult regeneration steps remain primary challenges to the commercialization of these biosensors. This review summarizes electrochemical (amperometric, potentiometric, impedimetric and conductometric) biosensors for hormone detection for the first time in the literature. After a brief description of the hormones, the immobilization steps and analytical performance of these biosensors are summarized. Linear ranges, LODs, reproducibilities, regenerations of developed biosensors are compared. Future outlooks in this area are also discussed. Copyright © 2014 Elsevier B.V. All rights reserved.

  15. SCENARIOS EVALUATION TOOL FOR CHLORINATED SOLVENT MNA

    Vangelas, K; Brian02 Looney, B; Michael J. Truex; Charles J. Newell

    2006-08-16

    Over the past three decades, much progress has been made in the remediation of chlorinated solvents from the subsurface. Yet these pervasive contaminants continue to present a significant challenge to the U.S. Department of Energy (DOE), other federal agencies, and other public and private organizations. The physical and chemical properties of chlorinated solvents make it difficult to rapidly reach the low concentrations typically set as regulatory limits. These technical challenges often result in high costs and long remediation time frames. In 2003, the DOE through the Office of Environmental Management funded a science-based technical project that uses the U.S. Environmental Protection Agency's technical protocol (EPA, 1998) and directives (EPA, 1999) on Monitored Natural Attenuation (MNA) as the foundation on which to introduce supporting concepts and new scientific developments that will support remediation of chlorinated solvents based on natural attenuation processes. This project supports the direction in which many site owners want to move to complete the remediation of their site(s), that being to complete the active treatment portion of the remedial effort and transition into MNA. The overarching objective of the effort was to examine environmental remedies that are based on natural processes--remedies such as Monitored Natural Attenuation (MNA) or Enhanced Attenuation (EA). The research program did identify several specific opportunities for advances based on: (1) mass balance as the central framework for attenuation based remedies, (2) scientific advancements and achievements during the past ten years, (3) regulatory and policy development and real-world experience using MNA, and (4) exploration of various ideas for integrating attenuation remedies into a systematic set of ''combined remedies'' for contaminated sites. These opportunities are summarized herein and are addressed in more detail in referenced project documents and

  16. Prompt gamma analysis of chlorine in concrete for corrosion study

    Naqvi, A.A. [Department of Physics, King Fahd University of Petroleum and Minerals, Dhahran 31261 (Saudi Arabia)]. E-mail: aanaqvi@kfupm.edu.sa; Nagadi, M.M. [Department of Physics, King Fahd University of Petroleum and Minerals, Dhahran 31261 (Saudi Arabia); Al-Amoudi, O.S.B. [Department of Civil Engineering, King Fahd University of Petroleum and Minerals, Dhahran 31261 (Saudi Arabia)

    2006-02-15

    Measurement of chlorine in concrete is very important for studying of corrosion of reinforcing steel in concrete. Corrosion of reinforcing steel is primarily ascribed to the penetration of chloride ions to the steel surface. Preventive measures for avoiding concrete structure reinforcement corrosion requires monitoring the chloride ion concentration in concrete so that its concentration does not exceed a threshold limit to initiate reinforcement concrete corrosion. An accelerator based prompt gamma neutron activation analysis (PGNAA) setup has been developed for non-destructive analysis of elemental composition of concrete samples. The setup has been used to measure chlorine concentration in concrete samples over a 1-3 wt% concentration range. Although a strong interference has been observed between the chlorine {gamma}-rays and calcium {gamma}-rays from concrete, the chlorine concentration in concrete samples has been successfully measured using the 1.164 and 7.643 MeV chlorine {gamma}-rays. The experimental data were compared with the results of the Monte Carlo simulations. An excellent agreement has been achieved between the experimental data and results of Monte Carlo simulations. The study has demonstrated the successful use of the accelerator-based PGNAA setup in non-destructive analysis of chlorine in concrete samples.

  17. Carboranyl-Chlorin e6 as a Potent Antimicrobial Photosensitizer.

    Elena O Omarova

    Full Text Available Antimicrobial photodynamic inactivation is currently being widely considered as alternative to antibiotic chemotherapy of infective diseases, attracting much attention to design of novel effective photosensitizers. Carboranyl-chlorin-e6 (the conjugate of chlorin e6 with carborane, applied here for the first time for antimicrobial photodynamic inactivation, appeared to be much stronger than chlorin e6 against Gram-positive bacteria, such as Bacillus subtilis, Staphyllococcus aureus and Mycobacterium sp. Confocal fluorescence spectroscopy and membrane leakage experiments indicated that bacteria cell death upon photodynamic treatment with carboranyl-chlorin-e6 is caused by loss of cell membrane integrity. The enhanced photobactericidal activity was attributed to the increased accumulation of the conjugate by bacterial cells, as evaluated both by centrifugation and fluorescence correlation spectroscopy. Gram-negative bacteria were rather resistant to antimicrobial photodynamic inactivation mediated by carboranyl-chlorin-e6. Unlike chlorin e6, the conjugate showed higher (compared to the wild-type strain dark toxicity with Escherichia coli ΔtolC mutant, deficient in TolC-requiring multidrug efflux transporters.

  18. Susceptibility of Legionella pneumophila to chlorine in tap water.

    Kuchta, J M; States, S J; McNamara, A M; Wadowsky, R M; Yee, R B

    1983-11-01

    A study was conducted to compare the susceptibility of legionellae and coliforms to disinfection by chlorine. The chlorine residuals used were similar to concentrations that might be found in the distribution systems of large public potable water supplies. The effects of various chlorine concentrations, temperatures, and pH levels were considered. A number of different Legionella strains, both environmental and clinical, were tested. The results indicate that legionellae are much more resistant to chlorine than are coliform bacteria. At 21 degrees C, pH 7.6, and 0.1 mg of free chlorine residual per liter, a 99% kill of L. pneumophila was achieved within 40 min, compared with less than 1 min for Escherichia coli. The observed resistance is enhanced as conditions for disinfection become less optimal. The required contact time for the removal of L. pneumophilia was twice as long at 4 degrees C than it was at 21 degrees C. These data suggest that legionellae can survive low levels of chlorine for relatively long periods of time.

  19. Quantifying Short-Chain Chlorinated Paraffin Congener Groups.

    Yuan, Bo; Bogdal, Christian; Berger, Urs; MacLeod, Matthew; Gebbink, Wouter A; Alsberg, Tomas; de Wit, Cynthia A

    2017-09-19

    Accurate quantification of short-chain chlorinated paraffins (SCCPs) poses an exceptional challenge to analytical chemists. SCCPs are complex mixtures of chlorinated alkanes with variable chain length and chlorination level; congeners with a fixed chain length (n) and number of chlorines (m) are referred to as a "congener group" C n Cl m . Recently, we resolved individual C n Cl m by mathematically deconvolving soft ionization high-resolution mass spectra of SCCP mixtures. Here we extend the method to quantifying C n Cl m by introducing C n Cl m specific response factors (RFs) that are calculated from 17 SCCP chain-length standards with a single carbon chain length and variable chlorination level. The signal pattern of each standard is measured on APCI-QTOF-MS. RFs of each C n Cl m are obtained by pairwise optimization of the normal distribution's fit to the signal patterns of the 17 chain-length standards. The method was verified by quantifying SCCP technical mixtures and spiked environmental samples with accuracies of 82-123% and 76-109%, respectively. The absolute differences between calculated and manufacturer-reported chlorination degrees were -0.9 to 1.0%Cl for SCCP mixtures of 49-71%Cl. The quantification method has been replicated with ECNI magnetic sector MS and ECNI-Q-Orbitrap-MS. C n Cl m concentrations determined with the three instruments were highly correlated (R 2 > 0.90) with each other.

  20. Electrochemically adsorbed Pb on Ag (111) studied with grazing- incidence x-ray scattering

    Kortright, J.B.; Ross, P.N.; Melroy, O.R.; Toney, M.F.; Borges, G.L.; Samant, M.G.

    1989-04-01

    Grazing-incidence x-ray scattering studies of the evolution of electrochemically deposited layers of lead on silver (111) as a function of applied electrochemical potential are presented. Measurements were made with the adsorbed layers in contact with solution in a specially designed sample cell. The observed lead structures are a function of the applied potential and range from an incommensurate monolayer, resulting from underpotential deposition, to randomly oriented polycrystalline bulk lead, resulting from lower deposition potentials. These early experiments demonstrate the ability of in situ x-ray diffraction measurements to determine structures associated with electrochemical deposition. 6 refs., 4 figs

  1. Tracking polaron generation in electrochemically doped polyaniline thin films

    Kalagi, S. S.; Patil, P. S.

    2018-04-01

    Electrochemically deposited polyaniline films on ITO substrates have been studied for their optical properties. π-π*transitions inducing the formation of polarons and bipolarons have been studied from the optical spectra. The generation of these quasiparticles and the corresponding quantum of energy stored has been analysed and calculated from the experimental data. The evolution of polaron with increased levels of protonation has been identified and the necessary energy required for the transitions have been explained with the help of band structure diagram.

  2. Pulsed Electrochemical Mass Spectrometry for Operando Tracking of Interfacial Processes in Small-Time-Constant Electrochemical Devices such as Supercapacitors.

    Batisse, Nicolas; Raymundo-Piñero, Encarnación

    2017-11-29

    A more detailed understanding of the electrode/electrolyte interface degradation during the charging cycle in supercapacitors is of great interest for exploring the voltage stability range and therefore the extractable energy. The evaluation of the gas evolution during the charging, discharging, and aging processes is a powerful tool toward determining the stability and energy capacity of supercapacitors. Here, we attempt to fit the gas analysis resolution to the time response of a low-gas-generation power device by adopting a modified pulsed electrochemical mass spectrometry (PEMS) method. The pertinence of the method is shown using a symmetric carbon/carbon supercapacitor operating in different aqueous electrolytes. The differences observed in the gas levels and compositions as a function of the cell voltage correlate to the evolution of the physicochemical characteristics of the carbon electrodes and to the electrochemical performance, giving a complete picture of the processes taking place at the electrode/electrolyte interface.

  3. Differences in the electrochemical behavior of ruthenium and iridium oxide in electrocatalytic coatings of activated titanium anodes prepared by the sol–gel procedure

    VLADIMIR V. PANIĆ

    2010-10-01

    Full Text Available The electrochemical characteristics of Ti0.6Ir0.4O2/Ti and Ti0.6Ru0.4O2/Ti anodes prepared by the sol–gel procedure from the corresponding oxide sols, obtained by force hydrolysis of the corresponding metal chlorides, were compared. The voltammetric properties in H2SO4 solution indicate that Ti0.6Ir0.4O2/Ti has more pronounced pseudocapacitive characteristics, caused by proton-assisted, solid state surface redox transitions of the oxide. At potentials negative to 0.0 VSCE, this electrode is of poor conductivity and activity, while the voltammetric behavior of the Ti0.6Ru0.4O2/Ti electrode is governed by proton injection/ejection into the oxide structure. The Ti0.6Ir0.4O2/Ti electrode had a higher electrocatalytical activity for oxygen evolution, while the investigated anodes were of similar activity for chlorine evolution. The potential dependence of the impedance characteristics showed that the Ti0.6Ru0.4O2/Ti electrode behaved like a capacitor over a wider potential range than the Ti0.6Ir0.4O2/Ti electrode, with fully-developed pseudocapacitive properties at potentials positive to 0.60 VSCE. However, the impedance characteristics of the Ti0.6Ir0.4O2/Ti electrode changed with increasing potential from resistor-like to capacitor-like behavior.

  4. Site-selective photofragmentation of chlorinated polymeric films observed around the chlorine K-edge

    Arantes, C., E-mail: csilva@inmetro.gov.br [Divisão de Metrologia de Materiais, Instituto Nacional de Metrologia, Qualidade e Tecnologia, Xerém 25250-020, Duque de Caxias, RJ (Brazil); Mendes, L.A.V. [Instituto de Física, Universidade Federal da Bahia, Ondina, 40210-340 Salvador, BA (Brazil); Pinho, R.R. [Departamento de Física-ICE, Universidade Federal de Juiz de Fora, Campus Universitário, 36036-330 Juiz de Fora, MG (Brazil); Ferreira, M. [PEMM/COPPE, Universidade Federal do Rio de Janeiro, Cidade Universitária, Ilha do Fundão, 21941-972 Rio de Janeiro, RJ (Brazil); Souza, G.G.B. de; Rocha, A.B.; Rocco, M.L.M. [Instituto de Química, Universidade Federal do Rio de Janeiro, Cidade Universitária, Ilha do Fundão, 21941-909 Rio de Janeiro, RJ (Brazil)

    2013-03-29

    Highlights: ► PVC and PVDC were studied by PSID and NEXAFS techniques at the Chlorine 1s-edge. ► PVC film presented isotope ratio of 3:1 in the PSID spectrum. ► Cl{sup +} ion yield curves reproduce the photoabsorption spectrum for both polymers. ► Site-selectivity of C–Cl bond breaking due to an efficient spectator Auger decay. - Abstract: Photon stimulated ion desorption (PSID) and Near-edge X-ray absorption fine structure (NEXAFS) studies have been performed on poly(vinyl chloride) (PVC) and poly(vinyl dichloride) (PVDC) around the chlorine 1s-edge. Experiments were performed using a synchrotron source operating in the single-bunch mode and a time-of-flight mass spectrometry for ion analysis. Cl{sup +} ion yields, as a function of the photon energy, reproduce the photoabsorption spectrum, showing significant increase at the 1s-resonance. Edge-jump ratios, defined as the ratio between edge-jumps (intensity ratio of the yields between above and below the absorption edge) of two different transitions, for Cl{sup +} ion yields were much higher than the equivalent electron yields, indicating site-selectivity in C–Cl bond breaking for both polymers, as a result of efficient spectator Auger decay. The expected isotope ratio of 3:1 for chlorine was measured for PVC. The interpretation of the NEXAFS spectrum was assisted by quantum mechanical calculations at a multireference perturbation theory level.

  5. Electrochemical hydrogen Storage Systems

    Dr. Digby Macdonald

    2010-08-09

    As the global need for energy increases, scientists and engineers have found a possible solution by using hydrogen to power our world. Although hydrogen can be combusted as a fuel, it is considered an energy carrier for use in fuel cells wherein it is consumed (oxidized) without the production of greenhouse gases and produces electrical energy with high efficiency. Chemical storage of hydrogen involves release of hydrogen in a controlled manner from materials in which the hydrogen is covalently bound. Sodium borohydride and aminoborane are two materials given consideration as chemical hydrogen storage materials by the US Department of Energy. A very significant barrier to adoption of these materials as hydrogen carriers is their regeneration from 'spent fuel,' i.e., the material remaining after discharge of hydrogen. The U.S. Department of Energy (DOE) formed a Center of Excellence for Chemical Hydrogen Storage, and this work stems from that project. The DOE has identified boron hydrides as being the main compounds of interest as hydrogen storage materials. The various boron hydrides are then oxidized to release their hydrogen, thereby forming a 'spent fuel' in the form of a lower boron hydride or even a boron oxide. The ultimate goal of this project is to take the oxidized boron hydrides as the spent fuel and hydrogenate them back to their original form so they can be used again as a fuel. Thus this research is essentially a boron hydride recycling project. In this report, research directed at regeneration of sodium borohydride and aminoborane is described. For sodium borohydride, electrochemical reduction of boric acid and sodium metaborate (representing spent fuel) in alkaline, aqueous solution has been investigated. Similarly to literature reports (primarily patents), a variety of cathode materials were tried in these experiments. Additionally, approaches directed at overcoming electrostatic repulsion of borate anion from the cathode, not

  6. Electrochemical hydrogen Storage Systems

    Macdonald, Digby

    2010-01-01

    As the global need for energy increases, scientists and engineers have found a possible solution by using hydrogen to power our world. Although hydrogen can be combusted as a fuel, it is considered an energy carrier for use in fuel cells wherein it is consumed (oxidized) without the production of greenhouse gases and produces electrical energy with high efficiency. Chemical storage of hydrogen involves release of hydrogen in a controlled manner from materials in which the hydrogen is covalently bound. Sodium borohydride and aminoborane are two materials given consideration as chemical hydrogen storage materials by the US Department of Energy. A very significant barrier to adoption of these materials as hydrogen carriers is their regeneration from 'spent fuel,' i.e., the material remaining after discharge of hydrogen. The U.S. Department of Energy (DOE) formed a Center of Excellence for Chemical Hydrogen Storage, and this work stems from that project. The DOE has identified boron hydrides as being the main compounds of interest as hydrogen storage materials. The various boron hydrides are then oxidized to release their hydrogen, thereby forming a 'spent fuel' in the form of a lower boron hydride or even a boron oxide. The ultimate goal of this project is to take the oxidized boron hydrides as the spent fuel and hydrogenate them back to their original form so they can be used again as a fuel. Thus this research is essentially a boron hydride recycling project. In this report, research directed at regeneration of sodium borohydride and aminoborane is described. For sodium borohydride, electrochemical reduction of boric acid and sodium metaborate (representing spent fuel) in alkaline, aqueous solution has been investigated. Similarly to literature reports (primarily patents), a variety of cathode materials were tried in these experiments. Additionally, approaches directed at overcoming electrostatic repulsion of borate anion from the cathode, not described in the

  7. Inactivation of antibiotic resistance genes in municipal wastewater effluent by chlorination and sequential UV/chlorination disinfection

    Zhang, Yingying; Zhuang, Yao; Geng, Jinju, E-mail: jjgeng@nju.edu.cn; Ren, Hongqiang, E-mail: hqren@nju.edu.cn; Zhang, Yan; Ding, Lili; Xu, Ke

    2015-04-15

    This study investigated disinfection methods including chlorination, ultraviolet (UV) irradiation and sequential UV/chlorination treatment on the inactivation of antibiotic resistance genes (ARGs). ARGs including sul1, tetX, tetG, intI1, and 16S rRNA genes in municipal wastewater treatment plant (MWTP) effluent were examined. The results indicated a positive correlation between the removal of ARGs and chlorine dosage (p = 0.007–0.014, n = 6),as well as contact time (p = 0.0001, n = 10). Greater free chlorine (FC) dosage leads to higher removal for all the genes and the maximum removal (1.30–1.49 logs) could be achieved at FC dosage of 30 mg L{sup −1}. The transformation kinetic data for ARGs removal (log C{sub 0} / C) followed the second-order reaction kinetic model with FC dosage (R{sup 2} = 0.6829–0.9999) and contact time (R{sup 2} = 0.7353–8634), respectively. Higher ammonia nitrogen (NH{sub 3}–N) concentration was found to lead to lower removal of ARGs at the same chlorine dosage. When the applied Cl{sub 2}:NH{sub 3}–N ratio was over 7.6:1, a significant reduction of ARGs (1.20–1.49 logs) was achieved. By using single UV irradiation, the log removal values of tetX and 16Ss rRNA genes were 0.58 and 0.60, respectively, while other genes were 0.36–0.40 at a fluence of 249.5 mJ cm{sup −2}, which was observed to be less effective than chlorination. With sequential UV/chlorination treatment, 0.006 to 0.31 log synergy values of target genes were observed under different operation parameters. - Highlights: • Chlorine is more effective than UV irradiation in removing ARGs from MWTP effluent. • The chlorination reaction followed the second-order reaction kinetic model. • Higher NH{sub 3}–N contents result in lower ARGs removal in the chlorination process. • FC is more effective than CC on the inactivation of ARGs. • UV irradiation followed by chlorination shows high efficiency in removing ARGs.

  8. Electrochemical Synthesis, Structure Elucidation and Antibacterial Evaluation of 9a-aza-9a-chloro-9a-homoerythromycin A

    Zoran Mandic

    2014-09-01

    Full Text Available Electrochemical synthesis, structure elucidation and antibacterial evaluation of 9a-aza-9a-chloro-9a-homoerythromycin A were carried out. It was found that the anodic oxidation of 9a-aza-9a-homoerythromycin A via electrogenerated reactive chlorine species leads to the chlorination of lactam nitrogen in high yield provided the pH of the reaction mixture is maintained above 3. NOESY spectra reveal the existence of the mixture of two conformational families in the solution, the "folding-out" conformer being slightly more abundant comparing to 9a-Aza-9a-homoerythromycin A. The chlorine substitution of lactam hydrogen resulted in improved antimicrobial potency against Sreptococcus pyogenes PSCB0542, Moraxella catarrhalis ATCC 25238, Haemophilus  influenzae ATCC 49247 and Enteroccocus faecalis ATCC 29212.

  9. Electrochemical alkaline Fe(VI) water purification and remediation.

    Licht, Stuart; Yu, Xingwen

    2005-10-15

    Fe(VI) is an unusual and strongly oxidizing form of iron, which provides a potentially less hazardous water-purifying agent than chlorine. A novel on-line electrochemical Fe(VI) water purification methodology is introduced. Fe(VI) addition had been a barrier to its effective use in water remediation, because solid Fe(VI) salts require complex (costly) syntheses steps and solutions of Fe(VI) decompose. Online electrochemical Fe(VI) water purification avoids these limitations, in which Fe(VI) is directly prepared in solution from an iron anode as the FeO42- ion, and is added to the contaminant stream. Added FeO42- decomposes, by oxidizing a wide range of water contaminants including sulfides (demonstrated in this study) and other sulfur-containing compounds, cyanides (demonstrated in this study), arsenic (demonstrated in this study), ammonia and other nitrogen-containing compounds (previously demonstrated), a wide range of organics (phenol demonstrated in this study), algae, and viruses (each previously demonstrated).

  10. Synthesis, photophysical and electrochemical properties of water–soluble phthalocyanines bearing 8-hydroxyquinoline-5-sulfonicacid derivatives

    Günsel, Armağan; Kocabaş, Sibel; Bilgiçli, Ahmet T. [Department of Chemistry, Sakarya University, 54140 Esentepe, Sakarya (Turkey); Güney, Sevgi [Department of Chemistry, Istanbul Technical University, 34469 Maslak, Istanbul (Turkey); Kandaz, Mehmet, E-mail: mkandaz@sakarya.edu.tr [Department of Chemistry, Sakarya University, 54140 Esentepe, Sakarya (Turkey)

    2016-08-15

    We have presented in this paper, the synthesis, characterization, photophysical properties and electrochemical characterization of water soluble phthalocyanines (Pcs) bearing 8-hydroxyquinoline-5-sulfonicacid conjugates and their cationic quaternized counterpart that play important roles their application in photodynamic therapy (PDT). The periphery and non-periphery substituted phthalocyanines show high solubility and low aggregation tendency due to bulky 8-hydroxyquinoline-5-sulfonicacid steric hindrance moieties and axially bound counter chlorine anion. Singlet oxygen quantum yields, photodegradation quantum yields, photophysical properties and also the nature of the substituent and solvent effect on the photophysical and photochemical parameters of α-ZnPc and β-ZnPc are reported. In electrovalent cobalt (II) and manganese (III) compounds, metal based electron transfer reactions have been observed in addition to the common phthalocyanine ring-based electron transfer processes. The effect of point of substitution on the electrochemical properties of newly synthesized phthalocyanines substituted with 8-hydroxyquinoline-5-sulfonicacid group were evaluated.

  11. Reductive dechlorination of chlorinated solvents in landfills

    Wang, J.Y.; Wu, C.

    2002-01-01

    The use of landfills as an in situ biological treatment system represents an alternative for source area remediation with a significant cost saving. The specific objective of this research is to investigate the intrinsic bioattenuation capacity of the landfill ecosystem for chlorinated aliphatic hydrocarbons (CAHs). The research was conducted in two complementary systems: simulated landfill bioreactors and batch degradation experiment in serum bottles. Refuse samples excavated from a landfill were tested in laboratory bioreactors designed and operated to facilitate refuse decomposition under landfilling conditions. Each bioreactor was operated with leachate recirculation and gas collection. Target CAHs, tetrachloroethene (PCE) and trichloroethene (TCE), were added to selected reactors and maintained at 20 μM each in leachate to simulate the effect of long-term exposure of refuse microorganisms to CAHs on the degradation potential of these chemicals in landfills. At two different stages of refuse decomposition, active refuse decomposition representing young landfills and maturation phase representing aged landfills, anaerobic microbial cultures were derived from selected bioreactors and tested in serum bottles for their abilities to biodegrade target CAHs. Results of this study suggest that landfills have an intrinsic reductive dechlorination capacity for PCE and TCE. The decomposition of refuse, a source of complex organics, enhances reductive dechlorination by the refuse cultures tested in this study. In addition, the test results suggest that it may be possible to develop engineering strategies to promote both CAHs degradation and refuse decomposition in landfills. (author)

  12. Inactivation of Mycobacterium avium with free chlorine.

    Luh, Jeanne; Mariñas, Benito J

    2007-07-15

    The inactivation kinetics of Mycobacterium avium with free chlorine was characterized by two stages: an initial phase at a relatively fast rate followed by a slower second stage of pseudo first-order kinetics. The inactivation rate of each stage was approximately the same for all experiments performed at a certain condition of pH and temperature; however, variability was observed for the disinfectant exposure at which the transition between the two stages occurred. This variability was not a function of the initial disinfectant concentration, the initial bacterial density, or the bacterial stock. However, the transition to the second stage varied more significantly at high temperatures (30 degrees C), while lower variability was observed at lower temperatures (5 and 20 degrees C). Experiments conducted at pH values in the range of 6-9 revealed that the inactivation of M. avium was primarily due to hypochlorous acid, with little contribution from hypochlorite ion within this pH range. The inactivation kinetics was represented with a two-population model. The activation energies for the resulting pseudo first-order rate constants for the populations with fast and slow kinetics were 100.3 and 96.5 kJ/mol, respectively. The magnitude of these values suggested that for waters of relatively high pH and low temperatures, little inactivation of M. avium would be achieved within treatment plants, providing a seeding source for distribution systems.

  13. Tolerance of anaerobic bacteria to chlorinated solvents.

    Koenig, Joanna C; Groissmeier, Kathrin D; Manefield, Mike J

    2014-01-01

    The aim of this research was to evaluate the effects of four chlorinated aliphatic hydrocarbons (CAHs), perchloroethene (PCE), carbon tetrachloride (CT), chloroform (CF) and 1,2-dichloroethane (1,2-DCA), on the growth of eight anaerobic bacteria: four fermentative species (Escherichia coli, Klebsiella sp., Clostridium sp. and Paenibacillus sp.) and four respiring species (Pseudomonas aeruginosa, Geobacter sulfurreducens, Shewanella oneidensis and Desulfovibrio vulgaris). Effective concentrations of solvents which inhibited growth rates by 50% (EC50) were determined. The octanol-water partition coefficient or log Po/w of a CAH proved a generally satisfactory measure of its toxicity. Most species tolerated approximately 3-fold and 10-fold higher concentrations of the two relatively more polar CAHs CF and 1,2-DCA, respectively, than the two relatively less polar compounds PCE and CT. EC50 values correlated well with growth rates observed in solvent-free cultures, with fast-growing organisms displaying higher tolerance levels. Overall, fermentative bacteria were more tolerant to CAHs than respiring species, with iron- and sulfate-reducing bacteria in particular appearing highly sensitive to CAHs. These data extend the current understanding of the impact of CAHs on a range of anaerobic bacteria, which will benefit the field of bioremediation.

  14. Analysis of residual chlorine in simple drinking water distribution system with intermittent water supply

    Goyal, Roopali V.; Patel, H. M.

    2015-09-01

    Knowledge of residual chlorine concentration at various locations in drinking water distribution system is essential final check to the quality of water supplied to the consumers. This paper presents a methodology to find out the residual chlorine concentration at various locations in simple branch network by integrating the hydraulic and water quality model using first-order chlorine decay equation with booster chlorination nodes for intermittent water supply. The explicit equations are developed to compute the residual chlorine in network with a long distribution pipe line at critical nodes. These equations are applicable to Indian conditions where intermittent water supply is the most common system of water supply. It is observed that in intermittent water supply, the residual chlorine at farthest node is sensitive to water supply hours and travelling time of chlorine. Thus, the travelling time of chlorine can be considered to justify the requirement of booster chlorination for intermittent water supply.

  15. Electrochemical treatment of graphite

    Podlovilin, V.I.; Egorov, I.M.; Zhernovoj, A.I.

    1983-01-01

    In the course of investigating various modes of electrochemical treatment (ECT) it has been found that graphite anode treatment begins under the ''glow mode''. A behaviour of some marks of graphite with the purpose of ECT technique development in different electrolytes has been tested. Electrolytes have been chosen of three types: highly alkaline (pH 13-14), neutral (pH-Z) and highly acidic (pH 1-2). For the first time parallel to mechanical electroerosion treatment, ECT of graphite and carbon graphite materials previously considered chemically neutral is proposed. ECT of carbon graphite materials has a number of advantages as compared with electroerrosion and mechanical ones with respect to the treatment rate and purity (ronghness) of the surface. A small quantity of sludge (6-8%) under ECT is in highly alkali electrolytes.

  16. Organic electrochemical transistors

    Rivnay, Jonathan; Inal, Sahika; Salleo, Alberto; Owens, Róisín M.; Berggren, Magnus; Malliaras, George G.

    2018-02-01

    Organic electrochemical transistors (OECTs) make effective use of ion injection from an electrolyte to modulate the bulk conductivity of an organic semiconductor channel. The coupling between ionic and electronic charges within the entire volume of the channel endows OECTs with high transconductance compared with that of field-effect transistors, but also limits their response time. The synthetic tunability, facile deposition and biocompatibility of organic materials make OECTs particularly suitable for applications in biological interfacing, printed logic circuitry and neuromorphic devices. In this Review, we discuss the physics and the mechanism of operation of OECTs, focusing on their identifying characteristics. We highlight organic materials that are currently being used in OECTs and survey the history of OECT technology. In addition, form factors, fabrication technologies and applications such as bioelectronics, circuits and memory devices are examined. Finally, we take a critical look at the future of OECT research and development.

  17. Electrochemical Hydrogen Compressor

    Lipp, Ludwig [FuelCell Energy, Inc., Torrington, CT (United States)

    2016-01-21

    Conventional compressors have not been able to meet DOE targets for hydrogen refueling stations. They suffer from high capital cost, poor reliability and pose a risk of fuel contamination from lubricant oils. This project has significantly advanced the development of solid state hydrogen compressor technology for multiple applications. The project has achieved all of its major objectives. It has demonstrated capability of Electrochemical Hydrogen Compression (EHC) technology to potentially meet the DOE targets for small compressors for refueling sites. It has quantified EHC cell performance and durability, including single stage hydrogen compression from near-atmospheric pressure to 12,800 psi and operation of EHC for more than 22,000 hours. Capital cost of EHC was reduced by 60%, enabling a path to meeting the DOE cost targets for hydrogen compression, storage and delivery ($2.00-2.15/gge by 2020).

  18. Fast electrochemical actuator

    Uvarov, I V; Postnikov, A V; Svetovoy, V B

    2016-01-01

    Lack of fast and strong microactuators is a well-recognized problem in MEMS community. Electrochemical actuators can develop high pressure but they are notoriously slow. Water electrolysis produced by short voltage pulses of alternating polarity can overcome the problem of slow gas termination. Here we demonstrate an actuation regime, for which the gas pressure is relaxed just for 10 μs or so. The actuator consists of a microchamber filled with the electrolyte and covered with a flexible membrane. The membrane bends outward when the pressure in the chamber increases. Fast termination of gas and high pressure developed in the chamber are related to a high density of nanobubbles in the chamber. The physical processes happening in the chamber are discussed so as problems that have to be resolved for practical applications of this actuation regime. The actuator can be used as a driving engine for microfluidics. (paper)

  19. Organic electrochemical transistors

    Rivnay, Jonathan

    2018-01-16

    Organic electrochemical transistors (OECTs) make effective use of ion injection from an electrolyte to modulate the bulk conductivity of an organic semiconductor channel. The coupling between ionic and electronic charges within the entire volume of the channel endows OECTs with high transconductance compared with that of field-effect transistors, but also limits their response time. The synthetic tunability, facile deposition and biocompatibility of organic materials make OECTs particularly suitable for applications in biological interfacing, printed logic circuitry and neuromorphic devices. In this Review, we discuss the physics and the mechanism of operation of OECTs, focusing on their identifying characteristics. We highlight organic materials that are currently being used in OECTs and survey the history of OECT technology. In addition, form factors, fabrication technologies and applications such as bioelectronics, circuits and memory devices are examined. Finally, we take a critical look at the future of OECT research and development.

  20. Development of a Site-Specific Kinetic Model for Chlorine Decay and the Formation of Chlorination By-Products in Seawater

    Suhur Saeed

    2015-07-01

    Full Text Available Chlorine is used commonly to prevent biofouling in cooling water systems. The addition of chlorine poses environmental risks in natural systems due to its tendency to form chlorination by-products (CBPs when exposed to naturally-occurring organic matter (NOM. Some of these CBPs can pose toxic risks to aquatic and benthic species in the receiving waters. It is, therefore, important to study the fate of residual chlorine and CBPs to fully understand the potential impacts of chlorination to the environment. The goal of this study was to develop improved predictions of how chlorine and CBP concentrations in seawater vary with time, chlorine dose and temperature. In the present study, chlorination of once-through cooling water at Ras Laffan Industrial City (RLIC, Qatar, was studied by collecting unchlorinated seawater from the RLIC cooling water system intake, treating it with chlorine and measuring time series of chlorine and CBP concentrations. Multiple-rate exponential curves were used to represent fast and slow chlorine decay and CBP formation, and site-specific chlorine kinetic relationships were developed. Through extensive analysis of laboratory measurements, it was found that only some of the control parameters identified in the literature were important for predicting residual chlorine and CBP concentrations for this specific location. The new kinetic relationships were able to significantly improve the predictability and validity of Generalized Environmental Modeling System for Surfacewaters (GEMSS-chlorine kinetics module (CKM, a three-dimensional hydrodynamic and chlorine kinetics and transport model when applied for RLIC outfall studies using actual field measurements.

  1. Tracking of electrochemical impedance of batteries

    Piret, H.; Granjon, P.; Guillet, N.; Cattin, V.

    2016-04-01

    This paper presents an evolutionary battery impedance estimation method, which can be easily embedded in vehicles or nomad devices. The proposed method not only allows an accurate frequency impedance estimation, but also a tracking of its temporal evolution contrary to classical electrochemical impedance spectroscopy methods. Taking into account constraints of cost and complexity, we propose to use the existing electronics of current control to perform a frequency evolutionary estimation of the electrochemical impedance. The developed method uses a simple wideband input signal, and relies on a recursive local average of Fourier transforms. The averaging is controlled by a single parameter, managing a trade-off between tracking and estimation performance. This normalized parameter allows to correctly adapt the behavior of the proposed estimator to the variations of the impedance. The advantage of the proposed method is twofold: the method is easy to embed into a simple electronic circuit, and the battery impedance estimator is evolutionary. The ability of the method to monitor the impedance over time is demonstrated on a simulator, and on a real Lithium ion battery, on which a repeatability study is carried out. The experiments reveal good tracking results, and estimation performance as accurate as the usual laboratory approaches.

  2. Chlorinated and Non chlorinated-Volatile Organic Compounds (Vocs) in Drinking Water of Peninsular Malaysia

    Mohd Pauzi Abdullah; Chian, S.S.

    2011-01-01

    A survey undertaken in Peninsular Malaysia has shown that volatile organic compounds (VOCs), both chlorinated and non-chlorinated, are present in selected drinking water samples. In this study, analyses of VOCs were performed by means of solid phase micro extraction (SPME) with a 100 μm polydimethylsiloxane (PDMS) fibre followed by gas chromatography - mass spectrometry detector (GC-MSD). Samples from different points of the distribution system networks were taken and analysed for 54 VOCs of different chemical families. The results of the study indicated that chloroform constituted the major portion of the VOCs in all samples analysed. In addition to trihalo methanes (THMs), other abundant compounds detected were cis and trans-1,2-dichloroethylene, trichloroethylene, 1,2-dibromoethane, benzene, toluene, ethylbenzene, chlorobenzene, 1,4-dichlorobenzene and 1,2-dichlorobenzene. However, the measured concentrations did not exceed the National Guideline for Drinking Water Quality 2000 in any case. No clear relationship between the status of development of a state in Malaysia to the levels and types of VOCs detected in its drinking water was noted. Nevertheless, the finding of anthropogenic chemicals, even at low concentrations, gave credibility to the viewpoint that improper development and disposal practices threatened the purity of the drinking water. (author)

  3. Electrochemical oxidation of recalcitrant organic compounds in biologically treated municipal solid waste leachate in a flow reactor.

    Quan, Xuejun; Cheng, Zhiliang; Chen, Bo; Zhu, Xincai

    2013-10-01

    Biologically-treated municipal solid waste (MSW) leachate still contains many kinds of bio-recalcitrant organic matter. A new plate and frame electrochemical reactor was designed to treat these materials under flow conditions. In the electrochemical oxidation process, NH3 and color could be easily removed by means of electro-generated chlorine/hypochlorite within 20 min. The effects of major process parameters on the removal of organic pollutants were investigated systematically. Under experimental conditions, the optimum operation parameters were current density of 65 mA/cm2, flow velocity of 2.6 cm/sec in electrode gap, and initial chloride ion concentration of 5000 mg/L. The COD in the leachate could be reduced below 100 mg/L after 1 hr of treatment. The kinetics and mechanism of COD removal were investigated by simultaneously monitoring the COD change and chlorine/hypochlorite production. The kinetics of COD removal exhibited a two-stage kinetic model, and the decrease of electro-generated chlorine/hypochlorite production was the major mechanism for the slowing down of the COD removal rate in the second stage. The narrowing of the electrode gap is beneficial for COD removal and energy consumption.

  4. Inactivation Effect of Antibiotic-Resistant Gene Using Chlorine Disinfection

    Takashi Furukawa

    2017-07-01

    Full Text Available The aim of this study was to elucidate the inactivation effects on the antibiotic-resistance gene (vanA of vancomycin-resistant enterococci (VRE using chlorination, a disinfection method widely used in various water treatment facilities. Suspensions of VRE were prepared by adding VRE to phosphate-buffered saline, or the sterilized secondary effluent of a wastewater treatment plant. The inactivation experiments were carried out at several chlorine concentrations and stirring time. Enterococci concentration and presence of vanA were determined. The enterococci concentration decreased as chlorine concentrations and stirring times increased, with more than 7.0 log reduction occurring under the following conditions: 40 min stirring at 0.5 mg Cl2/L, 20 min stirring at 1.0 mg Cl2/L, and 3 min stirring at 3.0 mg Cl2/L. In the inactivation experiment using VRE suspended in secondary effluent, the culturable enterococci required much higher chlorine concentration and longer treatment time for complete disinfection than the cases of suspension of VRE. However, vanA was detected in all chlorinated suspensions of VRE, even in samples where no enterococcal colonies were present on the medium agar plate. The chlorine disinfection was not able to destroy antibiotic-resistance genes, though it can inactivate and decrease bacterial counts of antibiotic-resistant bacteria (ARB. Therefore, it was suggested that remaining ARB and/or antibiotic-resistance gene in inactivated bacterial cells after chlorine disinfection tank could be discharged into water environments.

  5. Chlorination of tramadol: Reaction kinetics, mechanism and genotoxicity evaluation.

    Cheng, Hanyang; Song, Dean; Chang, Yangyang; Liu, Huijuan; Qu, Jiuhui

    2015-12-01

    Tramadol (TRA) is one of the most detected analgesics in environmental matrices, and it is of high significance to study the reactivity of TRA during chlorination considering its potential toxicity to the environment. The chlorine/TRA reaction is first order with respect to the TRA concentration, and a combination of first-order and second-order with respect to chlorine concentration. The pH dependence of the observed rate constants (kobs) showed that the TRA oxidation reactivity increased with increasing pH. kobs can be quantitatively described by considering all active species including Cl2, Cl2O and HOCl, and the individual rate constants of HOCl/TRA(0), HOCl/TRAH(+), Cl2/TRA and Cl2O/TRA reactions were calculated to be (2.61±0.29)×10(3)M(-1)s(-1), 14.73±4.17M(-1)s(-1), (3.93±0.34)×10(5)M(-1)s(-1) and (5.66±1.83)×10(6)M(-1)s(-1), respectively. Eleven degradation products were detected with UPLC-Q-TOF-MS, and the corresponding structures of eight products found under various pH conditions were proposed. The amine group was proposed to be the initial attack site under alkaline pH conditions, where reaction of the deprotonated amine group with HOCl is favorable. Under acidic and neutral pH conditions, however, two possible reaction pathways were proposed. One is an electrophilic substitution on the aromatic ring, and another is an electrophilic substitution on the nitrogen, leading to an N-chlorinated intermediate, which can be further oxidized. Finally, the SOS/umu test showed that the genotoxicity of TRA chlorination products increased with increasing dosage of chlorine, which was mostly attributed to the formation of some chlorine substitution products. Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. Modeling Groundwater-Surface Water Interaction and Contaminant Transport of Chlorinated Solvent Contaminated Site

    Yimer Ebrahim, Girma; Jonoski, Andreja; van Griensven, Ann; Dujardin, Juliette; Baetelaan, Okke; Bronders, Jan

    2010-05-01

    Chlorinated-solvent form one of the largest groups of environmental chemicals. Their use and misuse in industry have lead to a large entry of these chemicals into the environment, resulting in widespread dissemination and oftentimes environmental contamination. Chlorinated solvent contamination of groundwater resources has been widely reported. For instance, there has been much interest in the assessment of these contaminant levels and their evolutions with time in the groundwater body below the Vilvoorde-Machelen industrial area (Belgium). The long industrial history of the area has lead to complex patterns of pollution from multiple sources and the site has been polluted to the extent that individual plumes are not definable any more. Understanding of groundwater/surface water interaction is a critical component for determining the fate of contaminant both in streams and ground water due to the fact that groundwater and surface water are in continuous dynamic interaction in the hydrologic cycle. The interaction has practical consequences in the quantity and quality of water in either system in the sense that depletion and/or contamination of one of the system will eventually affect the other one. The transition zone between a stream and its adjacent aquifer referred to as the hyporheic zone plays a critical role in governing contaminant exchange and transformation during water exchange between the two water bodies. The hyporheic zone of Zenne River ( the main receptor ) is further complicated due to the fact that the river banks are artificially trained with sheet piles along its reach extending some 12 m below the surface. This study demonstrates the use of MODFLOW, a widely used modular three-dimensional block-centred finite difference, saturated flow model for simulating the flow and direction of movement of groundwater through aquifer and stream-aquifer interaction and the use of transport model RT3D, a three-dimensional multi-species reactive transport model

  7. Two-phase ozonation of chlorinated organics

    Bhattacharyya, D.; Freshour, A.; West, D.

    1995-01-01

    In the last few years the amount of research being conducted in the field of single-phase ozonation has grown extensively. However, traditional aqueous-phase ozonation systems are limited by a lack of selective oxidation potential, low ozone solubility in water, and slow intermediate decomposition rates. Furthermore, ozone may decompose before it can be utilized for pollutant destruction since ozone can be highly unstable in aqueous solutions. Naturally occurring compounds such as NaHCO 3 also affect ozone reactions by inhibiting the formation of OH-free radicals. To compensate for these factors, excess ozone is typically supplied to a reactor. Since ozone generation requires considerable electric power consumption (16 - 24 kWh/kg of O 3 ), attempts to enhance the ozone utilization rate and stability should lead to more efficient application of this process to hazardous waste treatment. To improve the process, ozonation may be more efficiently carried out in a two-phase system consisting of an inert solvent (saturated with O 3 ) contacted with an aqueous phase containing pollutants. The non-aqueous phase must meet the following criteria: (1) non-toxic, (2) very low vapor pressure, (3) high density (for ease of separation), (4) complete insolubility in water, (5) reusability, (6) selective pollutant extractability, (7) high oxidant solubility, and (8) extended O 3 stability. Previously published studies (1) have indicated that a number of fluorinated hydrocarbon compounds fit these criteria. For this project, FC40 (a product of 3M Co.) was chosen due to its low vapor pressure (3 mm Hg) and high specific gravity (1.9). The primary advantages of the FC40 solvent are that it is non-toxic, reusable, has an ozone solubility 10 times that of water, and that 85 % of the ozone remains in the solvent even after 2 hours. This novel two-phase process has been utilized to study the rapid destruction of organic chlorine compounds and organic mixtures

  8. Electrolytic recuperation of heavy metals and chlorine from fly-ashes and washwater of a household incinerator

    Maes, H.; Carpels, M.; Elslander, H.; Van Houtven, D.; Vereecken, J.; Kinnaer, L.; Hermans, N.; Gielen, C.; Van Kerckhoven, M.; Raats, L. [Vlaamse Instelling voor Technologisch Onderzoek (VITO), Mol (Belgium)

    1995-12-31

    The treatment and processing of the residues which result from the household incineration process were investigated in a study conducted in Belgium. Incineration produces large amounts of solid residue, particularly fly-ash, which contains a large degree of heavy metals. Also, the large amount of acid washwater flow which comes from the gas washer is highly concentrated with chlorine, and heavy metals. Presently, both the fly-ash and the wastewater are dumped at disposal sites. Two objectives for waste management were presented. The first was to improve the fly-ash for potential use as, for example, filler in road surfaces. The second was to reduce the wastewater flow and to use neutralizing reagents or an electro-chemical treatment on the washwater, in order to recuperate the chlorine. The fly-ash was treated by leaching with the acid washwater. The leached heavy metals were recuperated by electrolysis. It was concluded, however, that electrolytic recuperation of heavy metals from fly ash was not economically feasible. 2 refs., 7 tabs., 8 figs.

  9. Ametryn degradation by aqueous chlorine: Kinetics and reaction influences

    Xu Bin; Gao Naiyun; Cheng Hefa; Hu Chenyan; Xia Shengji; Sun Xiaofeng; Wang Xuejiao; Yang Shaogui

    2009-01-01

    The chemical oxidation of the herbicide ametryn was investigated by aqueous chlorination between pH 4 and 10 at a temperature of 25 deg. C. Ametryn was found to react very rapidly with aqueous chlorine. The reaction kinetics can be well described by a second-order kinetic model. The apparent second-order rate constants are greater than 5 x 10 2 M -1 s -1 under acidic and neutral conditions. The reaction proceeds much more slowly under alkaline conditions. The predominant reactions were found to be the reactions of HOCl with neutral ametryn and the charged ametryn, with rate constants equal to 7.22 x 10 2 and 1.58 x 10 3 M -1 s -1 , respectively. The ametryn degradation rate increases with addition of bromide and decreases with addition of ammonia during the chlorination process. Based on elementary chemical reactions, a kinetic model of ametryn degradation by chlorination in the presence of bromide or ammonia ion was also developed. By employing this model, we estimate that the rate constants for the reactions of HOBr with neutral ametryn and charged ametryn were 9.07 x 10 3 and 3.54 x 10 6 M -1 s -1 , respectively. These values are 10- to 10 3 -fold higher than those of HOCl, suggesting that the presence of bromine species during chlorination could significantly accelerate ametryn degradation.

  10. Chlorinated organic pesticides in marketed food: Barcelona, 2001-06

    Fontcuberta, M.; Arques, J.F.; Villalbi, J.R.; Martinez, M.; Centrich, F.; Serrahima, E.; Pineda, L.; Duran, J.; Casas, C.

    2008-01-01

    This paper reports concentration levels of 22 chlorinated organic compounds (both primary compounds and metabolites) in food marketed in the city of Barcelona (Catalonia, Spain) in 2001-06. Samples included meat products, fish and seafood, eggs, milk and dairy, vegetal oils, cereal products and derivates, vegetables, fresh fruits, dry fruits, spices, formula and baby food, tea and wine. Levels of chlorinated organic compounds were determined by gas chromatography with selective detectors: electron capture (ECD), flame photometric (FPD) and confirmation with mass-spectrometry. Chlorinated organic pesticides were detected in 7 of the 1,484 samples analyzed in the 2001-06 period (0.5%): 1 dairy product, 1 fruit, 1 olive oil and 4 vegetables. Specific pesticides detected are lindane and endosulfan α, β or sulphate. A decrease in both the proportion of samples with detectable residues and in the variety of chlorinated pesticides found is visible when comparing these results with those of the previous 1989-2000 period. These results suggest the gradual disappearance of regulated chlorinated organic pesticides as a consequence of the growing worldwide implementation of current regulatory agreements

  11. Bacterial repopulation of drinking water pipe walls after chlorination.

    Mathieu, Laurence; Francius, Grégory; El Zein, Racha; Angel, Edith; Block, Jean-Claude

    2016-09-01

    The short-term kinetics of bacterial repopulation were evaluated after chlorination of high-density polyethylene (HDPE) colonized with drinking water biofilms and compared with bare HDPE surfaces. The effect of chlorination was partial as a residual biofilm persisted and was time-limited as repopulation occurred immediately after water resupply. The total number of bacteria reached the same levels on both the bare and chlorinated biofilm-fouled HDPE after a seven-day exposure to drinking water. Due to the presence of a residual biofilm, the hydrophobicity of chlorinated biofilm-fouled surface exhibited much lower adhesion forces (2.1 nN) compared to bare surfaces (8.9 nN). This could explain the rapid repopulation after chlorination, with a twofold faster bacterial accumulation rate on the bare HDPE surface. γ-Proteobacteria dominated the early stages of repopulation of both surfaces and a shift in the dominance occurred over the colonization time. Such observations define a timescale for cleaning frequency in industrial environments and guidelines for a rinsing procedure using drinking water.

  12. Synthesis of magnesium aluminate spinel by periclase and alumina chlorination

    Orosco, Pablo; Barbosa, Lucía; Ruiz, María del Carmen

    2014-01-01

    Highlights: • Use of chlorination for the synthesis of magnesium aluminate spinel. • The reagents used were alumina, periclase and chlorine. • Isothermal and non-isothermal assays were performed in air and Cl 2 –N 2 flows. • The chlorination produced magnesium aluminate spinel at 700 °C. • Selectivity of the chlorination reaction to obtain spinel is very high. - Abstract: A pyrometallurgical route for the synthesis of magnesium aluminate spinel by thermal treatment of a mechanical mixture containing 29 wt% MgO (periclase) and 71 wt% Al 2 O 3 (alumina) in chlorine atmosphere was developed and the results were compared with those obtained by calcining the same mixture of oxides in air atmosphere. Isothermal and non-isothermal assays were performed in an experimental piece of equipment adapted to work in corrosive atmospheres. Both reagents and products were analyzed by differential thermal analysis (DTA), X-ray diffraction (XRD) and X-ray fluorescence (XRF). Thermal treatment in Cl 2 atmosphere of the MgO–Al 2 O 3 mixture produces magnesium aluminate spinel at 700 °C, while in air, magnesium spinel is generated at 930 °C. The synthesis reaction of magnesium aluminate spinel was complete at 800 °C

  13. Removal of trihalomethane from chlorinated seawater using gamma radiation.

    Rajamohan, R; Natesan, Usha; Venugopalan, V P; Rajesh, Puspalata; Rangarajan, S

    2015-12-01

    Chlorine addition as a biocide in seawater results in the formation of chlorination by-products such as trihalomethanes (THMs). Removal of THMs is of importance as they are potential mutagenic and carcinogenic agents. In this context, a study was conducted that used ionizing radiation to remove THMs from chlorinated (1, 3, and 5 mg/L) seawater by applying various dosages (0.4-5.0 kGy) of gamma radiation. Bromoform (BF) showed a faster rate of degradation as compared to other halocarbons such as bromodichloromethane (BDCM) and dibromochloromethane (DBCM). In chlorine-dosed seawater, total irradiation dose of 0.4 to 5 kGy caused percentage reduction in the range of 6.9 to 76.7%, 2.3 to 99.6%, and 45.7 to 98.3% for BDCM, DBCM, and BF, respectively. During the irradiation process, pH of the chlorinated seawater decreased with increase in the absorbed dose; however, no change in total organic carbon (TOC) was observed. The results show that gamma dose of 2.5 kGy was adequate for maximum degradation of THM; but for complete mineralization, higher dose would be required.

  14. Immobilization of chlorine dioxide modified cells for uranium absorption

    He, Shengbin; Ruan, Binbiao; Zheng, Yueping; Zhou, Xiaobin; Xu, Xiaoping

    2014-01-01

    There has been a trend towards the use of microorganisms to recover metals from industrial wastewater, for which various methods have been reported to be used to improve microorganism adsorption characteristics such as absorption capacity, tolerance and reusability. In present study, chlorine dioxide(ClO 2 ), a high-efficiency, low toxicity and environment-benign disinfectant, was first reported to be used for microorganism surface modification. The chlorine dioxide modified cells demonstrated a 10.1% higher uranium adsorption capacity than control ones. FTIR analysis indicated that several cell surface groups are involved in the uranium adsorption and cell surface modification. The modified cells were further immobilized on a carboxymethylcellulose (CMC) matrix to improve their reusability. The cell-immobilized adsorbent could be employed either in a high concentration system to move vast UO 2 2+ ions or in a low concentration system to purify UO 2 2+ contaminated water thoroughly, and could be repeatedly used in multiple adsorption-desorption cycles with about 90% adsorption capacity maintained after seven cycles. - Highlights: • Chlorine dioxide was first reported to be used for microorganism surface modification. • The chlorine dioxide modified cells demonstrated a 10.1% higher uranium adsorption capacity than control ones. • The chlorine dioxide modified cells were further immobilized by carboxymethylcellulose to improve their reusability

  15. Characterization of the bacterial community in shower water before and after chlorination

    Peters, Marjolein C. F. M.

    2017-12-22

    Bathers release bacteria in swimming pool water, but little is known about the fate of these bacteria and potential risks they might cause. Therefore, shower water was characterized and subjected to chlorination to identify the more chlorine-resistant bacteria that might survive in a chlorinated swimming pool and therefore could form a potential health risk. The total community before and after chlorination (1 mg Cl2 L−1 for 30 s) was characterized. More than 99% of the bacteria in the shower water were Gram-negative. The dominant bacterial families with a relative abundance of ≥10% of the total (non-chlorinated and chlorinated) communities were Flavobacteriaceae (24–21%), Xanthomonadaceae (23–24%), Moraxellaceae (12–11%) and Pseudomonadaceae (10–22%). The relative abundance of Pseudomonadaceae increased after chlorination and increased even more with longer contact times at 1 mg Cl2L−1. Therefore, Pseudomonadaceae were suggested to be relatively more chlorine resistant than the other identified bacteria. To determine which bacteria could survive chlorination causing a potential health risk, the relative abundance of the intact cell community was characterized before and after chlorination. The dominant bacterial families in the intact community (non-chlorinated and chlorinated) were Xanthomonadaceae (21–17%) and Moraxellaceae (48–57%). Moraxellaceae were therefore more chlorine resistant than the other identified intact bacteria present.

  16. Transformation of cefazolin during chlorination process: Products, mechanism and genotoxicity assessment

    Li, Liping, E-mail: lisaleercees807@yahoo.cn; Wei, Dongbin, E-mail: weidb@rcees.ac.cn; Wei, Guohua, E-mail: wgh@rcees.ac.cn; Du, Yuguo, E-mail: duyuguo@rcees.ac.cn

    2013-11-15

    Highlights: • Base-catalyzed electrophilic substitution occurred in cefazolin chlorination. • Oxidation of thioether in cefazolin was found in chlorination process. • The pH conditions impacted on the occurrence of reaction types. • Genotoxicity had an elevation after chlorination of cefazolin. • Reaction pathways of cefazolin chlorination were replayed in surface water matrix. -- Abstract: Large quantities of cephalosporins have entered into aquatic environment in recent years, posing potential adverse effect to human health and ecological safety. In this study, cefazolin, one of widely used cephalosporins, was targeted to explore its transformation behaviors in chlorination disinfection process. With the help of ultra high performance liquid chromatography and high resolution mass spectroscopy, one chlorinated product and four oxidation products were detected in cefazolin chlorination system. The corresponding transformation pathways of cefazolin were proposed. Two kinds of reactions occurred in chlorination system, one was oxidation of thioether-sulfur to sulfoxide and di-sulfoxide, and the other was base-catalyzed electrophilic substitution of alpha-H of amide by chlorine atom. The pH value determined the occurrence of reaction types, and increasing chlorine dose promoted transformation of cefazolin. More importantly, genotoxicity in SOS/umu assay had an elevation after chlorination, which might be attributed to the formation of chlorinated product and sulfoxide during chlorination process.

  17. Inactivation of Aspergillus flavus in drinking water after treatment with UV irradiation followed by chlorination

    Al-Gabr, Hamid Mohammad; Zheng, Tianling; Yu, Xin

    2013-01-01

    The disinfection process for inactivating microorganisms at drinking water treatment plants is aimed for safety of drinking water for humans from a microorganism, such as bacteria, viruses, algae, fungi by using chlorination, ozonation, UV irradiation, etc. In the present study, a combination of two disinfectants, UV irradiation followed by chlorination, was evaluated for inactivating Aspergillus flavus under low contact time and low dosage of UV irradiation. The results indicated an inverse correlation between the inactivation of A. flavus by using UV irradiation only or chlorination alone. By using UV radiation, the 2 log 10 control of A. flavus was achieved after 30 s of irradiation, while chlorination was observed to be more effective than UV, where the 2 log was achieved at chlorine concentration of 0.5, 1, 2 and 3 mg/l, in contact time of 60, 5, 1 and 1 min, respectively. However, combined use (UV irradiation followed by chlorination) was more effective than using either UV or chlorination alone; 5 s UV irradiation followed by chlorination produced 4 log 10 reduction of A. flavus at chlorine concentrations of 2 and 3 mg/l under a contact time of 15 min. The results indicated that efficiency of UV irradiation improves when followed by chlorination at low concentrations. - Highlights: • As a disinfectant, chlorine is more effective than UV in inactivating Aspergillus flavus. • As a combined method, UV irradiation followed by chlorination shows high efficiency. • UV irradiation can improve effectiveness of chlorination in reducing Aspergillus flavus

  18. Transformation of cefazolin during chlorination process: Products, mechanism and genotoxicity assessment

    Li, Liping; Wei, Dongbin; Wei, Guohua; Du, Yuguo

    2013-01-01

    Highlights: • Base-catalyzed electrophilic substitution occurred in cefazolin chlorination. • Oxidation of thioether in cefazolin was found in chlorination process. • The pH conditions impacted on the occurrence of reaction types. • Genotoxicity had an elevation after chlorination of cefazolin. • Reaction pathways of cefazolin chlorination were replayed in surface water matrix. -- Abstract: Large quantities of cephalosporins have entered into aquatic environment in recent years, posing potential adverse effect to human health and ecological safety. In this study, cefazolin, one of widely used cephalosporins, was targeted to explore its transformation behaviors in chlorination disinfection process. With the help of ultra high performance liquid chromatography and high resolution mass spectroscopy, one chlorinated product and four oxidation products were detected in cefazolin chlorination system. The corresponding transformation pathways of cefazolin were proposed. Two kinds of reactions occurred in chlorination system, one was oxidation of thioether-sulfur to sulfoxide and di-sulfoxide, and the other was base-catalyzed electrophilic substitution of alpha-H of amide by chlorine atom. The pH value determined the occurrence of reaction types, and increasing chlorine dose promoted transformation of cefazolin. More importantly, genotoxicity in SOS/umu assay had an elevation after chlorination, which might be attributed to the formation of chlorinated product and sulfoxide during chlorination process

  19. Characterization of Electrochemically Generated Silver

    Adam, Niklas; Martinez, James; Carrier, Chris

    2014-01-01

    Silver biocide offers a potential advantage over iodine, the current state of the art in US spacecraft disinfection technology, in that silver can be safely consumed by the crew. Low concentrations of silver (Silver does not require hardware to remove it from a water system, and therefore can provide a simpler means for disinfecting water. The Russian segment of the International Space Station has utilized an electrochemically generated silver solution, which is colloidal in nature. To be able to reliably provide a silver biocide to drinking water by electrochemical means would reduce mass required for removing another biocide such as iodine from the water. This would also aid in crew time required to replace iodine removal cartridges. Future long term missions would benefit from electrochemically produced silver as the biocide could be produced on demand and requires only a small concentration to be effective. Since it can also be consumed safely, there is less mass in removal hardware and little consumables required for production. The goal of this project initially is to understand the nature of the electrochemically produced silver, the particle sizes produced by the electrochemical cell and the effect that voltage adjustment has on the particle size. In literature, it has been documented that dissolved oxygen and pH have an effect on the ionization of the electrochemical silver so those parameters would be measured and possibly adjusted to understand their effect on the silver.

  20. Electrochemical processes in macro and microfluidic cells for the abatement of chloroacetic acid from water

    Scialdone, O.; Corrado, E.; Galia, A.; Sirés, I.

    2014-01-01

    Highlights: • The electrochemical abatement of chloroacetic acid in water was studied. • The performance of both macro and microfluidic reactors was examined. • Cathodic reduction and anodic oxidation was studied in detail. • Mediated oxidation by electro-Fenton and active chlorine was carried out. • Anodic oxidation at BDD gave better performances. • Microfluidic reactors gave better performances compared to conventional cells. - Abstract: The remediation of solutions contaminated with monochloroacetic acid (CAA), which is one of the most resistant haloacetic acids (HAAs) to chemical degradation, dramatically depends on the adopted electrochemical approach: (i) CAA is only poorly oxidized either by homogeneous hydroxyl radical in electro-Fenton (EF), electrogenerated active chlorine or electro-oxidation on Pt anode; (ii) it is moderately abated by direct reduction on silver or compact graphite cathodes (from 30% in macro cells to 60% in the microfluidic devices); (iii) it is quantitatively removed by direct electro-oxidation on a boron-doped diamond (BDD) anode. The use of a microreactor enables operation in the absence of supporting electrolyte and drastically enhances the performance of the cathodic process. Simultaneously performing direct oxidation on BDD and reduction on graphite in a microfluidic cell yields the fastest CAA removal with 100% abatement at low current densities (∼5 mA cm −2 )

  1. Lethality of chlorine, chlorine dioxide, and a commercial fruit and vegetable sanitizer to vegetative cells and spores of Bacillus cereus and spores of Bacillus thuringiensis.

    Beuchat, Larry R; Pettigrew, Charles A; Tremblay, Mario E; Roselle, Brian J; Scouten, Alan J

    2004-08-01

    Chlorine, ClO2, and a commercial raw fruit and vegetable sanitizer were evaluated for their effectiveness in killing vegetative cells and spores of Bacillus cereus and spores of Bacillus thuringiensis. The ultimate goal was to use one or both species as a potential surrogate(s) for Bacillus anthracis in studies that focus on determining the efficacy of sanitizers in killing the pathogen on food contact surfaces and foods. Treatment with alkaline (pH 10.5 to 11.0) ClO2 (200 microg/ml) produced by electrochemical technologies reduced populations of a five-strain mixture of vegetative cells and a five-strain mixture of spores of B. cereus by more than 5.4 and more than 6.4 log CFU/ml respectively, within 5 min. This finding compares with respective reductions of 4.5 and 1.8 log CFU/ml resulting from treatment with 200 microg/ml of chlorine. Treatment with a 1.5% acidified (pH 3.0) solution of Fit powder product was less effective, causing 2.5- and 0.4-log CFU/ml reductions in the number of B. cereus cells and spores, respectively. Treatment with alkaline ClO2 (85 microg/ml), acidified (pH 3.4) ClO2 (85 microg/ml), and a mixture of ClO2 (85 microg/ml) and Fit powder product (0.5%) (pH 3.5) caused reductions in vegetative cell/spore populations of more than 5.3/5.6, 5.3/5.7, and 5.3/6.0 log CFU/ml, respectively. Treatment of B. cereus and B. thuringiensis spores in a medium (3.4 mg/ml of organic and inorganic solids) in which cells had grown and produced spores with an equal volume of alkaline (pH 12.1) ClO2 (400 microg/ml) for 30 min reduced populations by 4.6 and 5.2 log CFU/ml, respectively, indicating high lethality in the presence of materials other than spores that would potentially react with and neutralize the sporicidal activity of ClO2.

  2. Electrochemical incineration of wastes

    Kaba, L.; Hitchens, G. D.; Bockris, J. OM.

    1989-01-01

    The disposal of domestic organic waste in its raw state is a matter of increasing public concern. Earlier, it was regarded as permissible to reject wastes into the apparently infinite sink of the sea but, during the last 20 years, it has become clear that this is environmentally unacceptable. On the other hand, sewage farms and drainage systems for cities and for new housing developments are cumbersome and expensive to build and operate. New technology whereby waste is converted to acceptable chemicals and pollution-free gases at site is desirable. The problems posed by wastes are particularly demanding in space vehicles where it is desirable to utilize treatments that will convert wastes into chemicals that can be recycled. In this situation, the combustion of waste is undesirable due to the inevitable presence of oxides of nitrogen and carbon monoxide in the effluent gases. Here, in particular, electrochemical techniques offer several advantages including the low temperatures which may be used and the absence of any NO and CO in the evolved gases. Work done in this area was restricted to technological papers, and the present report is an attempt to give a more fundamental basis to the early stages of a potentially valuable technology.

  3. Recovery of actinides from actinide-aluminium alloys by chlorination: Part III - Chlorination with HCl(g)

    Meier, Roland; Souček, Pavel; Walter, Olaf; Malmbeck, Rikard; Rodrigues, Alcide; Glatz, Jean-Paul; Fanghänel, Thomas

    2018-01-01

    Two steps of a pyrochemical route for the recovery of actinides from spent metallic nuclear fuel are being investigated at JRC-Karlsruhe. The first step consists in electrorefining the fuel in molten salt medium implying aluminium cathodes. The second step is a chlorination process for the separation of actinides (An) from An-Al alloys formed on the cathodes. The chlorination process, in turn, consists of three steps; the distillation of adhered salt (1), the chlorination of An-Al by HCl/Cl2 under formation of AlCl3 and An chlorides (2), and the subsequent sublimation of AlCl3 (3). In the present work UAl2, UAl3, NpAl2, and PuAl2 were chlorinated with HCl(g) in a temperature range between 300 and 400 °C forming UCl4, NpCl4 or PuCl3 as the major An containing phases, respectively. Thermodynamic calculations were carried out to support the experimental work. The results showed a high chlorination efficiency for all used starting materials and indicated that the sublimation step may not be necessary when using HCl(g).

  4. Chlorination and oxidation of sulfonamides by free chlorine: Identification and behaviour of reaction products by UPLC-MS/MS.

    Gaffney, Vanessa de Jesus; Cardoso, Vitor Vale; Benoliel, Maria João; Almeida, Cristina M M

    2016-01-15

    Sulfonamides (SAs) are one class of the most widely used antibiotics around the world and have been frequently detected in municipal wastewater and surface water in recent years. Their transformation in waste water treatment plants (WWTP) and in water treatment plants (WTP), as well as, their fate and transport in the aquatic environment are of concern. The reaction of six sulfonamides (sulfamethoxazole, sulfapyridine, sulfamethazine, sulfamerazine, sulfathiazole and sulfadiazine) with free chlorine was investigated at a laboratory scale in order to identify the main chlorination by-products. A previously validated method, liquid chromatography/mass spectrometry, was used to analyse SAs and their chlorination by-products. At room temperature, pH 6-7, reaction times of up to 2 h and an initial concentration of 2 mg/L of free chlorine, the majority of SAs suffered degradation of around 65%, with the exception of sulfamethoxazole and sulfathiazole (20%). The main reaction of SAs with free chlorine occurred in the first minute. Copyright © 2015 Elsevier Ltd. All rights reserved.

  5. Chlorin photosensitizers sterically designed to prevent self-aggregation.

    Uchoa, Adjaci F; de Oliveira, Kleber T; Baptista, Mauricio S; Bortoluzzi, Adailton J; Iamamoto, Yassuko; Serra, Osvaldo A

    2011-11-04

    The synthesis and photophysical evaluation of new chlorin derivatives are described. The Diels-Alder reaction between protoporphyrin IX dimethyl ester and substituted maleimides furnishes endo-adducts that completely prevent the self-aggregation of the chlorins. Fluorescence, resonant light scattering (RLS) and (1)H NMR experiments, as well as X-ray crystallographic have demonstrated that the configurational arrangement of the synthesized chlorins prevent π-stacking interactions between macrocycles, thus indicating that it is a nonaggregating photosensitizer with high singlet oxygen (Φ(Δ)) and fluorescence (Φ(f)) quantum yields. Our results show that this type of synthetic strategy may provide the lead to a new generation of PDT photosensitizers.

  6. The geochemistry of stable chlorine and bromine isotopes

    Eggenkamp, Hans [Onderzock and Beleving, Bussum (Netherlands)

    2014-11-01

    First book solely dedicated to the geochemistry of chlorine and bromine isotopes. Detailed description of analytical techniques, including their advantages and disadvantages. Indication of research fields where measurement of these isotopes is especially useful. This book provides detailed information on the history, analysis and applications of chlorine and bromine isotope geochemistry. Chlorine and bromine are geochemically unique as they prefer to exist as single charged negative ions. For this reason isotope fractionation reflects mostly processes that are not related to changes in the redox state and this fractionation is generally modest. The book will describe the processes that are most easily detected using these isotopes. Also isotope variations, and processes that cause them, measured in oxidised species such as perchlorates and in organic molecules will be described in this book.

  7. Biodegradation of chlorinated solvents in a water unsaturated topsoil

    Borch, T.; Ambus, P.; Laturnus, F.

    2003-01-01

    In order to investigate topsoils as potential sinks for chlorinated solvents from the atmosphere, the degradation of trichloromethane (CHCl3), 1,1,1-trichloroethane (CH3CCl3), tetrachloromethane (CCl4), trichloroethene (C2HCl3) and tetrachloroethene (C2Cl4) was studied in anoxic laboratory....... The headspace concentrations of all the chlorinated solvents except CH3CCl3 were significantly (P less than or equal to 0.05) lower after 41 days in biologically active batches as compared to sterile batches. For the compounds with significantly decreasing headspace concentrations, the decline was the least...... experiments designed to simulate denitrifying conditions in water unsanstrated by measuring the release of N-15 in N-2 to the headspace from added N-15 labeled nitrate. The degradation of chlorinated aliphatic compounds was followed by measuring their concentrations in the headspace above the soil...

  8. Enhanced reductive dechlorination in clay till contaminated with chlorinated solvents

    Damgaard, Ida

    Chlorinated solvents are among the most frequently found contaminants in groundwater. In fractured media, chlorinated ethenes and ethanes are transported downwards through preferential pathways with subsequent diffusion into the sediment matrix. Due to slow back diffusion it can serve as a long...... (direct push delivery, Gl. Kongevej). Degradation of chlorinated ethenes (and ethanes) in the clay till matrix and in embedded high permeability features was investigated by high resolution sampling of intact cores combined with groundwater sampling. An integrated approach using chemical analysis...... (hydraulic fracturing with gravitational injection and direct push delivery) were therefore tested in clay till by injection of amendment-comparable tracers to investigate the possibility to overcome diffusion limitations in the low permeability matrix. The study of hydraulic fracturing demonstrated...

  9. Epidemiological evidence of carcinogenicity of chlorinated organics in drinking water.

    Cantor, K P

    1982-12-01

    Concern has recently been voiced over possible chronic toxicity associated with chlorination of public drinking water supplies in the United States. This paper reviews the available evidence and the studies underway to further evaluate hypothesized associations between cancer risk and byproducts of chlorination. Preliminary data from measures of halogenated volatiles and personal exposure histories from respondents in a large epidemiologic study of bladder cancer are presented. These data support the use in epidemiologic studies of categorical measures of exposure and suggest that results from completed case-control studies, based on death certificates, may have underestimated the true risk of exposure to chlorination by-products. The current generation of studies which use a case-control interview design offer many advantages over earlier efforts to evaluate this issue.

  10. Analyzing Environmental Policies for Chlorinated Solvents with a Model of Markets and Regulations

    1991-01-01

    chlorine, fluorine , bromine, and iodine. Another broad term is chlorocarbons (fluorocarbons), which indicates the chlorinated ( fluorinated ) hydrocarbons... varnishes , and lacquers (Wolf, Yazdani, and Yates, 1990b). Process Substitutes. The only process modifications that are available for consumer paint

  11. State of the art on cyanotoxins in water and their behaviour towards chlorine.

    Merel, Sylvain; Clément, Michel; Thomas, Olivier

    2010-04-01

    The occurrence of cyanobacterial blooms is drastically increasing in temperate countries and drinking water resources are threatened. As a result, cyanotoxins should be considered in water treatment to protect human health. This study presents a state of the art on cyanotoxins in water and their behaviour towards chlorination, a common drinking water disinfection process. Chlorination efficiency on cyanotoxins alteration depends on pH, chlorine dose and oxidant nature. Microcystins and cylindrospermopsin are efficiently transformed by chlorine, with respectively 6 and 2 by-products identified. In addition, chlorination of microcystins and cylindrospermopsin is associated with a loss of acute toxicity. Even though they have been less investigated, saxitoxins and nodularins are also altered by chlorine. For these toxins, no by-products have been identified, but the chlorinated mixture does not show acute toxicity. On the contrary, the fact that anatoxin-a has a very slow reaction kinetics suggests that this toxin resists chlorination. Copyright 2009 Elsevier Ltd. All rights reserved.

  12. Chlorinated pesticide residues in sediments from the Arabian Sea along the Central West coast of India

    Sarkar, A.; SenGupta, R.

    Environmental contamination by persistent chlorinated pesticides has evoked major concern due to the presence of their residues in the environment. The quantitative distribution of chlorinated pesticides residues in the marine sediments from...

  13. Chlorine Dioxide: The State of Science, Regulatory, Environmental Issues, and Case Histories

    Burton, Dennis

    2001-01-01

    The use of chlorine by electric utilities and other surface water users to inhibit biofouling and the chlorination of wastewater by POTWs to eliminate the discharge of pathogenic organisms are widespread practices...

  14. Elaboration in the area of low temperature chlorination of rare-metal crude ore

    Mirsaidov, U.M.

    2002-01-01

    The chemical base of low temperature chlorination of rare-metal crude ore was elaborated. The chemical nature of chlorination process which pass at low temperature was decoded and scientifically elaborated

  15. Heat-Activated Persulfate Oxidation of Chlorinated Solvents in Sandy Soil

    Jialu Liu

    2014-01-01

    Full Text Available Heat-activated persulfate oxidative treatment of chlorinated organic solvents containing chlorinated ethenes and ethanes in soil was investigated with different persulfate dosages (20 g/L, 40 g/L, and 60 g/L and different temperatures (30°C, 40°C, and 50°C. Chlorinated organic solvents removal was increased as persulfate concentration increase. The persulfate dosage of 20 g/L with the highest OE (oxidant efficiency value was economically suitable for chlorinated organic solvents removal. The increasing temperature contributed to the increasing depletion of chlorinated organic solvents. Chlorinated ethenes were more easily removed than chlorinated ethanes. Moreover, the persulfate depletion followed the pseudo-first-order reaction kinetics (kps=0.0292 [PS]0+0.0008, R2=0.9771. Heat-activated persulfate appeared to be an effective oxidant for treatment of chlorinated hydrocarbons.

  16. Chlorine release from biomass. Part 6; Kloravgaang fraan biobraenslen. Del 6

    Zintl, Frank; Stroemberg, Birgitta [TPS Termiska Processer AB, Nykoeping (Sweden)

    2000-04-01

    Chlorine release from model compounds and different biomass fuels has been studied during thermal treatment in an electric oven in inert atmosphere (N{sub 2}) and with addition of 10% O{sub 2}. The amount of chlorine in all investigated materials has been kept to 2% with addition of KCl solution in methanol. The amount of chlorine was analysed before and after treatment in the decided atmosphere and to the temperature chosen. The influence from different functional groups on the chlorine release at low temperatures has been studied in pyrolysis experiments of simple model compounds with different structures. A good correlation between the chlorine release and the functional groups in the model substances was achieved. Results from the experiments shows that the early chlorine release, is most likely to occur in all biofuels, since all biomass fuels contains biological material with significant amounts of functional groups which can interact with fuel chlorine ( inorganic chlorine)

  17. Characterization of the bacterial community in shower water before and after chlorination

    Peters, Marjolein C. F. M.; Keuten, Maarten G. A.; Knezev, Aleksandra; van Loosdrecht, Mark C. M.; Vrouwenvelder, Johannes S.; Rietveld, Luuk C.; de Kreuk, Merle K.

    2017-01-01

    Gram-negative. The dominant bacterial families with a relative abundance of ≥10% of the total (non-chlorinated and chlorinated) communities were Flavobacteriaceae (24–21%), Xanthomonadaceae (23–24%), Moraxellaceae (12–11%) and Pseudomonadaceae (10

  18. Cooling-water chlorination: the kinetics of chlorine, bromine, and ammonia in sea water

    Johnson, J.D.; Inman, G.W. Jr.; Trofe, T.W.

    1982-11-01

    The major inorganic reaction pathways for the chlorination of saline waters were measured by a variety of techniques including: (1) amperometric titration, (2) amperometric membrane covered electrode, (3) uv spectrophotometry, (4) conventional kinetics methods for slow reactions, and (5) stopped-flow kinetics measurements with a microcomputer data acquisition system. The major reactions studied were: (1) the competitive reactions of ammonia and bromide ion with hypochlorous acid, (2) bromide oxidation by hypochlorous acid, (3) monochloramine formation in sea water, (4) monobromamine formation and subsequent disproportionation to form dibromamine, and (5) monochloramine oxidation of bromide to form bromochloramine. Reaction rates were determined in sodium chloride and sea water as a function of reactant concentration, pH, salinity, and ammonia concentration. Rate constants and corresponding rate laws and mechanisms were developed for each reaction

  19. Combined treatment of Pseudomonas aeruginosa biofilms with bacteriophages and chlorine.

    Zhang, Yanyan; Hu, Zhiqiang

    2013-01-01

    Bacterial biofilms are a growing concern in a broad range of areas. In this study, a mixture of RNA bacteriophages isolated from municipal wastewater was used to control and remove biofilms. At the concentrations of 400 and 4 × 10(7) PFU/mL, the phages inhibited Pseudomonas aeruginosa biofilm formation by 45 ± 15% and 73 ± 8%, respectively. At the concentrations of 6,000 and 6 × 10(7) PFU/mL, the phages removed 45 ± 9% and 75 ± 5% of pre-existing P. aeruginosa biofilms, respectively. Chlorine reduced biofilm growth by 86 ± 3% at the concentration of 210 mg/L, but it did not remove pre-existing biofilms. However, a combination of phages (3 × 10(7) PFU/mL) and chlorine at this concentration reduced biofilm growth by 94 ± 2% and removed 88 ± 6% of existing biofilms. In a continuous flow system with continued biofilm growth, a combination of phages (a one-time treatment at the concentration of 1.9 × 10(8) PFU/mL for 1 h first) with chlorine removed 97 ± 1% of biofilms after Day 5 while phage and chlorine treatment alone removed 89 ± 1% and 40 ± 5%, respectively. For existing biofilms, a combined use of a lower phage concentration (3.8 × 10(5) PFU/mL) and chlorination with a shorter time duration (12 h) followed by continuous water flushing removed 96 ± 1% of biofilms in less than 2 days. Laser scanning confocal microscopy supplemented with electron microscopy indicated that the combination treatment resulted in biofilms with lowest cell density and viability. These results suggest that the combination treatment of phages and chlorine is a promising method to control and remove bacterial biofilms from various surfaces. Copyright © 2012 Wiley Periodicals, Inc.

  20. Experimental cancer studies of chlorinated by-products

    Komulainen, Hannu

    2004-01-01

    Chlorinated drinking water contains a number of different by-products formed during the chlorination process from organic matter. The carcinogenicity of only a fraction of them have been evaluated in experimental animals. The focus has been on compounds and groups of compounds that are most abundant in chlorinated drinking water or the in vitro toxicity data have suggested genotoxic potential. From trihalomethanes, chloroform causes liver tumors in mice and female rats and renal tumors in male mice and rats. Tumor formation by chloroform is strongly associated with cytotoxicity and regenerative cell proliferation in tissues and that has been considered to be one determinant of its carcinogenicity. From halogenic acetic acids, dichloroacetic acid (DCA) and trichlotoacetic acid (TCA) are hepatocarcinogenic in mice and DCA in male rats. Their genotoxicity is equivocal and nongenotoxic mechanisms, such as peroxisome proliferation and hypomethylation of DNA in the liver, likely contribute to tumor development. From chlorinated furanones (CHFs), 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX) is a multisite carcinogen in rats (e.g. in thyroid glands and liver) and it has caused DNA damage in vivo. MX may be a complete carcinogen because it also has promoter properties in vitro. Chlorinated drinking water may also contain brominated by-products providing the raw water contains bromide. At least some of them (bromodichloromethane, bromoform) have been shown to be carcinogenic in laboratory animals. Altogether, although several by-products have been shown to have carcinogenic potential in laboratory animals, it not yet possible to state which compounds or groups of by-products cause the cancer risk in chlorinated drinking water. The cellular mechanisms of their effects and these effects at low concentrations are still poorly understood. The few studies with mixtures of these by-products suggest that the mixture effects may be complex and unpredictable (inhibitory

  1. Chlorinated hydrocarbon contaminants in arctic marine mammals.

    Norstrom, R J; Muir, D C

    1994-09-16

    By 1976, the presence of chlorinated hydrocarbon contaminants (CHCs) had been demonstrated in fur seal (Callorhinus ursinus), ringed seal (Phoca hispida), hooded seal (Cystophora cristata), bearded seal (Erignathus barbatus), walrus (Obdobenus rosmarus divergens), beluga (Delphinapterus leucas), porpoise (Phocoena phocoena) and polar bear (Ursus maritimus) in various parts of the Arctic. In spite of this early interest, very little subsequent research on contaminants in Arctic marine mammals was undertaken until the mid-1980s. Since that time, there has been an explosion of interest, resulting in a much expanded data base on contaminants in Arctic marine mammals. Except in the Russian Arctic, data have now been obtained on the temporospatial distribution of PCBs and other contaminants in ringed seal, beluga and polar bear. Contaminants in narwhal (Monodon monoceros) have also now been measured. On a fat weight basis, the sum of DDT-related compounds (S-DDT) and PCB levels are lowest in walrus (Polar bears have similar levels of PCBs as cetaceans (1-10 micrograms/g), but with a much simpler congener pattern. DDE levels are lowest in polar bear, indicating rapid metabolism. Effects of age and sex on residue levels are found for all species where this was measured. Among cetaceans and ringed seal, sexually mature females have lower levels than males due to lactation. Although PCB levels in adult male polar bears are about twice as high as females, there is only a trivial age effect in either sex apart from an initial decrease from birth to sexual maturity (age 0-5). Comparison of levels of S-DDT and PCBs in Arctic beluga and ringed seal with those in beluga in the Gulf of St. Lawrence and ringed seal in the Baltic Sea, indicate that overall contamination of the Arctic marine ecosystem is 10-50 times less than the most highly contaminated areas in the northern hemisphere temperate latitude marine environment. Geographic distribution of residue levels in polar bears

  2. Aspects of chlorination and its potential to produce niobium pentoxide

    Brocchi, E.A.; Jeffes, J.H.E.

    1984-01-01

    Reduction chlorination of niobium pentoxide were carried out under different experimental conditions in order to study the effects of some variables of the process. In order to evaluate the efficiency of the recovery of niobium pentoxide which could be obtained as condensed material a group of experiments were also carried out with pyrochlore concentrate. The results showed that a balance of factors such as temperature, percentage of carbon in the initial charge and porosity cause the progress of the reaction to be controlled by different mechanisms and indicate that chlorination can be used to produce niobium pentoxide-especially if applied on rich starting material. (Author) [pt

  3. [Changes of chlorine isotope composition characterize bacterial dehalogenation of dichloromethane].

    Ziakun, A M; Firsova, Iu E; Torgonskaia, M L; Doronina, N V; Trotsenko, Iu A

    2007-01-01

    Fractionation of dichloromethane (DCM) molecules with different chlorine isotopes by aerobic methylobacteria Methylobacterium dichloromethanicum DM4 and Albibacter nethylovorans DM10; cell-free extract of strain DM4; and transconjugant Methylobacterium evtorquens Al1/pME 8220, expressing the dcmA gene for DCM dehalogenase but unable to grow on DCM, was studied. Kinetic indices of DCM isotopomers for chlorine during bacterial dehalogenation and diffusion were compared. A two-step model is proposed, which suggests diffusional DCM transport to bacterial cells.

  4. Ultraviolet light: sterile water without chlorine smell and taste

    Anon.

    1977-01-01

    The use of chlorine and hypochlorite is necessary in larger waterworks, but it is a disadvantage in smaller plants, where overtreatment easily leads to smell and taste of chlorine in the water. Ultraviolet light with a wavelength of 2535 Angstrom gives 100% disinfection with a dose of 10 mWs/cm 2 for all known bacteria. In practice a dose of 40 mWs/cm 2 and an irradiation time of 15 minutes is desireable. A standard unit utilising six UV light tubes arranged concentrically around a quartz tube, through which the water flows, is described briefly. (JIW)

  5. Ultraviolet light: sterile water without chlorine smell and taste

    1977-02-14

    The use of chlorine and hypochlorite is necessary in larger waterworks, but it is a disadvantage in smaller plants, where overtreatment easily leads to smell and taste of chlorine in the water. Ultraviolet light with a wavelength of 2535 Angstrom gives 100% disinfection with a dose of 10 mWs/cm/sup 2/ for all known bacteria. In practice a dose of 40 mWs/cm/sup 2/ and an irradiation time of 15 minutes is desireable. A standard unit utilising six UV light tubes arranged concentrically around a quartz tube, through which the water flows, is described briefly.

  6. Tools for Management of Chlorinated Solvent - Contaminated Sites

    2009-12-03

    Movie Lee Ann Doner – (2008) MS CSU “Sandy aquifers” Image from Fred Payne /ARCADIS New Paradigm After NRC 2005 l~r SERDP. Advancing solvent plume...Situ Bioremediation Using Emulsified  Edible  Oil”   AFCEE (http://www.afcee.brooks.af.mil/products/techtrans/) - “Principles and Practices of Enhanced...Anaerobic Bioremediation of  Chlorinated Solvents”  - “Protocol for In Situ Bioremediation of Chlorinated Solvents Using  Edible  Oil” 232 Short Course

  7. Pepspectives of chlorine application in metallurgy of vanadium

    Korshunov, B.G.; Kutsenko, S.A.

    1983-01-01

    The most expedient variants of reprocessing of vanadium technical oxide (5), ferrovanadium and converter slags by chlorine technology with production of pure metal are considered. It is shown that production of vanadium by the way of electro- or metallothermal reduction of chlorides provides more plastic metal in comparison with reduction from oxides. The methods of production of VOCl 3 , VCl 4 and vanadium lowest chlorides are considered. Necessity of expansion of production of vanadium chlorine derivatives is dictated as well by their increasing application in different areas of national economy, in particular, as catalysts in organic synthesis

  8. Chlorine international thermodynamic tables of the fluid state

    Angus, S; de Reuck, K M

    1985-01-01

    Chlorine: International Thermodynamic Tables of the Fluid State-8 is a four-chapter book that covers available and estimated data on chlorine; estimation of the element's properties; the correlating equations for the element; and how the tabulated properties are calculated from chosen equation. The tables in this book give the volume, entropy, enthalpy, isobaric heat capacity, compression factor, fugacity/pressure ratio, Joule-Thomson coefficient, ratio of the heat capacities, and speed of sound as a function of pressure and temperature. Given in the tables as well are the pressure, entropy, i

  9. The optimization of the analysis of chlorine-36 in urine

    Joseph, S.; Kramer, G.H.

    1982-02-01

    A method has been developed and optimized for the analysis of chlorine-36 in urine. Problems such as sample size, photodecomposition of silver chloride and anion interferences have been solved and are discussed in detail. The analysis is performed by first removing interfering phosphates and sulphates from an untreated urine sample and isolating the chlorine-36 as silver chloride. The precipitate is counted in a planchet counter. Recoveries are estimated to be 90 +- 5% with a detection limit of 3 pCi (0.1 Bq) for a routine sample (counting time 10 minutes, counting efficiency 10%, sample size 100 mL)

  10. Oxidation of pharmaceuticals by chlorine dioxide in biologically treated wastewater

    Hey, G.; Grabic, R.; Ledin, A.

    2012-01-01

    Biologically treated wastewater spiked with a mixture of 56 active pharmaceutical ingredients (APIs) was treated with 0–20mg/L chlorine dioxide (ClO2) solution in laboratory-scale experiments. Wastewater effluents were collected from two wastewater treatment plants in Sweden, one with extended......O2, while in high COD effluent a significant increase in API oxidation was observed after treatment with 8mg/L ClO2. This study illustrates the successful degradation of several APIs during treatment of wastewater effluents with chlorine dioxide....

  11. Inactivation of Giardia muris cysts by free chlorine.

    Leahy, J G; Rubin, A J; Sproul, O J

    1987-01-01

    The chlorine resistance of cysts of the flagellate protozoan Giardia muris was examined. This organism, which is pathogenic to mice, is being considered as a model for the inactivation of the human pathogen Giardia lamblia. Excystation was used as the criterion for cyst viability. Experiments were performed at pH 5, 7, and 9 at 25 degrees C and pH 7 at 5 degrees C. Survival curves were "stepladder"-shaped, but concentration-time data generally conformed to Watson's Law. Chlorine was most effe...

  12. Chlorine cycling and fates of 36Cl in terrestrial environments

    Bastviken, David; Svensson, Teresia; Sandén, Per; Kylin, Henrik

    2013-01-01

    Chlorine-36 (36Cl), a radioisotope of chlorine (Cl) with a half-life of 301,000 years, is present in some types of nuclear waste and is disposed in repositories for radioactive waste. As the release of 36Cl from such repositories to the near surface environment has to be taken into account it is of interest to predict possible fates of 36Cl under various conditions as a part of the safety assessments of repositories for radioactive waste. This report aims to summarize the state of the art kno...

  13. Evaluation of sea water chlorine demand in condenser cooling water at TAPS 1 and 2

    Papachan, Deepa; Gupta, P.K.; Patil, D.P.; Save, C.B.; Anilkumar, K.R.

    2008-01-01

    To prevent microbiological growth in the condenser tubes, condenser cooling water chlorination is very important. For effective chlorination, chlorine dose rate and frequency of dosing has to be determined on the basis of sea water chlorine demand. TAPS 1 and 2 is located near Arabian sea and draws water from this sea for its condenser cooling. The present practice of chlorine dosing at TAPS 1 and 2, based on the analysis carried out by GE in 1969, is 2500 kg/day/CWpump and 90 kg/day/SSWpump for a contact period of 25 minutes. Normal frequency of dosing is once per 8 hour and booster dose is once in a week at the same rate for 1 hour. The criteria of effective chlorination is to get residual chlorine of 2-3 ppm at the condenser water box outlet during chlorination at water box inlet/CW pump suction header in the recommended dose rate. The other option of chlorination was continuous dosing to get 0.5 ppm residual chlorine. This option has its own limitations as it is more expensive and also that micro organisms get immune to chlorine eventually due to continuous dosing. Nevertheless higher chlorine dosing is detrimental to AI-brass condenser tubes. Therefore the second option was not adopted at TAPS 1 and 2. Tarapur Atomic Power Station-1 is in the process of replacement of condenser tubes due to frequent condenser tube failures in the recent years. It was essential to analyse the present sea water chlorine demand and re-determine the chlorine dose rate because of development of industries under Maharashtra Industrial Development Corporation (MIDC) and simultaneous population growth around this area over a period of three decades. This paper discusses the experimental observations regarding significant change in sea water chlorine demand over this period and the effect of seasonal changes on sea water chlorine demand. (author)

  14. Chlorinated cooling waters in the marine environment: development of effluent guidelines

    Capuzzo, J M; Goldman, J C; Davidson, J A; Lawrence, S A

    1977-07-01

    The effects of free chlorine and chloramine on stage I lobster larvae and juvenile killifish were investigated in continuous flow bioassay units. In comparing mortality and changes in standard respiration rates during and after exposure to either chlorine form, significant respiratory stress was observed with exposure to sublethal levels. Sublethal responses to free and combined chlorine should be considered when establishing regulations for chlorine residuals in cooling waters.

  15. Assessing chlorinated ethene degradation in a large scale contaminant plume by dual carbon–chlorine isotope analysis and quantitative PCR

    Hunkeler, D.; Abe, Y.; Broholm, Mette Martina

    2011-01-01

    The fate of chlorinated ethenes in a large contaminant plume originating from a tetrachloroethene (PCE) source in a sandy aquifer in Denmark was investigated using novel methods including compound-specific carbon and chlorine isotope analysis and quantitative real-time polymerase chain reaction (q...... reduction by pyrite as indicated by the formation of cDCE and stable carbon isotope data. TCE and cDCE showed carbon isotope trends typical for reductive dechlorination with an initial depletion of 13C in the daughter products followed by an enrichment of 13C as degradation proceeded. At 1000 m downgradient......DCE. The significant enrichment of 13C in VC indicates that VC was transformed further, although the mechanismcould not be determined. The transformation of cDCEwas the rate limiting step as no accumulation of VC occurred. In summary, the study demonstrates that carbon–chlorine isotope analysis and qPCR combinedwith...

  16. Determination of Residual Chlorine and Turbidity in Drinking Water. Instructor's Manual.

    Office of Water Program Operations (EPA), Cincinnati, OH. National Training and Operational Technology Center.

    This instructor's guide presents analytical methods for residual chlorine and turbidity. Topics include sample handling, permissable concentration levels, substitution of residual chlorine for bacteriological work, public notification, and the required analytical techniques to determine residual chlorine and turbidity. This publication is intended…

  17. Determination of Residual Chlorine and Turbidity in Drinking Water. Student Manual.

    Office of Water Program Operations (EPA), Cincinnati, OH. National Training and Operational Technology Center.

    This student's manual covers analytical methods for residual chlorine and turbidity. Topics include sample handling, permissable concentration levels, substitution of residual chlorine for bacteriological work, public notification, and the required analytical techniques to determine residual chlorine and turbidity. The publication is intended for…

  18. Kinetic study on the chlorination of β-spodumene for lithium extraction with Cl2 gas

    Barbosa, L.I.; Valente, N.G.; González, J.A.

    2013-01-01

    Highlights: ► β-Spodumene was chlorinated to extract lithium with pure chlorine. ► The kinetics of the chlorination was studied in the range of 1000–1100 °C. ► Cl 2 flow rate, sample mass, and Cl 2 partial pressure were the operating variables. ► Experimental data were best fitted by the sequential nucleation and growth model. - Abstract: In this paper, the kinetics chlorination of β-spodumene for the extraction of lithium has been studied using gaseous chlorine as chlorinating agent. The effect of chlorine flow rate, temperature, mass of the sample, and partial pressure of Cl 2 was investigated. The study of the effect of chlorine flow rate indicated that the chlorination of β-spodumene may be carried out in the presence of active chlorinating species The chlorine partial pressure was found to have an appreciable effect on the system reactivity. The temperature was found to be the most important variable affecting the reaction rate. The β-spodumene chlorination process by Cl 2 was characterized by an apparent activation energy of about 359 kJ/mol in the range from 1000 to 1100 °C. Reaction was of non-catalytic gas–solid nature and experimental data fitted the sequential nucleation and growth model

  19. Estimates of Gibbs free energies of formation of chlorinated aliphatic compounds

    Dolfing, Jan; Janssen, Dick B.

    1994-01-01

    The Gibbs free energy of formation of chlorinated aliphatic compounds was estimated with Mavrovouniotis' group contribution method. The group contribution of chlorine was estimated from the scarce data available on chlorinated aliphatics in the literature, and found to vary somewhat according to the

  20. Electrochemical depth profiling of multilayer metallic structures: An aluminum brazing sheet

    Afshar, F. Norouzi; Ambat, R.; Kwakernaak, C.

    2012-01-01

    Combinatory localized electrochemical cell and glow discharge optical emission spectrometry (GDOES) measurements were performed to obtain a thorough in depth electrochemical characterization of an aluminum brazing sheet. By defining electrochemical criteria i.e. breakdown potential, corrosion...... potential, cathodic and anodic reactivities, and tracking their changes as a function of depth, the evolution of electrochemical responses through out the material thickness were analyzed and correlated to the corresponding microstructural features. Polarization curves in 1wt% NaCl solution at pH 2.8 were...... obtained at different depths from the surface using controlled sputtering in a glow discharge optical emission spectrometer as a sample preparation technique. The anodic and cathodic reactivity of the top surface areas were significantly higher than that of the bulk, thus indicating these areas to be more...

  1. Argon plasma treatment to enhance the electrochemical reactivity of screen-printed carbon surfaces

    Ghamouss, F.; Luais, E. [Universite de Nantes, Faculte des Sciences et des Techniques, Chimie et Interdisciplinarite: Synthese, Analyse, Modelisation (CEISAM), UMR CNRS no 6230, 2, rue de la Houssiniere, BP 92208, 44322 NANTES Cedex 3 (France); Universite de Nantes, Institut des Materiaux Jean Rouxel IMN - CNRS, 2 rue de la Houssiniere, BP 32229, 44322 Nantes Cedex 3 (France); Thobie-Gautier, C. [Universite de Nantes, Faculte des Sciences et des Techniques, Chimie et Interdisciplinarite: Synthese, Analyse, Modelisation (CEISAM), UMR CNRS no 6230, 2, rue de la Houssiniere, BP 92208, 44322 NANTES Cedex 3 (France); Tessier, P.-Y. [Universite de Nantes, Faculte des Sciences et des Techniques, Chimie et Interdisciplinarite: Synthese, Analyse, Modelisation (CEISAM), UMR CNRS no 6230, 2, rue de la Houssiniere, BP 92208, 44322 NANTES Cedex 3 (France); Universite de Nantes, Institut des Materiaux Jean Rouxel IMN - CNRS, 2 rue de la Houssiniere, BP 32229, 44322 Nantes Cedex 3 (France); Boujtita, M. [Universite de Nantes, Faculte des Sciences et des Techniques, Chimie et Interdisciplinarite: Synthese, Analyse, Modelisation (CEISAM), UMR CNRS no 6230, 2, rue de la Houssiniere, BP 92208, 44322 NANTES Cedex 3 (France)], E-mail: mohammed.boujtita@univ-nantes.fr

    2009-04-15

    Radiofrequency argon plasma was used for screen-printed carbon electrodes (SPCE) surface treatment. The cyclic voltammetry of ferri/ferrocyanide as redox couple showed a remarkable improvement of the electrochemical reactivity of the SPCE after the plasma treatment. The effect of the plasma growth conditions on the efficiency of the treatment procedure was evaluated in term of electrochemical reactivity of the SPCE surface. The electrochemical study showed that the electrochemical reactivity of the treated electrodes was strongly dependant on radiofrequency power, treatment time and argon gas pressure. X-ray photoelectron spectroscopy (XPS) analysis showed a considerable evolution on the surface chemistry of the treated electrodes. Our results clearly showed that the argon plasma treatment induces a significant increase in the C{sub sp2}/C{sub sp3} ratio. The scanning electron micrograph (SEM) also showed a drastic change on the surface morphology of the treated SPCEs.

  2. Simultaneously Coupled Mechanical-Electrochemical-Thermal Simulation of Lithium-Ion Cells: Preprint

    Zhang, Chao; Santhanagopalan, Shriram; Sprague, Michael A.; Pesaran, Ahmad A.

    2016-08-01

    Understanding the combined electrochemical-thermal and mechanical response of a system has a variety of applications, for example, structural failure from electrochemical fatigue and the potential induced changes of material properties. For lithium-ion batteries, there is an added concern over the safety of the system in the event of mechanical failure of the cell components. In this work, we present a generic multi-scale simultaneously coupled mechanical-electrochemical-thermal model to examine the interaction between mechanical failure and electrochemical-thermal responses. We treat the battery cell as a homogeneous material while locally we explicitly solve for the mechanical response of individual components using a homogenization model and the electrochemical-thermal responses using an electrochemical model for the battery. A benchmark problem is established to demonstrate the proposed modeling framework. The model shows the capability to capture the gradual evolution of cell electrochemical-thermal responses, and predicts the variation of those responses under different short-circuit conditions.

  3. Electrochemical performance in the hydrogen evolution reaction of Ni-TR (TR= La, Ce) materials synthesized using the solid state reaction method; Desempeno electroquimico en la reaccion de evolucion de hidrogeno de materiales de electrodo Ni-TR (TR = La, Ce) sintetizados por el metodo de reaccion de estado solido

    Torres-Huerta, A. M.; Dominguez-Crespo, M. A.; Ramirez-Meneses, E.; Yanez-Zamora, C. [CICATA, IPN, Altamira, Tamaulipas (Mexico); Avila-Garcia, I. [IPN, ESIQIE, UPALM, Mexico, D.F. (Mexico)]. E-mail: mdominguezc@ipn.mx; adcrespo2000@yahoo.com.mx

    2009-09-15

    At the industrial level, the use of fuel cell technology is still limited because of the high costs of its parts and costs related to its operations. Although the electrode material with greater electroactivity is Pt, because of its high cost, alternative electrocatalysts have been sought that balance cost and activity. One of the materials that have been most widely used is nickel, along with some of its alloys. This material has shown good performance using low overpotentials in traditional reactions such as hydrogen (HER) and oxygen (OER) evolution, as well as high resistance to corrosion and low costs. In particular, binary and ternary alloys have shown significant increases in HER activity when compared to materials in the pure or massive state. Therefore, in the search for new alternatives with acceptable efficiency and low-cost, this work obtained Ni-TR (TR = La, Ce) using solid-state reaction with metallic acetylacetonates and metallic powder. These materials were synthesized for 3 h at different temperatures (795 or 920, 1000 and 1200 degrees Celsius) in order to evaluate the effect on the electrochemical performance of the electrocatalysts. The structural and morphological characterization of materials was performed with XRD and SEM techniques, respectively. In addition, the electrochemical performance of electrode materials was evaluated with HER using cyclic voltametry (CV) and potentiodynamic curves. The results obtained show that a combination of oxides was obtained (NiO, CeO{sub 2} and LaNiO{sub 3}) at low temperatures; nonetheless, as the synthesis temperatures increase, NiO-CeO{sub 2} and NiO-LaNiO{sub 3} alloys are formed, respectively. A clear dependence was also observed between electrocatalytic activity and the source for obtaining these materials(Ni-TR). [Spanish] A nivel industrial, el uso de la tecnologia de celdas de combustible esta todavia limitada debido sobre todo a los altos costos de las partes que la constituyen y los costos

  4. Electrochemical oxidation of organic waste

    Almon, A.C.; Buchanan, B.R.

    1990-01-01

    Both silver catalyzed and direct electrochemical oxidation of organic species are examined in analytical detail. This paper describes the mechanisms, reaction rates, products, intermediates, capabilities, limitations, and optimal reaction conditions of the electrochemical destruction of organic waste. A small bench-top electrocell being tested for the treatment of small quantities of laboratory waste is described. The 200-mL electrochemical cell used has a processing capacity of 50 mL per day, and can treat both radioactive and nonradioactive waste. In the silver catalyzed process, Ag(I) is electrochemically oxidized to Ag(II), which attacks organic species such as tributylphosphate (TBP), tetraphenylborate (TPB), and benzene. In direct electrochemical oxidation, the organic species are destroyed at the surface of the working electrode without the use of silver as an electron transfer agent. This paper focuses on the destruction of tributylphosphate (TBP), although several organic species have been destroyed using this process. The organic species are converted to carbon dioxide, water, and inorganic acids

  5. Photoproduction of Hydrogen by Decamethylruthenocene Combined with Electrochemical Recycling.

    Rivier, Lucie; Peljo, Pekka; Vannay, Laurent A C; Gschwend, Grégoire C; Méndez, Manuel A; Corminboeuf, Clémence; Scanlon, Micheál D; Girault, Hubert H

    2017-02-20

    The photoinduced hydrogen evolution reaction (HER) by decamethylruthenocene, Cp 2 *Ru II (Cp*=C 5 Me 5 ), is reported. The use of a metallocene to photoproduce hydrogen is presented as an alternative strategy to reduce protons without involving an additional photosensitizer. The mechanism was investigated by (spectro)electrochemical and spectroscopic (UV/Vis and 1 H NMR) measurements. The photoactivated hydride involved was characterized spectroscopically and the resulting [Cp 2 *Ru III ] + species was electrochemically regenerated in situ on a fluorinated tin oxide electrode surface. A promising internal quantum yield of 25 % was obtained. Optimal experimental conditions- especially the use of weakly coordinating solvent and counterions-are discussed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Ultramicrosensors based on transition metal hexacyanoferrates for scanning electrochemical microscopy

    Maria A. Komkova

    2013-10-01

    Full Text Available We report here a way for improving the stability of ultramicroelectrodes (UME based on hexacyanoferrate-modified metals for the detection of hydrogen peroxide. The most stable sensors were obtained by electrochemical deposition of six layers of hexacyanoferrates (HCF, more specifically, an alternating pattern of three layers of Prussian Blue and three layers of Ni–HCF. The microelectrodes modified with mixed layers were continuously monitored in 1 mM hydrogen peroxide and proved to be stable for more than 5 h under these conditions. The mixed layer microelectrodes exhibited a stability which is five times as high as the stability of conventional Prussian Blue-modified UMEs. The sensitivity of the mixed layer sensor was 0.32 A·M−1·cm−2, and the detection limit was 10 µM. The mixed layer-based UMEs were used as sensors in scanning electrochemical microscopy (SECM experiments for imaging of hydrogen peroxide evolution.

  7. The study of marine corrosion of copper alloys in chlorinated condenser cooling circuits: the role of microbiological components.

    Carvalho, Maria L; Doma, Jemimah; Sztyler, Magdalena; Beech, Iwona; Cristiani, Pierangela

    2014-06-01

    The present paper reports the on-line monitoring of corrosion behavior of the CuNi 70:30 and Al brass alloys exposed to seawater and complementary offline microbiological analyses. An electrochemical equipment with sensors specifically set for industrial application and suitable to estimate the corrosion (by linear polarization resistance technique), the biofilm growth (by the BIOX electrochemical probe), the chlorination treatment and other physical-chemical parameters of the water has been used for the on-line monitoring. In order to identify and better characterize the bacteria community present on copper alloys, tube samples were collected after a long period (1year) and short period (2days) of exposition to treated natural seawater (TNSW) and natural seawater (NSW). From the collected samples, molecular techniques such as DNA extraction, polymerase chain reaction (PCR), denaturing gradient gel electrophoresis (DGGE) and identification by sequencing were performed to better characterize and identify the microbial biodiversity present in the samples. The monitoring data confirmed the significant role played by biofouling deposition against the passivity of these Cu alloys in seawater and the positive influence of antifouling treatments based on low level dosages. Molecular analysis indicated biodiversity with the presence of Marinobacter, Alteromonas and Pseudomonas species. Copyright © 2013 Elsevier B.V. All rights reserved.

  8. Superhydrophobic surfaces by electrochemical processes.

    Darmanin, Thierry; Taffin de Givenchy, Elisabeth; Amigoni, Sonia; Guittard, Frederic

    2013-03-13

    This review is an exhaustive representation of the electrochemical processes reported in the literature to produce superhydrophobic surfaces. Due to the intensive demand in the elaboration of superhydrophobic materials using low-cost, reproducible and fast methods, the use of strategies based on electrochemical processes have exponentially grown these last five years. These strategies are separated in two parts: the oxidation processes, such as oxidation of metals in solution, the anodization of metals or the electrodeposition of conducting polymers, and the reduction processed such as the electrodeposition of metals or the galvanic deposition. One of the main advantages of the electrochemical processes is the relative easiness to produce various surface morphologies and a precise control of the structures at a micro- or a nanoscale. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Comparison of antimicrobial activities of brine salting, Chlorinated ...

    Chemical preservatives can be used to reduce the overall microbial populations in fish and fish products. This study was set to determine the antimicrobial activities of brine salting, chlorinated solution, and Moringa oleifera plant extracts treatments on enteric bacteria in Rastrineobola argentea and Oreochromis niloticus fish ...

  10. Structural and optical properties of chlorinated plasma polymers

    Turri, Rafael; Davanzo, Celso U.; Schreiner, Wido; Dias da Silva, José Humberto; Appolinario, Marcelo Borgatto; Durrant, Steven F.

    2011-01-01

    Amorphous hydrogenated chlorinated carbon (a-C:H:Cl) films were produced by the plasma polymerization of chloroform–acetylene–argon mixtures in a radiofrequency plasma enhanced chemical vapor deposition system. The main parameter of interest was the proportion of chloroform in the feed, R C , which was varied from 0 to 80%. Deposition rates of 80 nm min −1 were typical for the chlorinated films. Infrared reflection–absorption spectroscopy revealed the presence of C–Cl groups in all the films produced with chloroform in the feed. X-ray photoelectron spectroscopy confirmed this finding, and revealed a saturation of the chlorine content at ∼ 47 at.% for R C ≥ 40%. The refractive index and optical gap, E 04 , of the films were roughly in the 1.6 to 1.7, and the 2.8 to 3.7 eV range. These values were calculated from transmission ultraviolet–visible-near infrared spectra. Chlorination leads to an increase in the water surface contact angle from ∼ 40° to ∼ 77°.

  11. The chlorine isotope fingerprint of the lunar magma ocean.

    Boyce, Jeremy W; Treiman, Allan H; Guan, Yunbin; Ma, Chi; Eiler, John M; Gross, Juliane; Greenwood, James P; Stolper, Edward M

    2015-09-01

    The Moon contains chlorine that is isotopically unlike that of any other body yet studied in the Solar System, an observation that has been interpreted to support traditional models of the formation of a nominally hydrogen-free ("dry") Moon. We have analyzed abundances and isotopic compositions of Cl and H in lunar mare basalts, and find little evidence that anhydrous lava outgassing was important in generating chlorine isotope anomalies, because (37)Cl/(35)Cl ratios are not related to Cl abundance, H abundance, or D/H ratios in a manner consistent with the lava-outgassing hypothesis. Instead, (37)Cl/(35)Cl correlates positively with Cl abundance in apatite, as well as with whole-rock Th abundances and La/Lu ratios, suggesting that the high (37)Cl/(35)Cl in lunar basalts is inherited from urKREEP, the last dregs of the lunar magma ocean. These new data suggest that the high chlorine isotope ratios of lunar basalts result not from the degassing of their lavas but from degassing of the lunar magma ocean early in the Moon's history. Chlorine isotope variability is therefore an indicator of planetary magma ocean degassing, an important stage in the formation of terrestrial planets.

  12. Aerobic biodegradation of a mixture of chlorinated organics in ...

    STORAGESEVER

    2008-07-04

    Jul 4, 2008 ... DCM; and 0.232 – 0.588 week-1 for DCA in both water microcosms with higher degradation generally observed in New ... Key words: Bioaugmentation, biodegradation, biostimulation, chlorinated aliphatic hydrocarbons, microcosms. ... culture (OD of 1 at λ600) of the consortia was added separately to.

  13. Chlorine stress mediates microbial surface attachment in drinking water systems.

    Liu, Li; Le, Yang; Jin, Juliang; Zhou, Yuliang; Chen, Guowei

    2015-03-01

    Microbial attachment to drinking water pipe surfaces facilitates pathogen survival and deteriorates disinfection performance, directly threatening the safety of drinking water. Notwithstanding that the formation of biofilm has been studied for decades, the underlying mechanisms for the origins of microbial surface attachment in biofilm development in drinking water pipelines remain largely elusive. We combined experimental and mathematical methods to investigate the role of environmental stress-mediated cell motility on microbial surface attachment in chlorination-stressed drinking water distribution systems. Results show that at low levels of disinfectant (0.0-1.0 mg/L), the presence of chlorine promotes initiation of microbial surface attachment, while higher amounts of disinfectant (>1.0 mg/L) inhibit microbial attachment. The proposed mathematical model further demonstrates that chlorination stress (0.0-5.0 mg/L)-mediated microbial cell motility regulates the frequency of cell-wall collision and thereby controls initial microbial surface attachment. The results reveal that transport processes and decay patterns of chlorine in drinking water pipelines regulate microbial cell motility and, thus, control initial surface cell attachment. It provides a mechanistic understanding of microbial attachment shaped by environmental disinfection stress and leads to new insights into microbial safety protocols in water distribution systems.

  14. Morphological study of synthesized chlorinated polyethylene by inductive plasma

    Olayo, M.G.; Cruz, G.; Carapia, L.; Fernandez, G.; Morales, J.

    2004-01-01

    In this work a morphological study on the synthesis of Chlorinated polyethylene for plasma starting from Trichloroethylene in a polymerization process and ablation simultaneous of metals, where silver atoms and copper are inserted directly during the growth of the polymer from the gas phase to the one solid is presented. (Author)

  15. Natural attenuation of chlorinated ethenes in hyporheic zones

    Weatherill, John J.; Atashgahi, Siavash; Schneidewind, Uwe; Krause, Stefan; Ullah, Sami; Cassidy, Nigel; Rivett, Michael O.

    2018-01-01

    Chlorinated ethenes (CEs) are legacy contaminants whose chemical footprint is expected to persist in aquifers around the world for many decades to come. These organohalides have been reported in river systems with concerning prevalence and are thought to be significant chemical stressors in urban

  16. PHYTOREMEDIATION POTENTIAL OF A CHLORINATED SOLVENTS PLUME IN CENTRAL FLORIDA

    The potential for phytoremediation of a shallow chlorinated solvent plume was assessed by application of ground water flow and evapotranspiration (ET) models for a site in Orlando, Florida. The focus of the work was on the hydrologic and hydraulic factors that influence phytoreme...

  17. Riverine input of chlorinated hydrocarbons in the coastal pollution

    Sarkar, A.; Everaarts, J.M.

    of various chlorinated hydrocarbons. It deals with an in-depth analysis of pollution of the coastal ecosystem around the Netherlands, U.K. and Germany due to inputs of contaminants from the rivers namely, Elbe, Weser, Ems Ijssel, Rhine, Meuse, Scheldt, Thames...

  18. Analysis of alternative flow sheets for the hybrid chlorine cycle

    Gooding, Charles H. [Department of Chemical and Biomolecular Engineering, 209 Earle Hall, Clemson University, Clemson, SC 29634-0909 (United States)

    2009-05-15

    This paper reports the results of the most complete conceptual study conducted to date on hydrogen production using the hybrid chlorine cycle. Three alternative process flow sheets were developed, each capable of producing hydrogen at 35 C (308 K) and 21 bar. The alternative approaches differ primarily in the way HCl is isolated and converted to hydrogen and chlorine gases. Aspen Plus trademark simulation software was used to model the unit processes, supplemented where necessary by custom Excel spreadsheets. Major equipment was sized for a 200-million kg/yr plant; feasible materials of construction were identified; fixed capital investments and variable costs were estimated. Estimated net thermal efficiencies of the flow sheets range from 30% to 36%, based on the lower heating value of the hydrogen produced. With electrical power valued at $0.05/kWh, the cost of hydrogen produced by the hybrid chlorine cycle would be at least $3/kg. These results indicate that direct electrolysis of water is a more attractive way to produce hydrogen than any presently conceived version of the hybrid chlorine cycle. (author)

  19. Structural and optical properties of chlorinated plasma polymers

    Turri, Rafael [Laboratorio de Plasmas Tecnologicos, Campus Experimental de Sorocaba, Universidade Estadual Paulista (UNESP), Avenida Tres de Marco 511, Alto de Boa Vista, 18087-180, Sorocaba, SP (Brazil); Davanzo, Celso U. [Instituto de Quimica, Universidade Estadual de Campinas, Campinas, SP (Brazil); Schreiner, Wido [Departamento de Fisica, Universidade Federal de Parana, PR (Brazil); Dias da Silva, Jose Humberto [Faculdade de Ciencias, Universidade Estadual Paulista (UNESP), Bauru, SP (Brazil); Appolinario, Marcelo Borgatto [Laboratorio de Plasmas Tecnologicos, Campus Experimental de Sorocaba, Universidade Estadual Paulista (UNESP), Avenida Tres de Marco 511, Alto de Boa Vista, 18087-180, Sorocaba, SP (Brazil); Durrant, Steven F., E-mail: steve@sorocaba.unesp.br [Laboratorio de Plasmas Tecnologicos, Campus Experimental de Sorocaba, Universidade Estadual Paulista (UNESP), Avenida Tres de Marco 511, Alto de Boa Vista, 18087-180, Sorocaba, SP (Brazil)

    2011-12-30

    Amorphous hydrogenated chlorinated carbon (a-C:H:Cl) films were produced by the plasma polymerization of chloroform-acetylene-argon mixtures in a radiofrequency plasma enhanced chemical vapor deposition system. The main parameter of interest was the proportion of chloroform in the feed, R{sub C}, which was varied from 0 to 80%. Deposition rates of 80 nm min{sup -1} were typical for the chlorinated films. Infrared reflection-absorption spectroscopy revealed the presence of C-Cl groups in all the films produced with chloroform in the feed. X-ray photoelectron spectroscopy confirmed this finding, and revealed a saturation of the chlorine content at {approx} 47 at.% for R{sub C} {>=} 40%. The refractive index and optical gap, E{sub 04}, of the films were roughly in the 1.6 to 1.7, and the 2.8 to 3.7 eV range. These values were calculated from transmission ultraviolet-visible-near infrared spectra. Chlorination leads to an increase in the water surface contact angle from {approx} 40 Degree-Sign to {approx} 77 Degree-Sign .

  20. DFT application for chlorin derivatives photosensitizer drugs modeling

    Machado, Neila; Carvalho, B. G.; Téllez Soto, C. A.; Martin, A. A.; Favero, P. P.

    2018-04-01

    Photodynamic therapy is an alternative form of cancer treatment that meets the desire for a less aggressive approach to the body. It is based on the interaction between a photosensitizer, activating light, and molecular oxygen. This interaction results in a cascade of reactions that leads to localized cell death. Many studies have been conducted to discover an ideal photosensitizer, which aggregates all the desirable characteristics of a potent cell killer and generates minimal side effects. Using Density Functional Theory (DFT) implemented in the program Vienna Ab-initio Simulation Package, new chlorin derivatives with different functional groups were simulated to evaluate the different absorption wavelengths to permit resonant absorption with the incident laser. Gaussian 09 program was used to determine vibrational wave numbers and Natural Bond Orbitals. The chosen drug with the best characteristics for the photosensitizer was a modified model of the original chlorin, which was called as Thiol chlorin. According to our calculations it is stable and is 19.6% more efficient at optical absorption in 708 nm in comparison to the conventional chlorin e6. Vibrational modes, optical and electronic properties were predicted. In conclusion, this study is an attempt to improve the development of new photosensitizer drugs through computational methods that save time and contribute to decrease the numbers of animals for model application.

  1. Degradation of chlorinated compounds in an anaerobic-aerobic process

    Alfan-Guzman, R.; Guerrero-Barajas, C.; Garcia-Pena, I.

    2009-07-01

    Remediation technologies that involves gas transport (e.g., soil vapor extraction and air sparging of groundwater) cause the emission of gases contaminated with chlorinated solvents. Under anaerobic conditions, reductive dechlorination of trichloroethylene (TCE) proceeds via the formation of cis and trans dichloroethene (DCEs) and vinyl chloride (VC) as intermediates. (Author)

  2. A Plume Scale Model of Chlorinated Ethene Degradation

    Murray, Alexandra Marie; Broholm, Mette Martina; Badin, Alice

    leaked from a dry cleaning facility, and a 2 km plume extends from the source in an unconfined aquifer of homogenous fluvio-glacial sand. The area has significant iron deposits, most notably pyrite, which can abiotically degrade chlorinated ethenes. The source zone underwent thermal (steam) remediation...

  3. Chlorinated paraffins wrapping of carbon nanotubes: A theoretical investigation

    Ding, Qiuyue; Ding, Ning; Chen, Xiangfeng; Wu, Chi-Man Lawrence

    2018-04-01

    How nanomaterials interact with pollutants is the central for understanding their environmental behavior and practical application. In this work, molecular dynamics (MD) and density functional theoretical (DFT) methods were used to investigated the influence of carbon chain length, degree of chlorination, chain configuration, and chirality of chlorinated paraffin (CP) and diameter of single-walled carbon nanotubes (SWNTs) on the interaction between CPs and SWNTs. The simulation results demonstrated that CP chain length and chlorination degree played considerably important roles in determining interaction strength between SWNTs and CPs. The interaction energies increased with increasing chain length and chlorination degree. The chirality of SWNT exerted negligible influence on the interaction energy between SWNTs and CPs. On the contrary, interaction energy increased with increasing radius of SWNTs due to the surface curvatures. This result was rationalized by considering the decrease in SWNT curvature with increasing radius, which resulted in plane-like CNT wall. The negligible influence of CP chain configurations was attributed to relative flexibility of CP carbon chains, which can wrap on tubes through conformational changes with low-energy barriers. MD results indicated that CPs could adsorb on SWNT surface rapidly in aqueous environment. Charge transfer and electronic density results indicated that the interaction between CPs and SWNTs was physisorption in nature. This work provides fundamental information regarding SWNTs as sorbents for CPs extraction and adsorptive removal from environmental water system.

  4. Rate of absorption and interfacial area of chlorine into aqueous ...

    Due to excellent mass transfer characteristics with energy efficiency jet ejectors can be used in place of conventional countercurrent systems, namely, packed bed contactors as well as venturi scrubbers, cyclones and airlift pumps. The removal of chlorine from certain gases by absorption in aqueous solutions of sodium ...

  5. Dose and temperature criteria for radiation chlorination of ethane

    Prasil, Z.

    1979-01-01

    General criteria determining the region of dose rates and temperatures at which a radiation-induced chain reaction proceeds are applied to a series of subsequent and competitive chain reactions of the chlorination of ethane and its derivatives. The calculations presume that the reactions proceed in an ideal through-flow chemical reactor with a piston flow. (M.S.)

  6. Effectiveness of chlorination and ozonation methods on pure ...

    Other oxidants, such as ozone, could be used for bulking control. In view of the fact that chlorine and ozone are both non-selective chemical agents affecting filamentous and floc-forming micro-organisms, the determination of optimum dosage conditions becomes essential to minimise the impact produced on the activated ...

  7. Chlorinated Iridoid Glucosides from Veronica longifolia and their Antioxidant Activity

    Jensen, Søren Rosendal; Gotfredsen, Charlotte Held; Harput, U. Sebnem

    2010-01-01

    From Veronica longifolia were isolated three chlorinated iridoid glucosides, namely asystasioside E (6) and its 6-O-esters 6a and 6b, named longifoliosides A and B, respectively. The structures of 6a and 6b were proved by analysis of their spectroscopic data and by conversion to the catalpol ester...

  8. Degradation of Chlorinated Aromatic Compounds in UASB Reactors

    Christiansen, Nina; Hendriksen, Hanne Vang; Järvinen, Kimmo T.

    1995-01-01

    Data on anaerobic degradation of chloroaromatic compounds in Upflow Anaerobic Sludge Blanket Reactors (UASB-reactor) are presented and compared. Special attention is given to the metabolic pathways for degradation of chlorinated phenols by granular sludge. Results indicate that PCP can be degraded...

  9. Transformation of chlorinated compounds by methanogenic granular sludge

    Eekert, van M.H.A.

    1999-01-01

    Chlorinated compounds are an important group of contaminants often found in sediments, groundwater, soils, wastewaters, and off-gasses. Many of these pollutants are found on the EPA list of Priority Pollutants indicating their potential hazard for the environment. Initial degradation can

  10. 75 FR 51113 - Chlorinated Isocyanurates From China and Spain

    2010-08-18

    ... Isocyanurates From China and Spain AGENCY: United States International Trade Commission. ACTION: Scheduling of... and Spain. SUMMARY: The Commission hereby gives notice of the scheduling of expedited reviews pursuant... revocation of the antidumping duty orders on chlorinated isocyanurates from China and Spain would be likely...

  11. Effectiveness of chlorination and ozonation methods on pure ...

    2005-01-16

    Jan 16, 2005 ... dising agents on the metabolic activity and the viability of the micro-organisms. Ozone was found to ..... the antimicrobial action of ozone and chlorine. This strain was ... The pH of the culture medium was adjusted to 7.0 with ..... indicated that lysis of the cells can result for high concentrations or extended ...

  12. Inhibition of lipopolysaccharide induced acute inflammation in lung by chlorination.

    Zhang, Jinshan; Xue, Jinling; Xu, Bi; Xie, Jiani; Qiao, Juan; Lu, Yun

    2016-02-13

    Lipopolysaccharide (LPS, also called endotoxin) is a pro-inflammatory constituent of gram negative bacteria and cyanobacteria, which causes a potential health risk in the process of routine urban application of reclaimed water, such as car wash, irrigation, scenic water refilling, etc. Previous studies indicated that the common disinfection treatment, chlorination, has little effect on endotoxin activity removal measured by Limulus amebocyte lysate (LAL) assay. However, in this study, significant decrease of acute inflammatory effects was observed in mouse lung, while LAL assay still presented a moderate increase of endotoxin activity. To explore the possible mechanisms, the nuclear magnetic resonance (NMR) results showed the chlorination happened in alkyl chain of LPS molecules, which could affect the interaction between LPS and LPS-binding protein. Also the size of LPS aggregates was found to drop significantly after treatment, which could be another results of chlorination caused polarity change. In conclusion, our observation demonstrated that chlorination is effective to reduce the LPS induced inflammation in lung, and it is recommended to use health effect-based methods to assess risk removal of water treatment technologies. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. Chlorination and cleavage of lignin structures by fungal chloroperoxidases

    Patricia Ortiz-Bermudez; Ewald Srebotnik; Kenneth E. Hammel

    2003-01-01

    Two fungal chloroperoxidases (CPOs), the heme enzyme from Caldariomyces fumago and the vanadium enzyme from Curvularia inaequalis, chlorinated 1-(4-ethoxy-3-methoxyphenyl)-2-(2-methoxyphenoxy)-1,3-dihydroxypropane, a dimeric model compound that represents the major nonphenolic structure in lignin. Both enzymes also cleaved this dimer to give 1-chloro-4-ethoxy-3-...

  14. Challenges in subsurface in situ remediation of chlorinated solvents

    Broholm, Mette Martina; Fjordbøge, Annika Sidelmann; Christiansen, Camilla Maymann

    2014-01-01

    Chlorinated solvent source zones in the subsurface pose a continuous threat to groundwater quality at many sites worldwide. In situ remediation of these sites is particularly challenging in heterogeneous fractured media and where the solvents are present as DNAPL. In situ remediation by chemical...

  15. Chlorinative stress in age-related diseases: a literature review.

    Casciaro, Marco; Di Salvo, Eleonora; Pace, Elisabetta; Ventura-Spagnolo, Elvira; Navarra, Michele; Gangemi, Sebastiano

    2017-01-01

    Aging is an agglomerate of biological long-lasting processes that result being inevitable. Main actors in this scenario are both long-term inflammation and oxidative stress. It has been proved that oxidative stress induce alteration in proteins and this fact itself is critically important in the pathophysiological mechanisms leading to diseases typical of aging. Among reactive species, chlorine ones such as hypochlorous acid (HOCl) are cytotoxic oxidants produced by activated neutrophils during chronic inflammation processes. HOCl can also cause damages by reacting with biological molecules. HOCl is generated by myeloperoxidase (MPO) and augmented serum levels of MPO have been described in acute and chronic inflammatory conditions in cardiovascular patients and has been implicated in many inflammatory diseases such as atherosclerosis, neurodegenerative conditions, and some cancers. Due to these data, we decided to conduct an up-to-date review evaluating chlorinative stress effects on every age-related disease linked; potential anti-oxidant countermeasures were also assessed. Results obtained associated HOCl generation to the aging processes and confirmed its connection with diseases like neurodegenerative and cardiovascular pathologies, atherosclerosis and cancer; chlorination was mainly linked to diseases where molecular (protein) alteration constitute the major suspected cause: i.e. inflammation, tissue lesions, DNA damages, apoptosis and oxidative stress itself. According data collected, a healthy lifestyle together with some dietary suggestion and/or the administration of nutracetical antioxidant integrators could balance the effects of chlorinative stress and, in some cases, slow down or prevent the onset of age-releated diseases.

  16. Inactivation of human and simian rotaviruses by chlorine dioxide

    Chen, Yu-Shiaw (Brookhaven National Lab., Upton, NY (USA)); Vaughn, J.M. (Univ. of New England College of Medicine, Biddeford, ME (USA))

    1990-05-01

    The inactivation of single-particle stocks of human (type 2, Wa) and simian (SA-11) rotaviruses by chlorine dioxide was investigated. Experiments were conducted at 4{degree}C in a standard phosphate-carbonate buffer. Both virus types were rapidly inactivated, within 20 s under alkaline conditions, when chlorine dioxide concentrations ranging from 0.05 to 0.2 mg/liter were used. Similar reductions of 10{sup 5}-fold in infectivity required additional exposure time of 120 s at 0.2 mg/liter for Wa and at 0.5 mg/liter for SA-11, respectively, at pH 6.0. The inactivation of both virus types was moderate a neutral pH, and the sensitivities to chlorine dioxide were similar. The observed enhancement of virucidal efficiency with increasing pH was contrary to earlier findings with chlorine- and ozone-treated rotavirus particles, where efficiencies decreased with increasing alkalinity. Comparison of 99.9% virus inactivation times revealed ozone to be the most effective virucidal agent among these three disinfectants.

  17. Bromination of Marine Dissolved Organic Matter following Full Scale Electrochemical Ballast Water Disinfection.

    Gonsior, Michael; Mitchelmore, Carys; Heyes, Andrew; Harir, Mourad; Richardson, Susan D; Petty, William Tyler; Wright, David A; Schmitt-Kopplin, Philippe

    2015-08-04

    An extensively diverse array of brominated disinfection byproducts (DBPs) were generated following electrochemical disinfection of natural coastal/estuarine water, which is one of the main treatment methods currently under consideration for ballast water treatment. Ultra-high-resolution mass spectrometry revealed 462 distinct brominated DBPs at a relative abundance in the mass spectra of more than 1%. A brominated DBP with a relative abundance of almost 22% was identified as 2,2,4-tribromo-5-hydroxy-4-cyclopentene-1,3-dione, which is an analogue to several previously described 2,2,4-trihalo-5-hydroxy-4-cyclopentene-1,3-diones in drinking water. Several other brominated molecular formulas matched those of other known brominated DBPs, such as dibromomethane, which could be generated by decarboxylation of dibromoacetic acid during ionization, dibromophenol, dibromopropanoic acid, dibromobutanoic acid, bromohydroxybenzoic acid, bromophenylacetic acid, bromooxopentenoic acid, and dibromopentenedioic acid. Via comparison to previously described chlorine-containing analogues, bromophenylacetic acid, dibromooxopentenoic acid, and dibromopentenedioic acid were also identified. A novel compound at a 4% relative abundance was identified as tribromoethenesulfonate. This compound has not been previously described as a DBP, and its core structure of tribromoethene has been demonstrated to show toxicological implications. Here we show that electrochemical disinfection, suggested as a candidate for successful ballast water treatment, caused considerable production of some previously characterized DBPs in addition to novel brominated DBPs, although several hundred compounds remain structurally uncharacterized. Our results clearly demonstrate that electrochemical and potentially direct chlorination of ballast water in estuarine and marine systems should be approached with caution and the concentrations, fate, and toxicity of DBP need to be further characterized.

  18. Chlorine-36 and the initial value problem

    Davis, Stanley N.; Cecil, DeWayne; Zreda, Marek; Sharma, Pankaj

    Chlorine-36 is a radionuclide with a half-life of 3.01×105a. Most 36Cl in the hydrosphere originates from cosmic radiation interacting with atmospheric gases. Large amounts were also produced by testing thermonuclear devices during 1952-58. Because the monovalent anion, chloride, is the most common form of chlorine found in the hydrosphere and because it is extremely mobile in aqueous systems, analyses of both total Cl- as well as 36Cl have been important in numerous hydrologic studies. In almost all applications of 36Cl, a knowledge of the initial, or pre-anthropogenic, levels of 36Cl is useful, as well as essential in some cases. Standard approaches to the determination of initial values have been to: (a) calculate the theoretical cosmogenic production and fallout, which varies according to latitude; (b) measure 36Cl in present-day precipitation and assume that anthropogenic components can be neglected; (c) assume that shallow groundwater retains a record of the initial concentration; (d) extract 36Cl from vertical depth profiles in desert soils; (e) recover 36Cl from cores of glacial ice; and (f) calculate subsurface production of 36Cl for water that has been isolated from the atmosphere for more than one million years. The initial value from soil profiles and ice cores is taken as the value that occurs directly below the depth of the easily defined bomb peak. All six methods have serious weaknesses. Complicating factors include 36Cl concentrations not related to cosmogenic sources, changes in cosmogenic production with time, mixed sources of chloride in groundwater, melting and refreezing of water in glaciers, and seasonal groundwater recharge that does not contain average year-long concentrations of 36Cl. Résumé Le chlore-36 est un radionucléide de période 3.01×105a. Pour l'essentiel, le 36Cl dans l'hydrosphère provient des effets du rayonnement cosmique sur les gaz atmosphériques. De grandes quantités de 36Cl ont aussi été produites au cours des

  19. Gas-permeable hydrophobic tubular membranes for ammonia recovery in bio-electrochemical systems

    Kuntke, P.; Zamora, P.; Saakes, M.; Buisman, C.J.N.; Hamelers, H.V.M.

    2016-01-01

    The application of a gas-permeable hydrophobic tubular membrane in bio-electrochemical systems enables efficient recovery of ammonia (NH3) from their cathode compartments. Due to a hydrogen evolution reaction at the cathode, no chemical addition was required to increase the pH for

  20. Theoretical Insight into the Trends that Guide the Electrochemical Reduction of Carbon Dioxide to Formic Acid

    Yoo, J.S.; Christensen, Rune; Vegge, Tejs

    2016-01-01

    The electrochemical reduction (electroreduction) of CO2 to formic acid (HCOOH) and its competing reactions, that is, the electroreduction of CO2 to CO and the hydrogen evolution reaction (HER), on twenty-seven different metal surfaces have been investigated using density functional theory (DFT) c...

  1. Reaction Front Evolution during Electrochemical Lithiation of Crystalline Silicon Nanopillars

    Lee, Seok Woo

    2012-12-01

    The high theoretical specific capacity of Si as an anode material is attractive in lithium-ion batteries, although the issues caused by large volume changes during cycling have been a major challenge. Efforts have been devoted to understanding how diffusion-induced stresses cause fracture, but recent observations of anisotropic volume expansion in single-crystalline Si nanostructures require new theoretical considerations of expansion behavior during lithiation. Further experimental investigation is also necessary to better understand the anisotropy of the lithiation process. Here, we present a method to reveal the crystalline core of partially lithiated Si nanopillars with three different crystallographic orientations by using methanol to dissolve the Li atoms from the amorphous Li-Si alloy. The exposed crystalline cores have flat {110} surfaces at the pillar sidewalls; these surfaces represent the position of the reaction front between the crystalline core and the amorphous Li-Si alloy. It was also found that an amorphous Si structure remained on the flat surfaces of the crystalline core after dissolution of the Li, which was presumed to be caused by the accumulation of Si atoms left over from the removal of Li from the Li-Si alloy. © 2012 Wiley-VCH Verlag GmbH &Co. KGaA, Weinheim.

  2. Reaction Front Evolution during Electrochemical Lithiation of Crystalline Silicon Nanopillars

    Lee, Seok Woo; Berla, Lucas A.; McDowell, Matthew T.; Nix, William D.; Cui, Yi

    2012-01-01

    The high theoretical specific capacity of Si as an anode material is attractive in lithium-ion batteries, although the issues caused by large volume changes during cycling have been a major challenge. Efforts have been devoted to understanding how diffusion-induced stresses cause fracture, but recent observations of anisotropic volume expansion in single-crystalline Si nanostructures require new theoretical considerations of expansion behavior during lithiation. Further experimental investigation is also necessary to better understand the anisotropy of the lithiation process. Here, we present a method to reveal the crystalline core of partially lithiated Si nanopillars with three different crystallographic orientations by using methanol to dissolve the Li atoms from the amorphous Li-Si alloy. The exposed crystalline cores have flat {110} surfaces at the pillar sidewalls; these surfaces represent the position of the reaction front between the crystalline core and the amorphous Li-Si alloy. It was also found that an amorphous Si structure remained on the flat surfaces of the crystalline core after dissolution of the Li, which was presumed to be caused by the accumulation of Si atoms left over from the removal of Li from the Li-Si alloy. © 2012 Wiley-VCH Verlag GmbH &Co. KGaA, Weinheim.

  3. Selective synthesis and characterization of chlorins as sensitizers for photodynamic therapy

    Montforts, Franz-Peter; Kusch, Dirk; Hoper, Frank; Braun, Stefan; Gerlach, Benjamin; Brauer, Hans-Dieter; Schermann, Guido; Moser, Joerg G.

    1996-04-01

    Chlorin type sensitizers have ideal photophysical properties for an application in PDT. The basic chlorin framework of these sensitizers has to be modified by attachment of lipophilic and hydrophilic residues to achieve a good cell uptake and tumor enrichment. In the present study we describe the selective synthesis of amphiphilic chlorins starting from the readily accessible red blood pigment heme. The photophysical properties of the well defined synthetic chlorins are characterized by photophysical investigations. The kinetic of cell uptake, the localization in the cell and the photodynamic behavior of the amphiphilic sensitizers are demonstrated by incubation of A 375 cancer cell lines with structurally different chlorins.

  4. Stratospheric chlorine injection by volcanic eruptions - HCl scavenging and implications for ozone

    Tabazadeh, A.; Turco, R. P.

    1993-01-01

    Because the output of volatile chlorine during a major volcanic event can greatly exceed the annual anthropogenic emissions of chlorine to the atmosphere, the fate of volcanic chlorine must be known. Although numerous observations have shown that volcanoes do not significantly contribute to the stratospheric chlorine burden, no quantitative explanation has been published. Hydrogen chloride (HCl) scavenging processes during the early phases of a volcanic eruption are discussed. A plume dynamics and thermodynamics model is used to show that HCl removal in condensed supercooled water can reduce HCl vapor concentrations by up to four orders of magnitude, preventing substantial stratospheric chlorine injection.

  5. Determination of chlorine in nuclear-grade uranium compounds by ion-selective electrode

    Yang Chunqing; Liu Fuyun; Huang Dianfan.

    1989-01-01

    The determination of microamount chlorine in nuclear-grade uranium compounds is described. Chlorine is separated from uranium oxide pyrohydrolytically with stream of wet oxygen in a furnace at 800-900 deg C. Chlorine is volatilized as hydrochloric acid, which then is absorbed in a dilute alkaline solution and measured with chlorine selective electrode. This method covers the concentration range of 10-500 ppm chlorine in uranium oxide. The relative standard diviation is better than 10% and recovery of 85-108% has been reported

  6. Comprehensive Model for Enhanced Biodegradation of Chlorinated Solvents in Groundwater

    Kouznetsova, I.; Gerhard, J. I.; Mao, X.; Robinson, C.; Barry, A. D.; Harkness, M.; Mack, E. E.; Dworatzek, S.

    2007-12-01

    SABRE (Source Area BioREmediation) is a public/private consortium whose charter is to de-termine if enhanced anaerobic bioremediation can result in effective treatment of chlorinated solvent DNAPL source areas. The focus of this 4-year, $5.7 million research and development project is a field site in the United Kingdom containing TCE DNAPL. A comprehensive numerical model for simulating dehalogenation of chlorinated ethenes has been developed. The model considers the kinetic dissolution of DNAPL and nonaqueous organic amendments, bacterial growth and decay, and the interaction of biological and geochemical reactions that might influence biological activity. The model accounts for inhibitory effects of high chlorin-ated solvent concentrations as well as the link between fermentation and dehalogenation due to dynamic hydrogen concentration (the direct electron donor). In addition to the standard biodegradation pathways, sulphate reduction, mineral dissolution and precipitation kinetics are incorporated. These latter processes influence the soil buffering capacity and thus the net acidity generated. One-dimensional simulations were carried out to reproduce the data from columns packed with site soil and groundwater exhibiting both intermediate (250 mg/L) and near solubility (1100 mg/L) TCE concentrations. The modelling aims were to evaluate the key processes underpinning bioremediation success and provide a tool for investigating field sys-tem sensitivity to site data and design variables. This paper will present the model basis and validation and examine sensitivity to key processes including chlorinated ethene partitioning into soybean oil, sulphate reduction, and geochemical influences such as pH and the role of buffering in highly dechlorinating systems.

  7. Bulk chlorine uptake by polyamide active layers of thin-film composite membranes upon exposure to free chlorine-kinetics, mechanisms, and modeling.

    Powell, Joshua; Luh, Jeanne; Coronell, Orlando

    2014-01-01

    We studied the volume-averaged chlorine (Cl) uptake into the bulk region of the aromatic polyamide active layer of a reverse osmosis membrane upon exposure to free chlorine. Volume-averaged measurements were obtained using Rutherford backscattering spectrometry with samples prepared at a range of free chlorine concentrations, exposure times, and mixing, rinsing, and pH conditions. Our volume-averaged measurements complement previous studies that have quantified Cl uptake at the active layer surface (top ≈ 7 nm) and advance the mechanistic understanding of Cl uptake by aromatic polyamide active layers. Our results show that surface Cl uptake is representative of and underestimates volume-averaged Cl uptake under acidic conditions and alkaline conditions, respectively. Our results also support that (i) under acidic conditions, N-chlorination followed by Orton rearrangement is the dominant Cl uptake mechanism with N-chlorination as the rate-limiting step; (ii) under alkaline conditions, N-chlorination and dechlorination of N-chlorinated amide links by hydroxyl ion are the two dominant processes; and (iii) under neutral pH conditions, the rates of N-chlorination and Orton rearrangement are comparable. We propose a kinetic model that satisfactorily describes Cl uptake under acidic and alkaline conditions, with the largest discrepancies between model and experiment occurring under alkaline conditions at relatively high chlorine exposures.

  8. Electrochemical depth profiling of multilayer metallic structures: An aluminum brazing sheet

    Afshar, F. Norouzi; Ambat, R.; Kwakernaak, C.; Wit, J.H.W. de; Mol, J.M.C.; Terryn, H.

    2012-01-01

    Highlights: ► Localized electrochemical cell and glow discharge optical emission spectrometry were used. ► An electrochemical depth profile of an aluminum brazing sheet was obtained. ► The electrochemical responses were correlated to the microstructural features. - Abstract: Combinatory localized electrochemical cell and glow discharge optical emission spectrometry (GDOES) measurements were performed to obtain a thorough in depth electrochemical characterization of an aluminum brazing sheet. By defining electrochemical criteria i.e. breakdown potential, corrosion potential, cathodic and anodic reactivities, and tracking their changes as a function of depth, the evolution of electrochemical responses through out the material thickness were analyzed and correlated to the corresponding microstructural features. Polarization curves in 1 wt% NaCl solution at pH 2.8 were obtained at different depths from the surface using controlled sputtering in a glow discharge optical emission spectrometer as a sample preparation technique. The anodic and cathodic reactivity of the top surface areas were significantly higher than that of the bulk, thus indicating these areas to be more susceptible to localized attack. Consistent with this, optical microscopy and scanning electron microscope analysis revealed a relatively high density of fine intermetallic and silicon particles at these areas. The corrosion mechanism of the top layers was identified to be intergranular and pitting corrosion, while lower sensitivity to these localized attacks were detected toward the brazing sheet core. The results highlight the successful application of the electrochemical depth profiling approach in prediction of the corrosion behavior of the aluminum brazing sheet and the importance of the electrochemical activity of the outer 10 μm in controlling the corrosion performance of the aluminum brazing sheet.

  9. Chlorination for biofouling control in power plant cooling water system - a review

    Satpathy, K.K.; Ruth Nithila, S.D.

    2008-01-01

    Fresh water is becoming a rare commodity day by day and thus power plant authorities are turning into sea to make use of the copious amount of seawater available at an economical rate for condenser cooling. Unfortunately, biofouling; the growth and colonization of marine organisms affect the smooth operation of power plant cooling water systems. This is more so, if the plant is located in tropical climate having clean environment, which enhances the variety and density of organisms. Thus, biofouling needs to be controlled for efficient operation of the power plant. Biocide used for biofouling control is decided based on three major criteria viz: it should be economically, operationally and environmentally acceptable to the power plant authorities. Chlorine among others stands out on the top and meets all the above requirements in spite of a few shortcomings. Therefore it is no wonder that still chlorine rules the roost and chlorination remains the most common method of biofouling control in power plant cooling water system all over the world. Although, it is easier said than done, a good amount of R and D work is essential before a precise chlorination regime is put into pragmatic use. This paper discusses in details the chemistry of chlorination such as chlorine demand, chlorine decay, break point chlorination, speciation of chlorine residual and role of temperature and ammonia on chlorination in biofouling control. Moreover, targeted and pulse chlorination are also discussed briefly. (author)

  10. Temperature sensitivity indicates that chlorination of organic matter in forest soil is primarily biotic.

    Bastviken, David; Svensson, Teresia; Karlsson, Susanne; Sandén, Per; Oberg, Gunilla

    2009-05-15

    Old assumptions that chloride is inert and that most chlorinated organic matter in soils is anthropogenic have been challenged by findings of naturally formed organochlorines. Such natural chlorination has been recognized for several decades, but there are still very few measurements of chlorination rates or estimates of the quantitative importance of terrestrial chlorine transformations. While much is known about the formation of specific compounds, bulk chlorination remains poorly understood in terms of mechanisms and effects of environmental factors. We quantified bulk chlorination rates in coniferous forest soil using 36Cl-chloride in tracer experiments at different temperatures and with and without molecular oxygen (O2). Chlorination was enhanced by the presence of O2 and had a temperature optimum at 20 degrees C. Minimum rates were found at high temperatures (50 degrees C) or under anoxic conditions. The results indicate (1) that most of the chlorination between 4 and 40 degrees C was biotic and driven by O2 dependent enzymes, and (2) that there is also slower background chlorination occurring under anoxic conditions at 20 degrees C and under oxic conditions at 50 degrees C. Hence, while oxic and biotic chlorination clearly dominated, chlorination by other processes including possible abiotic reactions was also detected.

  11. Formation of trichloromethane in chlorinated water and fresh-cut produce and as a result of reacting with citric acid

    Chlorine (sodium hypochlorite) is commonly used by the fresh produce industry to sanitize wash water, fresh and fresh-cut fruits and vegetables. However, possible formation of harmful chlorine by-products is a concern. The objectives of this study were to compare chlorine and chlorine dioxide in t...

  12. ASCORBIC ACID REDUCTION OF ACTIVE CHLORINE PRIOR TO DETERMINING AMES MUTAGENICITY OF CHLORINATED NATURAL ORGANIC MATTER (NOM)

    Many potable water disinfection byproducts (DBPs) that result from the reaction of natural organic matter (NOM) with oxidizing chlorine are known or suspected to be carcinogenic and mutagenic. The Ames assay is routinely used to assess an overall level of mutagenicity for all com...

  13. Chloride pyrometallurgy of uranium ore. 1. Chlorination of phosphate ore using solid or gas chlorinating agent and carbon

    Taki, Tomihiro; Komoto, Shigetoshi; Otomura, Keiichiro; Takenaka, Toshihide; Sato, Nobuaki; Fujino, Takeo.

    1995-01-01

    A thermodynamical and pyrometallurgical study to recover uranium from the phosphate ores was undertaken using the chloride volatilization method. Iron was chlorinated with solid chlorinating agents such as NaCl and CaCl 2 in combination with activated carbon, which will be used for removing this element from the ore, but uranium was not. On the other hand, the chlorination using Cl 2 gas and activated carbon gave a good result at 1,223 K. Not only uranium but also iron, phosphorus, aluminum and silicon were found to form volatile chlorides which vaporized out of the ore, while calcium remained in the ore as non-volatile CaCl 2 . The chlorination condition was studied as functions of temperature, reaction time and carbon content. The volatilization ratio of uranium around 95% was obtained by heating the mixture of the ore and activated carbon (35 wt%) in a mixed gas flow of Cl 2 (200 ml/min) and N 2 (200 ml/min) at 1,223 K for 120 min. (author)

  14. Electrochemical degradation of sulfonamides at BDD electrode: Kinetics, reaction pathway and eco-toxicity evaluation

    Fabiańska, Aleksandra; Białk-Bielińska, Anna; Stepnowski, Piotr [Faculty of Chemistry, University of Gdansk, ul. Wita Stwosza 63, 80-952 Gdansk (Poland); Stolte, Stefan [Faculty of Chemistry, University of Gdansk, ul. Wita Stwosza 63, 80-952 Gdansk (Poland); UFT-Centre of Environmental Research and Sustainable Technology, University of Bremen, Leobener Straße UFT, D-28359 Bremen (Germany); Siedlecka, Ewa Maria, E-mail: ewa.siedlecka@ug.edu.pl [Faculty of Chemistry, University of Gdansk, ul. Wita Stwosza 63, 80-952 Gdansk (Poland)

    2014-09-15

    Highlights: • SNs were electrochemically oxidized at BDD in one compartment reactor. • The efficiency of SN degradation was the highest in effluents from municipal WWTP. • The electro-degradation SNs based on oxidation but reduction was also possible. • Electrochemical oxidation of SNs led in some cases to mixtures toxic to L. minor. - Abstract: The investigation dealt with electrochemical oxidation of five sulfonamides (SNs): sulfadiazine (SDZ), sulfathiazole (STZ), sulfamerazine (SMR), sulfamethazine (SMN) and sulfadimethoxine (SDM) in aqueous solution at boron-doped diamond (BDD) electrode. All studied sulfonamides were degraded according to a pseudo first order kinetics. The structure of SNs had no significant effect on the values of pseudo first order rate constants. Increased degradation efficiency was observed in higher temperature and in acidic pH. Due to the presence of chlorine and nitrate SNs were more effectively oxidized from municipal wastewater treatment plant (WWTP) effluents than from pure supporting electrolyte Na{sub 2}SO{sub 4}. The intermediates identified by LC–MS and GC–MS analysis suggested that the hydroxyl radicals attack mainly the S-N bond, but also the aromatic ring systems (aniline, pyrimidine or triazole) of SNs. Finally, the toxicity of the SNs solutions and effluents after electrochemical treatment was assessed through the measurement of growth inhibition of green algae (Scenedesmus vacualatus) and duckweed (Lemna minor). Toxicity of SMR, STZ, SMN solutions before and after electrochemical oxidation and SDM solution after the process in L. minor test was observed. No significant toxicity of studied SNs was observed in algae test.

  15. Electrochemical degradation of sulfonamides at BDD electrode: Kinetics, reaction pathway and eco-toxicity evaluation

    Fabiańska, Aleksandra; Białk-Bielińska, Anna; Stepnowski, Piotr; Stolte, Stefan; Siedlecka, Ewa Maria

    2014-01-01

    Highlights: • SNs were electrochemically oxidized at BDD in one compartment reactor. • The efficiency of SN degradation was the highest in effluents from municipal WWTP. • The electro-degradation SNs based on oxidation but reduction was also possible. • Electrochemical oxidation of SNs led in some cases to mixtures toxic to L. minor. - Abstract: The investigation dealt with electrochemical oxidation of five sulfonamides (SNs): sulfadiazine (SDZ), sulfathiazole (STZ), sulfamerazine (SMR), sulfamethazine (SMN) and sulfadimethoxine (SDM) in aqueous solution at boron-doped diamond (BDD) electrode. All studied sulfonamides were degraded according to a pseudo first order kinetics. The structure of SNs had no significant effect on the values of pseudo first order rate constants. Increased degradation efficiency was observed in higher temperature and in acidic pH. Due to the presence of chlorine and nitrate SNs were more effectively oxidized from municipal wastewater treatment plant (WWTP) effluents than from pure supporting electrolyte Na 2 SO 4 . The intermediates identified by LC–MS and GC–MS analysis suggested that the hydroxyl radicals attack mainly the S-N bond, but also the aromatic ring systems (aniline, pyrimidine or triazole) of SNs. Finally, the toxicity of the SNs solutions and effluents after electrochemical treatment was assessed through the measurement of growth inhibition of green algae (Scenedesmus vacualatus) and duckweed (Lemna minor). Toxicity of SMR, STZ, SMN solutions before and after electrochemical oxidation and SDM solution after the process in L. minor test was observed. No significant toxicity of studied SNs was observed in algae test

  16. Studies on electrochemical treatment of wastewater contaminated with organotin compounds

    Arevalo, Eduardo [Hamburg University of Technology, Institute of Environmental Technology and Energy Economics, Eissendorfer Strasse 40, D-21073 Hamburg (Germany); Calmano, Wolfgang [Hamburg University of Technology, Institute of Environmental Technology and Energy Economics, Eissendorfer Strasse 40, D-21073 Hamburg (Germany)]. E-mail: calmano@tuhh.de

    2007-07-31

    Different anode materials were tested to evaluate their suitability to eliminate organotin compounds electrochemically from shipyard process waters. The capacity of two types of anode materials was investigated: niobium coated with boron-doped diamond (BDD) and titanium coated with iridium dioxide (Ti/IrO{sub 2}). The aim of this work was to characterize the performance of the process using both anode materials at different current densities, and also to evaluate the generation of by-products. A further objective of this work was to evaluate if operating at low potentials with BDD anodes (to avoid the generation of elemental oxygen) the consumption of energy for degradation of pollutants could be minimized. The processes were tested on synthetic and real shipyard water containing approximately 25,000 ng L{sup -1} of tributyltin (TBT) (as Sn) and 5000 ng L{sup -1} dibutyltin. The range of current densities was between 6 and 70 mA cm{sup -2}. The results showed that electrochemical treatment is suitable to eliminate organotins down to very low concentrations following a stepwise debutylation mechanism. Both anode materials exhibited a similar performance with energy consumption in the range of 7-10 kWh m{sup -3} in order to decrease organotins down to 100 ng L{sup -1} (as Sn). For the water composition tested, BDD did not outperform Ti/IrO{sub 2} as initially expected, most probably because organotins were not only oxidized by {center_dot}OH, but also by active chlorine compounds generated by the oxidation of chloride present in the wastewater (1.6 g L{sup -1}, Cl{sup -}) with both anode materials. It was also found that the residual oxidants remaining in the treated effluent had to be eliminated if the water is to be discharged safely in the aquatic environment.

  17. Studies on electrochemical treatment of wastewater contaminated with organotin compounds

    Arevalo, Eduardo; Calmano, Wolfgang

    2007-01-01

    Different anode materials were tested to evaluate their suitability to eliminate organotin compounds electrochemically from shipyard process waters. The capacity of two types of anode materials was investigated: niobium coated with boron-doped diamond (BDD) and titanium coated with iridium dioxide (Ti/IrO 2 ). The aim of this work was to characterize the performance of the process using both anode materials at different current densities, and also to evaluate the generation of by-products. A further objective of this work was to evaluate if operating at low potentials with BDD anodes (to avoid the generation of elemental oxygen) the consumption of energy for degradation of pollutants could be minimized. The processes were tested on synthetic and real shipyard water containing approximately 25,000 ng L -1 of tributyltin (TBT) (as Sn) and 5000 ng L -1 dibutyltin. The range of current densities was between 6 and 70 mA cm -2 . The results showed that electrochemical treatment is suitable to eliminate organotins down to very low concentrations following a stepwise debutylation mechanism. Both anode materials exhibited a similar performance with energy consumption in the range of 7-10 kWh m -3 in order to decrease organotins down to 100 ng L -1 (as Sn). For the water composition tested, BDD did not outperform Ti/IrO 2 as initially expected, most probably because organotins were not only oxidized by ·OH, but also by active chlorine compounds generated by the oxidation of chloride present in the wastewater (1.6 g L -1 , Cl - ) with both anode materials. It was also found that the residual oxidants remaining in the treated effluent had to be eliminated if the water is to be discharged safely in the aquatic environment

  18. SUPPLEMENTARY INFORMATION A combined Electrochemical ...

    DELL

    A combined Electrochemical and Theoretical study of pyridine-based Schiff bases as novel corrosion inhibitors for mild steel in hydrochloric acid medium. PARUL DOHAREa, M A QURAISHIb* and I B OBOTb. aDepartment of Chemistry, Indian Institute of Technology, Banaras Hindu University, Varanasi, Uttar. Pradesh 221 ...

  19. Electrolytes for magnesium electrochemical cells

    Burrell, Anthony K.; Sa, Niya; Proffit, Danielle Lee; Lipson, Albert; Liao, Chen; Vaughey, John T.; Ingram, Brian J.

    2017-07-04

    An electrochemical cell includes a high voltage cathode configured to operate at 1.5 volts or greater; an anode including Mg.sup.0; and an electrolyte including an ether solvent and a magnesium salt; wherein: a concentration of the magnesium salt in the ether is 1 M or greater.

  20. All-Polymer Electrochemical Sensors

    Kafka, Jan Robert

    This thesis presents fabrication strategies to produce different types of all-polymer electrochemical sensors based on electrodes made of the highly conductive polymer poly(3,4-ethylenedioxythiophene) (PEDOT). Three different systems are presented, fabricated either by using microdrilling or by hot...