Sample records for water proton kinetic

  1. Kinetics of proton transport in water

    DEFF Research Database (Denmark)

    Kornyshev, A.A.; Kuznetsov, A.M.; Spohr, E.


    +), (ii) proton transfer from hydronium to a neighboring water molecule, and (iii) structural diffusion of the Zundel complex (H5O2+), the processes all controlled by orientational fluctuations or hydrogen bond breaking in neighboring hydration shells. Spontaneous conversion of excess proton states...... are brought into the framework of quantum mechanical PT theory in condensed media. Both the nature of the elementary act and the reaction coordinates are, however, different for the two types of PT clusters. The corresponding rate constants are calculated and compared with MD simulations. Within the framework...

  2. Proton transfer pathways, energy landscape, and kinetics in creatine-water systems. (United States)

    Ivchenko, Olga; Whittleston, Chris S; Carr, Joanne M; Imhof, Petra; Goerke, Steffen; Bachert, Peter; Wales, David J


    We study the exchange processes of the metabolite creatine, which is present in both tumorous and normal tissues and has NH2 and NH groups that can transfer protons to water. Creatine produces chemical exchange saturation transfer (CEST) contrast in magnetic resonance imaging (MRI). The proton transfer pathway from zwitterionic creatine to water is examined using a kinetic transition network constructed from the discrete path sampling approach and an approximate quantum-chemical energy function, employing the self-consistent-charge density-functional tight-binding (SCC-DFTB) method. The resulting potential energy surface is visualized by constructing disconnectivity graphs. The energy landscape consists of two distinct regions corresponding to the zwitterionic creatine structures and deprotonated creatine. The activation energy that characterizes the proton transfer from the creatine NH2 group to water was determined from an Arrhenius fit of rate constants as a function of temperature, obtained from harmonic transition state theory. The result is in reasonable agreement with values obtained in water exchange spectroscopy (WEX) experiments.

  3. Surface Proton Hopping and Fast-Kinetics Pathway of Water Oxidation on Co3O4 (001) Surface

    Energy Technology Data Exchange (ETDEWEB)

    Pham, Hieu H. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis and Chemical Sciences Division; Cheng, Mu-Jeng [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis and Chemical Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Frei, Heinz [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Biophysics and Integrated Bioimaging Division; Wang, Lin-Wang [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis and Chemical Sciences Division; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division


    A mechanism of water splitting on cobalt oxide surface is proposed, with atomistic thermodynamic and kinetic details. The density-functional theory studies suggest that the oxidation process could proceed with several nonelectrochemical (spontaneous) intermediate steps, following the initial electrochemical hydroxyl-to-oxo conversion. More specifically, the single oxo sites CoIV=O can hop (via surface proton/electron hopping) to form oxo pair CoIV(=O)-O-CoIV=O, which will undergo nucleophilic attack by a water molecule and form the hydroperoxide CoIII -OOH. Encounter with another oxo would generate a superoxo CoIII-OO, followed by the O2 release. Finally the addition and deprotonation of a fresh water molecule will restart the catalytic cycle by forming the hydroxyl CoIII-OH at this active site. Our theoretical investigations indicate that all nonelectrochemical reactions are kinetically fast and thermodynamically downhill. This hypothesis is supported by recent in situ spectroscopic observations of surface superoxo that is stabilized by hydrogen bonding to adjacent hydroxyl group as an intermediate on fast-kinetics Co catalytic site.

  4. Proton-transport mechanisms in cytochrome c oxidase revealed by studies of kinetic isotope effects (United States)

    Johansson, Ann-Louise; Chakrabarty, Suman; Siöberg, Catrine Berthold; Högbom, Martin; Warshel, Arieh; Brzezinski, Peter


    Cytochrome c oxidase (CytcO) is a membrane-bound enzyme, which catalyzes the reduction of di-oxygen to water and uses a major part of the free energy released in this reaction to pump protons across the membrane. In the Rhodobacter sphaeroides aa3 CytcO all protons that are pumped across the membrane, as well as one half of the protons that are used for O2 reduction, are transferred through one specific intraprotein proton pathway, which holds a highly conserved Glu286 residue. Key questions that need to be addressed in order to understand the function of CytcO at a molecular level are related to the timing of proton transfers from Glu286 to a “pump site” and the catalytic site, respectively. Here, we have investigated the temperature dependencies of the H/D kinetic-isotope effects of intramolecular proton-transfer reactions in the wild-type CytcO as well as in two structural CytcO variants, one in which proton uptake from solution is delayed and one in which proton pumping is uncoupled from O2 reduction. These processes were studied for two specific reaction steps linked to transmembrane proton pumping, one that involves only proton transfer (peroxy–ferryl, P→F, transition) and one in which the same sequence of proton transfers is also linked to electron transfer to the catalytic site (ferryl–oxidized, F→O, transition). An analysis of these reactions in the framework of theory indicates that that the simpler, P→F reaction is rate-limited by proton transfer from Glu286 to the catalytic site. When the same proton-transfer events are also linked to electron transfer to the catalytic site (F→O), the proton-transfer reactions are gated by a protein structural change, which presumably ensures that the proton-pumping stoichiometry is maintained also in the presence of a transmembrane electrochemical gradient. PMID:21463601

  5. Variation of kinetic isotope effect in multiple proton transfer reactions

    Indian Academy of Sciences (India)

    Variation of kinetic isotope effect in multiple proton transfer reactions. #. B SARITHA and M DURGA PRASAD. ∗. School of Chemistry, University of Hyderabad, Hyderabad 500 046, India e-mail: Abstract. Recently, we had suggested that the motion along the promoter mode in the first part of the IRC.

  6. Proton-pumping mechanism of cytochrome c oxidase: A kinetic master-equation approach (United States)

    Kim, Young C.; Hummer, Gerhard


    Cytochrome c oxidase (CcO) is an efficient energy transducer that reduces oxygen to water and converts the released chemical energy into an electrochemical membrane potential. As a true proton pump, CcO translocates protons across the membrane against this potential. Based on a wealth of experiments and calculations, an increasingly detailed picture of the reaction intermediates in the redox cycle has emerged. However, the fundamental mechanism of proton pumping coupled to redox chemistry remains largely unresolved. Here we examine and extend a kinetic master-equation approach to gain insight into redox-coupled proton pumping in CcO. Basic principles of the CcO proton pump emerge from an analysis of the simplest kinetic models that retain essential elements of the experimentally determined structure, energetics, and kinetics, and that satisfy fundamental physical principles. The master-equation models allow us to address the question of how pumping can be achieved in a system in which all reaction steps are reversible. Whereas proton pumping does not require the direct modulation of microscopic reaction barriers, such kinetic gating greatly increases the pumping efficiency. Further efficiency gains can be achieved by partially decoupling the proton uptake pathway from the ative-site region. Such a mechanism is consistent with the proposed Glu valve, in which the side chain of a key glutamic acid shuttles between the D channel and the active-site region. We also show that the models predict only small proton leaks even in the absence of turnover. The design principles identified here for CcO provide a blueprint for novel biology-inspired fuel cells, and the master-equation formulation should prove useful also for other molecular machines. PMID:21946020

  7. Alternating electron and proton transfer steps in photosynthetic water oxidation. (United States)

    Klauss, André; Haumann, Michael; Dau, Holger


    Water oxidation by cyanobacteria, algae, and plants is pivotal in oxygenic photosynthesis, the process that powers life on Earth, and is the paradigm for engineering solar fuel-production systems. Each complete reaction cycle of photosynthetic water oxidation requires the removal of four electrons and four protons from the catalytic site, a manganese-calcium complex and its protein environment in photosystem II. In time-resolved photothermal beam deflection experiments, we monitored apparent volume changes of the photosystem II protein associated with charge creation by light-induced electron transfer (contraction) and charge-compensating proton relocation (expansion). Two previously invisible proton removal steps were detected, thereby filling two gaps in the basic reaction-cycle model of photosynthetic water oxidation. In the S(2) → S(3) transition of the classical S-state cycle, an intermediate is formed by deprotonation clearly before electron transfer to the oxidant (Y Z OX). The rate-determining elementary step (τ, approximately 30 µs at 20 °C) in the long-distance proton relocation toward the protein-water interface is characterized by a high activation energy (E(a) = 0.46 ± 0.05 eV) and strong H/D kinetic isotope effect (approximately 6). The characteristics of a proton transfer step during the S(0) → S(1) transition are similar (τ, approximately 100 µs; E(a) = 0.34 ± 0.08 eV; kinetic isotope effect, approximately 3); however, the proton removal from the Mn complex proceeds after electron transfer to . By discovery of the transient formation of two further intermediate states in the reaction cycle of photosynthetic water oxidation, a temporal sequence of strictly alternating removal of electrons and protons from the catalytic site is established.

  8. Vlasov simulations of kinetic Alfvén waves at proton kinetic scales

    Energy Technology Data Exchange (ETDEWEB)

    Vásconez, C. L. [Dipartimento di Fisica, Università della Calabria, I-87036 Cosenza (Italy); Observatorio Astronómico de Quito, Escuela Politécnica Nacional, Quito (Ecuador); Valentini, F.; Veltri, P. [Dipartimento di Fisica, Università della Calabria, I-87036 Cosenza (Italy); Camporeale, E. [Centrum Wiskunde and Informatica, Amsterdam (Netherlands)


    Kinetic Alfvén waves represent an important subject in space plasma physics, since they are thought to play a crucial role in the development of the turbulent energy cascade in the solar wind plasma at short wavelengths (of the order of the proton gyro radius ρ{sub p} and/or inertial length d{sub p} and beyond). A full understanding of the physical mechanisms which govern the kinetic plasma dynamics at these scales can provide important clues on the problem of the turbulent dissipation and heating in collisionless systems. In this paper, hybrid Vlasov-Maxwell simulations are employed to analyze in detail the features of the kinetic Alfvén waves at proton kinetic scales, in typical conditions of the solar wind environment (proton plasma beta β{sub p} = 1). In particular, linear and nonlinear regimes of propagation of these fluctuations have been investigated in a single-wave situation, focusing on the physical processes of collisionless Landau damping and wave-particle resonant interaction. Interestingly, since for wavelengths close to d{sub p} and β{sub p} ≃ 1 (for which ρ{sub p} ≃ d{sub p}) the kinetic Alfvén waves have small phase speed compared to the proton thermal velocity, wave-particle interaction processes produce significant deformations in the core of the particle velocity distribution, appearing as phase space vortices and resulting in flat-top velocity profiles. Moreover, as the Eulerian hybrid Vlasov-Maxwell algorithm allows for a clean almost noise-free description of the velocity space, three-dimensional plots of the proton velocity distribution help to emphasize how the plasma departs from the Maxwellian configuration of thermodynamic equilibrium due to nonlinear kinetic effects.

  9. Kinetics of proton transfer in a green fluorescent protein: A laser ...

    Indian Academy of Sciences (India)


    protonation kinetics showed dependence on the bulk viscosity of the solvent, and therefore implicates bulk solvent-controlled protein dynamics in the protonation process. The protonation is proposed to be a sequential process involving two steps: (a) proton transfer from solvent to the chromophore, and (b) internal structural.

  10. Proton translocation in cytochrome c oxidase: insights from proton exchange kinetics and vibrational spectroscopy. (United States)

    Ishigami, Izumi; Hikita, Masahide; Egawa, Tsuyoshi; Yeh, Syun-Ru; Rousseau, Denis L


    Cytochrome c oxidase is the terminal enzyme in the electron transfer chain. It reduces oxygen to water and harnesses the released energy to translocate protons across the inner mitochondrial membrane. The mechanism by which the oxygen chemistry is coupled to proton translocation is not yet resolved owing to the difficulty of monitoring dynamic proton transfer events. Here we summarize several postulated mechanisms for proton translocation, which have been supported by a variety of vibrational spectroscopic studies. We recently proposed a proton translocation model involving proton accessibility to the regions near the propionate groups of the heme a and heme a3 redox centers of the enzyme based by hydrogen/deuterium (H/D) exchange Raman scattering studies (Egawa et al., PLoS ONE 2013). To advance our understanding of this model and to refine the proton accessibility to the hemes, the H/D exchange dependence of the heme propionate group vibrational modes on temperature and pH was measured. The H/D exchange detected at the propionate groups of heme a3 takes place within a few seconds under all conditions. In contrast, that detected at the heme a propionates occurs in the oxidized but not the reduced enzyme and the H/D exchange is pH-dependent with a pKa of ~8.0 (faster at high pH). Analysis of the thermodynamic parameters revealed that, as the pH is varied, entropy/enthalpy compensation held the free energy of activation in a narrow range. The redox dependence of the possible proton pathways to the heme groups is discussed. This article is part of a Special Issue entitled: Vibrational spectroscopies and bioenergetic systems. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. Proton transport and the water environment in nafion fuel cell membranes and AOT reverse micelles. (United States)

    Spry, D B; Goun, A; Glusac, K; Moilanen, David E; Fayer, M D


    The properties of confined water and diffusive proton-transfer kinetics in the nanoscopic water channels of Nafion fuel cell membranes at various hydration levels are compared to water in a series of well-characterized AOT reverse micelles with known water nanopool sizes using the photoacid pyranine as a molecular probe. The side chains of Nafion are terminated by sulfonate groups with sodium counterions that are arrayed along the water channels. AOT has sulfonate head groups with sodium counterions that form the interface with the reverse micelle's water nanopool. The extent of excited-state deprotonation is observed by steady-state fluorescence measurements. Proton-transfer kinetics and orientational relaxation are measured by time-dependent fluorescence using time-correlated single photon counting. The time dependence of deprotonation is related to diffusive proton transport away from the photoacid. The fluorescence reflecting the long time scale proton transport has an approximately t-0.8 power law decay in contrast to bulk water, which has a t-3/2 power law. For a given hydration level of Nafion, the excited-state proton transfer and the orientational relaxation are similar to those observed for a related size AOT water nanopool. The effective size of the Nafion water channels at various hydration levels are estimated by the known size of the AOT reverse micelles that display the corresponding proton-transfer kinetics and orientational relaxation.

  12. Influence of Proton Acceptors on the Proton-Coupled Electron Transfer Reaction Kinetics of a Ruthenium-Tyrosine Complex. (United States)

    Lennox, J Christian; Dempsey, Jillian L


    A polypyridyl ruthenium complex with fluorinated bipyridine ligands and a covalently bound tyrosine moiety was synthesized, and its photo-induced proton-coupled electron transfer (PCET) reactivity in acetonitrile was investigated with transient absorption spectroscopy. Using flash-quench methodology with methyl viologen as an oxidative quencher, a Ru 3+ species is generated that is capable of initiating the intramolecular PCET oxidation of the tyrosine moiety. Using a series of substituted pyridine bases, the reaction kinetics were found to vary as a function of proton acceptor concentration and identity, with no significant H/D kinetic isotope effect. Through analysis of the kinetics traces and comparison to a control complex without the tyrosine moiety, PCET reactivity was found to proceed through an equilibrium electron transfer followed by proton transfer (ET-PT) pathway in which irreversible deprotonation of the tyrosine radical cation shifts the ET equilibrium, conferring a base dependence on the reaction. Comprehensive kinetics modeling allowed for deconvolution of complex kinetics and determination of rate constants for each elementary step. Across the five pyridine bases explored, spanning a range of 4.2 pK a units, a linear free-energy relationship was found for the proton transfer rate constant with a slope of 0.32. These findings highlight the influence that proton transfer driving force exerts on PCET reaction kinetics.

  13. Noninvasive detection of nanoparticle clustering by water proton NMR

    Energy Technology Data Exchange (ETDEWEB)

    Taraban, Marc B.; Truong, Huy C.; Ilavsky, Jan; DePaz, Roberto A.; Lobo, Brian; Yu, Y. Bruce


    It is shown that water proton NMR can detect uncontrolled clustering of inert nanoparticles (NPs) formulated as aqueous suspensions. The clustering of NPs causes the compartmentalization of water molecules, leading to accelerated proton spin de-coherence, and hence, much faster water transverse relaxation rates. The results suggest that water proton NMR can be used to noninvasively inspect NP products by commercial end users and researchers.

  14. Communication: Slow proton-charge diffusion in nanoconfined water. (United States)

    van der Loop, Tibert H; Ottosson, Niklas; Vad, Thomas; Sager, Wiebke F C; Bakker, Huib J; Woutersen, Sander


    We investigate proton-charge mobility in nanoscopic water droplets with tuneable size. We find that the diffusion of confined proton charges causes a dielectric relaxation process with a maximum-loss frequency determined by the diffusion constant. In volumes less than ∼5 nm in diameter, proton-charge diffusion slows down significantly with decreasing size: for diameters <1 nm, the diffusion constant is about 100 times smaller than in bulk water. The low mobility probably results from the more rigid hydrogen-bond network of nanoconfined water, since proton-charge mobility in water relies on collective hydrogen-bond rearrangements.

  15. Shrink-wrapping water to conduct protons (United States)

    Shimizu, George K. H.


    For proton-conducting metal-organic frameworks (MOFs) to find application as the electrolyte in proton-exchange membrane fuel cells, materials with better stability and conductivity are required. Now, a structurally flexible MOF that is also highly stable is demonstrated to possess high proton conductivity over a range of humidities.

  16. Kinetic isotope effect on the proton-transfer in indigo carmine (United States)

    Iwakura, Izumi; Yabushita, Atsushi; Kobayashi, Takayoshi


    We have found that photo-excited indigo carmine causes stepwise proton transfer to generate mono-alcohol intermediate, which immediately returns to the parent molecule [I. Iwakura, A. Yabushita, T. Kobayashi, Chem. Lett. 38 (2009) 1020]. The kinetic isotope effect in the proton transfer of this system has been studied by direct observation of the real-time molecular vibrational amplitude during the reaction including the transition state using a sub-5-fs laser pulse. The kaH/kaD ratio for the proton transfer after photo-excitation is observed to be 1.5 ± 0.1.

  17. Hydrated Excess Protons Can Create Their Own Water Wires. (United States)

    Peng, Yuxing; Swanson, Jessica M J; Kang, Seung-gu; Zhou, Ruhong; Voth, Gregory A


    Grotthuss shuttling of an excess proton charge defect through hydrogen bonded water networks has long been the focus of theoretical and experimental studies. In this work we show that there is a related process in which water molecules move ("shuttle") through a hydrated excess proton charge defect in order to wet the path ahead for subsequent proton charge migration. This process is illustrated through reactive molecular dynamics simulations of proton transport through a hydrophobic nanotube, which penetrates through a hydrophobic region. Surprisingly, before the proton enters the nanotube, it starts "shooting" water molecules into the otherwise dry space via Grotthuss shuttling, effectively creating its own water wire where none existed before. As the proton enters the nanotube (by 2-3 Å), it completes the solvation process, transitioning the nanotube to the fully wet state. By contrast, other monatomic cations (e.g., K(+)) have just the opposite effect, by blocking the wetting process and making the nanotube even drier. As the dry nanotube gradually becomes wet when the proton charge defect enters it, the free energy barrier of proton permeation through the tube via Grotthuss shuttling drops significantly. This finding suggests that an important wetting mechanism may influence proton translocation in biological systems, i.e., one in which protons "create" their own water structures (water "wires") in hydrophobic spaces (e.g., protein pores) before migrating through them. An existing water wire, e.g., one seen in an X-ray crystal structure or MD simulations without an explicit excess proton, is therefore not a requirement for protons to transport through hydrophobic spaces.

  18. Proton Transfer in Nucleobases is Mediated by Water

    Energy Technology Data Exchange (ETDEWEB)

    Khistyaev, Kirill; Golan, Amir; Bravaya, Ksenia B.; Orms, Natalie; Krylov, Anna I.; Ahmed, Musahid


    Water plays a central role in chemistry and biology by mediating the interactions between molecules, altering energy levels of solvated species, modifying potential energy proles along reaction coordinates, and facilitating ecient proton transport through ion channels and interfaces. This study investigates proton transfer in a model system comprising dry and microhydrated clusters of nucleobases. With mass spectrometry and tunable vacuum ultraviolet synchrotron radiation, we show that water shuts down ionization-induced proton transfer between nucleobases, which is very ecient in dry clusters. Instead, a new pathway opens up in which protonated nucleo bases are generated by proton transfer from the ionized water molecule and elimination of a hydroxyl radical. Electronic structure calculations reveal that the shape of the potential energy prole along the proton transfer coordinate depends strongly on the character of the molecular orbital from which the electron is removed, i.e., the proton transfer from water to nucleobases is barrierless when an ionized state localized on water is accessed. The computed energetics of proton transfer is in excellent agreement with the experimental appearance energies. Possible adiabatic passage on the ground electronic state of the ionized system, while energetically accessible at lower energies, is not ecient. Thus, proton transfer is controlled electronically, by the character of the ionized state, rather than statistically, by simple energy considerations.

  19. Clinical effects of proton pump inhibitors: Focus on pharmacogenetics, kinetics and dynamics

    NARCIS (Netherlands)

    N.G.M. Hunfeld (Nicole)


    textabstractThis thesis describes the clinical effects of proton pump inhibitors, with focus on pharmacogenetics, kinetics and dynamics. The aims were to investigate the occurence of Rebound Acid Hypersecretion and to investigate the speed of onset, the duration of effect and the difference in

  20. Proton Kinetic Effects and Turbulent Energy Cascade Rate in the Solar Wind (United States)

    Osman, K.; Matthaeus, W. H.; Kiyani, K. H.; Hnat, B.; Chapman, S. C.


    The first observed connection between kinetic instabilities driven by proton temperature anisotropy and estimated energy cascade rates in the turbulent solar wind is reported using measurements from the Wind spacecraft at 1 AU. We find enhanced cascade rates are concentrated along the boundaries of the (β‖,T⊥/T‖)-plane, which includes regions theoretically unstable to the mirror and firehose instabilities. A strong correlation is observed between the estimated cascade rates and kinetic effects such as temperature anisotropy and plasma heating, resulting in protons 5-6 times hotter and 70-90% more anisotropic than under typical isotropic plasma conditions. These results offer new insights into kinetic processes in a turbulent regime.

  1. Electron and proton kinetics and dynamics in flaring atmospheres

    CERN Document Server

    Zharkova, Valentina


    This timely book presents new research results on high-energy particle physics related to solar flares, covering the theory and applications of the reconnection process in a clear and comprehensible way. It investigates particle kinetics and dynamics in flaring atmospheres and their diagnostics from spectral observations, while providing an analysis of the observation data and techniques and comparing various models. Written by an internationally acclaimed expert, this is vital reading for all solar, astro-, and plasma physicists working in the field.

  2. Mechanism and kinetics of sulfamethoxazole photocatalytic ozonation in water. (United States)

    Beltrán, Fernando J; Aguinaco, Almudena; García-Araya, Juan F


    The photocatalytic ozonation of sulfamethoxazole (SMT) has been studied in water under different experimental conditions. The effect of gas flow rate, initial concentration of ozone, SMT and TiO2 has been investigated to establish the importance of mass transfer and chemical reaction. Under the conditions investigated the process is chemically controlled. Both, SMT and TOC kinetics have been considered. Fast and slow kinetic regime of ozone reactions have been observed for SMT and TOC oxidation, respectively. Application of different inhibitors allows for the establishment of reaction mechanism involving direct ozonation, direct photolysis, hydroxyl radical reactions and photocatalytic reactions. Rate constants of the direct reaction between ozone and protonated, non-protonated and anionic SMT species have been determined to be 1.71 x 10(5), 3.24 x 10(5) and 4.18 x 10(5) M(-1) s(-1), respectively. SMT quantum yield at 313 nm was found to be 0.012 moles per Einstein at pH 5 and 0.003 moles per Einstein at pHs 7 and 9. Main contributions to SMT removal were direct ozone reaction, positive hole oxidation and hydroxyl radical reactions. For TOC removal, main contributions were due to positive hole oxidation and hydroxyl radical reactions.

  3. Vanadium proton exchange membrane water electrolyser (United States)

    Noack, Jens; Roznyatovskaya, Nataliya; Pinkwart, Karsten; Tübke, Jens


    In order to reverse the reactions of vanadium oxygen fuel cells and to regenerate vanadium redox flow battery electrolytes that have been oxidised by atmospheric oxygen, a vanadium proton exchange membrane water electrolyser was set up and investigated. Using an existing cell with a commercial and iridium-based catalyst coated membrane, it was possible to fully reduce V3.5+ and V3+ solutions to V2+ with the formation of oxygen and with coulomb efficiencies of over 96%. The cell achieved a maximum current density of 75 mA/cm2 during this process and was limited by the proximity of the V(III) reduction to the hydrogen evolution reaction. Due to the specific reaction mechanisms of V(IV) and V(III) ions, V(III) solutions were reduced with an energy efficiency of 61%, making this process nearly twice as energy efficient as the reduction of V(IV) to V(III). Polarisation curves and electrochemical impedance spectroscopy were used to further investigate the losses of half-cell reactions and to find ways of further increasing efficiency and performance levels.

  4. Hydrogen peroxide decomposition kinetics in aquaculture water

    DEFF Research Database (Denmark)

    Arvin, Erik; Pedersen, Lars-Flemming


    Hydrogen peroxide (HP) is used in aquaculture systems where preventive or curative water treatments occasionally are required. Use of chemical agents can be challenging in recirculating aquaculture systems (RAS) due to extended water retention time and because the agents must not damage the fish ...... in RAS by addressing disinfection demand and identify efficient and safe water treatment routines.......Hydrogen peroxide (HP) is used in aquaculture systems where preventive or curative water treatments occasionally are required. Use of chemical agents can be challenging in recirculating aquaculture systems (RAS) due to extended water retention time and because the agents must not damage the fish...... reared or the nitrifying bacteria in the biofilters at concentrations required to eliminating pathogens. This calls for quantitative insight into the fate of the disinfectant residuals during water treatment. This paper presents a kinetic model that describes the HP decomposition in aquaculture water...

  5. Carbon, Helium, and Proton Kinetic Temperatures in a Cygnus Loop Shock Wave (United States)

    Raymond, John C.; Edgar, Richard J.; Ghavamian, Parviz; Blair, William P.


    Observations of SN 1006 have shown that ions and electrons in the plasma behind fast supernova remnant shock waves are far from equilibrium, with the electron temperature much lower than the proton temperature and ion temperatures approximately proportional to ion mass. In the ˜360 km s-1shock waves of the Cygnus Loop, on the other hand, electron and ion temperatures are roughly equal, and there is evidence that the oxygen kinetic temperature is not far from the proton temperature. In this paper, we report observations of the He ii λ1640 line and the C iv λ1550 doublet in a 360 km s-1shock in the Cygnus Loop. While the best-fit kinetic temperatures are somewhat higher than the proton temperature, the temperatures of He and C are consistent with the proton temperature and the upper limits are 0.5 and 0.3 times the mass-proportional temperatures, implying efficient thermal equilibration in this collisionless shock. The equilibration of helium and hydrogen affects the conversion between proton temperatures determined from Hα line profiles and shock speeds, and the efficient equilibration found here reduces the shock speed estimates and the distance estimate to the Cygnus Loop of Medina et al. to about 800 pc.

  6. Protons migrate along interfacial water without significant contributions from jumps between ionizable groups on the membrane surface (United States)

    Springer, Andreas; Hagen, Volker; Cherepanov, Dmitry A.; Antonenko, Yuri N.; Pohl, Peter


    Proton diffusion along membrane surfaces is thought to be essential for many cellular processes such as energy transduction. Commonly, it is treated as a succession of jumps between membrane-anchored proton-binding sites. Our experiments provide evidence for an alternative model. We released membrane-bound caged protons by UV flashes and monitored their arrival at distant sites by fluorescence measurements. The kinetics of the arrival is probed as a function of distance for different membranes and for different water isotopes. We found that proton diffusion along the membrane is fast even in the absence of ionizable groups in the membrane, and it decreases strongly in D2O as compared to H2O. We conclude that the fast proton transport along the membrane is dominated by diffusion via interfacial water, and not via ionizable lipid moieties. PMID:21859952

  7. Water versus DNA: new insights into proton track-structure modelling in radiobiology and radiotherapy. (United States)

    Champion, C; Quinto, M A; Monti, J M; Galassi, M E; Weck, P F; Fojón, O A; Hanssen, J; Rivarola, R D


    Water is a common surrogate of DNA for modelling the charged particle-induced ionizing processes in living tissue exposed to radiations. The present study aims at scrutinizing the validity of this approximation and then revealing new insights into proton-induced energy transfers by a comparative analysis between water and realistic biological medium. In this context, a self-consistent quantum mechanical modelling of the ionization and electron capture processes is reported within the continuum distorted wave-eikonal initial state framework for both isolated water molecules and DNA components impacted by proton beams. Their respective probability of occurrence-expressed in terms of total cross sections-as well as their energetic signature (potential and kinetic) are assessed in order to clearly emphasize the differences existing between realistic building blocks of living matter and the controverted water-medium surrogate. Consequences in radiobiology and radiotherapy will be discussed in particular in view of treatment planning refinement aiming at better radiotherapy strategies.

  8. The protonation state around TyrD/TyrD(•) in photosystem II is reflected in its biphasic oxidation kinetics. (United States)

    Sjöholm, Johannes; Ho, Felix; Ahmadova, Nigar; Brinkert, Katharina; Hammarström, Leif; Mamedov, Fikret; Styring, Stenbjörn


    The tyrosine residue D2-Tyr160 (TyrD) in photosystem II (PSII) can be oxidized through charge equilibrium with the oxygen evolving complex in PSII. The kinetics of the electron transfer from TyrD has been followed using time-resolved EPR spectroscopy after triggering the oxidation of pre-reduced TyrD by a short laser flash. After its oxidation TyrD is observed as a neutral radical (TyrD(•)) indicating that the oxidation is coupled to a deprotonation event. The redox state of TyrD was reported to be determined by the two water positions identified in the crystal structure of PSII [Saito et al. (2013) Proc. Natl. Acad. Sci. USA 110, 7690]. To assess the mechanism of the proton coupled electron transfer of TyrD the oxidation kinetics has been followed in the presence of deuterated buffers, thereby resolving the kinetic isotope effect (KIE) of TyrD oxidation at different H/D concentrations. Two kinetic phases of TyrD oxidation - the fast phase (msec-sec time range) and the slow phase (tens of seconds time range) were resolved as was previously reported [Vass and Styring (1991) Biochemistry 30, 830]. In the presence of deuterated buffers the kinetics was significantly slower compared to normal buffers. Furthermore, although the kinetics were faster at both high pH and pD values the observed KIE was found to be similar (~2.4) over the whole pL range investigated. We assign the fast and slow oxidation phases to two populations of PSII centers with different water positions, proximal and distal respectively, and discuss possible deprotonation events in the vicinity of TyrD. Copyright © 2016 Elsevier B.V. All rights reserved.

  9. Hydrogen isotope exchange kinetics of single protons in bovine pancreatic trypsin inhibitor

    Energy Technology Data Exchange (ETDEWEB)

    Woodward, C.K.; Hilton, B.C.


    The exchange kinetics of the slowest exchanging BPTI ..beta..-sheet protons are complex compared to model peptides; the activation energy, E/sub a/, and the pH dependence are temperature dependent. We have measured the exchange kinetics in the range pH 1 to 11, 33 to 71/sup 0/C, particularly the temperature dependence. The data are fit to a model in which exchange of each proton is determined by two discrete dynamical processes, one with E/sub a/ approx. 65 kcal/mol and less than first order dependence on catalyst ion, and one with E/sub a/ 20 to 30 kcal/mol and approaching first order in catalyst ion. The low activation energy process is the mechanism of interest in the native conformation of globular proteins and involves low energy, small amplitude fluctuations; the high activation energy process involves major unfolding. The model is simple, has a precedent in the hydrogen exchange literature, and explains quantitatively the complex feature of the exchange kinetics of single protons in BPTI.

  10. Outer-Sphere and Inner-Sphere Ligand Protonation in Metal Complexation Kinetics: The Lability of EDTA Complexes

    NARCIS (Netherlands)

    Leeuwen, van H.P.; Town, R.M.


    A generic framework, based on the Eigen mechanism, is formulated to describe the formation/dissociation kinetics of inner-sphere metal complexes that may undergo protonation. In principle, all protonated forms of the ligand contribute to the formation of the precursor outer-sphere complexes, but

  11. Kinetic Distributions of Coronal Hole Protons in the Solar Wind Generation Region (United States)

    Isenberg, P. A.; Vasquez, B. J.


    We solve the inhomogeneous kinetic guiding-center equation for the collisionless proton distribution function in a model polar coronal hole. The protons react to the local forces due to gravity, charge separation electric field, focusing in the decreasing magnetic field, and ponderomotive wave pressure. They are also heated through resonant cyclotron diffusion by a broad spectrum of obliquely-propagating ion cyclotron waves. We model the resonant wave intensities by a power-law extrapolation from the Alfvén wave results of Cranmer and van Ballegooijen (2005), multiplied by an additional scaling factor to represent the inefficient turbulent transport to resonant frequencies. We find that a scaling factor as low as 0.01 gives sufficient proton heating to yield a fast solar wind. The resulting proton distributions have a distinctive shape, compressed in the sunward half of velocity space, and more spread out (that is, hotter) in the anti-sunward half. Observation of similarly-shaped distributions in the fast wind by instruments on Solar Probe would provide evidence for resonant cyclotron heating as the generation mechanism for the solar wind. We will present results for the radial evolution of the model proton distribution, as well as moment quantities such as flow speed, temperatures and heating rates.

  12. The State of Water in Proton Conducting Membranes

    Energy Technology Data Exchange (ETDEWEB)

    Allcock, Harry R.; Benesi, Alan; Macdonald, Digby D.


    The research carried out under grant No. DE-FG02-07ER46371, "The State of Water in Proton Conducting Membranes", during the period June 1, 2008 - May 31, 2010 was comprised of three related parts. These are: 1. An examination of the state of water in classical proton conduction membranes with the use of deuterium T1 NMR spectroscopy (Allcock and Benesi groups). 2. A dielectric relaxation examination of the behavior of water in classical ionomer membranes (Macdonald program). 3. Attempts to synthesize new proton-conduction polymers and membranes derived from the polyphosphazene system. (Allcock program) All three are closely related, crucial aspects of the design and development of new and improved polymer electrolyte fuel cell membranes on which the future of fuel cell technology for portable applications depends.

  13. Studies of Water V. Five Phonons in Protonic Semiconductor Lattice Model of Pure Liquid Water (United States)

    Jie, Binbin; Sah, Chihtang


    We report physics based confirmation (~1% RMS deviation), by existing experimental data, of proton-prohol (proton-hole) ion product (pH) and mobilities in pure liquid water (0-100{}{{o}}C, 1-atm pressure) anticipated from our melted-ice Hexagonal-Close-Packed (H{}2O){}4 Lattice Model. Five phonons are identified. (1) A propagating protonic phonon (520.9 meV from lone-pair-blue-shifted stretching mode of isolated water molecule) absorbed to generate a proton-prohol pair or detrap a tightly-bound proton. (2) Two (173.4 and 196.6 meV) bending-breathing protonic-proholic or protonic phonons absorbed during de-trapping-limited proton or proton-prohol mobilities. (3) Two propagating oxygenic-wateric Debye-Dispersive phonons (30.3 and 27.5 meV) absorbed during scattering-limited proton or proton-prohol mobilities. Summer School in Theoretical Physics funded by the National Natural Science Foundation of China, on Soft Materials Physics, hosted by the Physics Department of Xiamen University, China, during August 1 to 14, 2016. This was also just presented at the 2017 March Meeting (March 14 to 16) of the American Physical Society in New Orleans, USA.

  14. Parity Nonconservation in Proton-Proton and Proton-Water Scattering at 1.5 GeV/c (United States)

    Mischke, R. E.; Bowman, J. D.; Carlini, R.; MacArthur, D.; Nagle, D. E.; Frauenfelder, H.; Harper, R. W.; Yuan, V.; McDonald, A. B.; Talaga, R. L.


    Experiments searching for parity nonconservation in the scattering of 1.5 GeV/c (800 MeV) polarized protons from an unpolarized water target and a liquid hydrogen target are described. The intensity of the incident proton beam was measured upstream and downstream of the target by a pair of ionization detectors. The beam helicity was reversed at a 30-Hz rate. Auxiliary detectors monitored beam properties that could give rise to false effects. The result for the longitudinal asymmetry from the water is A{sub L} = (1.7 +- 3.3 +- 1.4) x 10{sup -7}, where the first error is statistical and the second is an estimate of systematic effects. The hydrogen data yield a preliminary result of A{sub L} = (1.0 +- 1.6) x 10{sup -7}. The systematic errors for p-p are expected to be < 1 x 10{sup -7}.

  15. Parity nonconservation in proton-proton and proton-water scattering at 1. 5 GeV/c

    Energy Technology Data Exchange (ETDEWEB)

    Mischke, R.E.; Bowman, J.D.; Carlini, R.; MacArthur, D.; Nagle, D.E.; Frauenfelder, H.; Harper, R.W.; Yuan, V.; McDonald, A.B.; Talaga, R.L.


    Experiments searching for parity nonconservation in the scattering of 1.5 GeV/c (800 MeV) polarized protons from an unpolarized water target and a liquid hydrogen target are described. The intensity of the incident proton beam was measured upstream and downstream of the target by a pair of ionization detectors. The beam helicity was reversed at a 30-Hz rate. Auxiliary detectors monitored beam properties that could give rise to false effects. The result for the longitudinal asymmetry from the water is A/sub L/ = (1.7 +- 3.3 +- 1.4) x 10/sup -7/, where the first error is statistical and the second is an estimate of systematic effects. The hydrogen data yield a preliminary result of A/sub L/ = (1.0 +- 1.6) x 10/sup -7/. The systematic errors for p-p are expected to be < 1 x 10/sup -7/.

  16. Channeling of protons in double-walled carbon nanotubes in kinetic model

    Energy Technology Data Exchange (ETDEWEB)

    You Shuyan; Song Yuanhong [School of Physics and Optoelectronic Technology, Dalian University of Technology, Dalian 116023 (China); Wang Younian [School of Physics and Optoelectronic Technology, Dalian University of Technology, Dalian 116023 (China)], E-mail:


    A kinetic model combined with the dielectric response theory is employed to study the electronic excitation on the nanotube walls during the channeling of protons through double-walled carbon nanotubes. Analytical expressions of the self-energy and stopping power are obtained with protons moving along the axis of the double-walled nanotubes. Calculation results show us interesting double-peak curves of the self-energy and stopping power, under strong influence of the damping factor and the special double-walled nanotube geometry. Relatively increasing the damping factor and the chiral parameter of the outer wall can reduce the interference effects between the two walls and weaken the double-peak to one-peak shapes.

  17. Non-enzymatic browning kinetics analysed through water-solids interactions and water mobility in dehydrated potato. (United States)

    Acevedo, Nuria C; Schebor, Carolina; Buera, Pilar


    Non-enzymatic browning (NEB) development was studied in dehydrated potato at 70°C. It was related to the macroscopic and molecular properties and to water-solid interactions over a wide range of water activities. Time resolved (1)H NMR, thermal transitions and water sorption isotherms were evaluated. Although non-enzymatic browning could be detected in the glassy state; colour development was higher in the supercooled state. The reaction rate increased up to a water content of 26g/100g of solids (aw=0.84) and then decreased at higher water contents, concomitantly with the increase of water proton mobility. The joint analyses of NEB kinetics, water sorption isotherm and proton relaxation behaviour made it evident that the point at which the reaction rate decreased, after a maximum value, could be related to the appearance of highly mobile water. The results obtained in this work indicate that the prediction of chemical reaction kinetics can be performed through the integrated analysis of water sorption, water and solids mobility and the physical state of the matrix. Copyright © 2007 Elsevier Ltd. All rights reserved.

  18. Proton conduction in water ices under an electric field. (United States)

    Cassone, Giuseppe; Giaquinta, Paolo V; Saija, Franz; Saitta, A Marco


    We report on a first-principles study of the effects produced by a static electric field on proton conduction in ordinary hexagonal ice (phase Ih) and in its proton-ordered counterpart (phase XI). We performed ab initio molecular dynamics simulations of both phases and investigated the effects produced by the field on the structure of the material, with particular attention paid to the phenomenon of proton transfer. We observed that in ice Ih molecules start to dissociate for field intensities around 0.25 V/Å, as in liquid water, whereas fields stronger than 0.36 V/Å are needed to induce a permanent proton flow. In contrast, in ice XI, electric fields as intense as 0.22 V/Å are already able to induce and sustain, through correlated proton jumps, an ionic current; this behavior suggests, somewhat counterintuitively, that the ordering of protons favors the autoprotolysis phenomenon. However, the same is not true for static conductivities. In fact, both crystalline phases show an ohmic behavior in the conduction regime, but the conductivity of ice Ih turns out to be larger than that of ice XI. We finally discuss the qualitative and quantitative importance of the conspicuous concentration of ionic defects generated by intense electric fields in determining the value of the conductivity, also through a comparison with the experimental data available for saline ices.

  19. Water-assisted Proton Transfer in Ferredoxin I* (United States)

    Lutz, Stephan; Tubert-Brohman, Ivan; Yang, Yonggang; Meuwly, Markus


    The role of water molecules in assisting proton transfer (PT) is investigated for the proton-pumping protein ferredoxin I (FdI) from Azotobacter vinelandii. It was shown previously that individual water molecules can stabilize between Asp15 and the buried [3Fe-4S]0 cluster and thus can potentially act as a proton relay in transferring H+ from the protein to the μ2 sulfur atom. Here, we generalize molecular mechanics with proton transfer to studying proton transfer reactions in the condensed phase. Both umbrella sampling simulations and electronic structure calculations suggest that the PT Asp15-COOH + H2O + [3Fe-4S]0 → Asp15-COO− + H2O + [3Fe-4S]0 H+ is concerted, and no stable intermediate hydronium ion (H3O+) is expected. The free energy difference of 11.7 kcal/mol for the forward reaction is in good agreement with the experimental value (13.3 kcal/mol). For the reverse reaction (Asp15-COO− + H2O + [3Fe-4S]0H+ → Asp15-COOH + H2O + [3Fe-4S]0), a larger barrier than for the forward reaction is correctly predicted, but it is quantitatively overestimated (23.1 kcal/mol from simulations versus 14.1 from experiment). Possible reasons for this discrepancy are discussed. Compared with the water-assisted process (ΔE ≈ 10 kcal/mol), water-unassisted proton transfer yields a considerably higher barrier of ΔE ≈ 35 kcal/mol. PMID:21531725

  20. Proton Momentum Distribution and Diffusion Coefficient in Water: Two Sides of the Same Coin? (United States)

    Bruni, F; Giuliani, A; Mayers, J; Ricci, M A


    Water, the prototype of a liquid to ordinary people, is the most anomalous liquid to physicists, showing regions of the temperature-density (T,ρ) plane where its microscopic structure, diffusion coefficient, and density have anomalous behaviors. Structural anomalies occur over a broad bell-shaped T,ρ region. This region contains, as a matryoshka, two smaller regions, one delimiting dynamical and the other delimiting thermodynamic anomalies. Water anomalous behavior in each of these regions manifests itself as a decrease of order or an increase of the diffusion coefficient upon increasing pressure and as a decrease of density upon cooling. Here, we show that the radial momentum distribution of water protons and their mean kinetic energy have a peculiar, theoretically unpredicted anomaly in the region of dynamical anomalies. This anomaly can be rationalized as due to two distinct "families" of water protons, experiencing quite distinct local environments, leading to an enhancement of the momentum fluctuations along with an increase of kinetic energy.

  1. Proton cycling, buffering, and reaction stoichiometry in natural waters

    NARCIS (Netherlands)

    Hofmann, A.F.; Middelburg, J.J.; Soetaert, K.E.R.; Wolf-Gladrow, D.; Meysman, F.J.R.


    Ongoing acidification of the global ocean necessitates a solid understanding of how biogeochemical processes are driving proton cycling and observed pH changes in natural waters. The standard way of calculating the pH evolution of an aquatic system is to specify first how biogeochemical processes

  2. Superconductivity and Fast Proton Transport in Nanoconfined Water

    CERN Document Server

    Johnson, K H


    A real-space molecular-orbital description of Cooper pairing in conjunction with the dynamic Jahn-Teller mechanism for high-Tc superconductivity predicts that electron-doped water confined to the nanoscale environment of a carbon nanotube or biological macromolecule should superconduct below and exhibit fast proton transport above the transition temperature, Tc = 230 degK (-43 degC).

  3. Kinetics of Hydrogen Evolution on Copper Electrode Involving Organic Acids as Proton Donors

    Directory of Open Access Journals (Sweden)

    A. Survila


    Full Text Available Linear potential sweep (LPS voltammetry was applied to study the kinetics of hydrogen evolution in solutions containing glycolic, malic, tartaric, and gluconic acids. The CE mechanism of hydrogen evolution was analyzed invoking the 2nd Fick's law equations supplemented by terms that account for chemical interactions between diffusing particles. Acids are considered as components that are capable of releasing hydrated protons taking part in the charge-transfer step. Current peaks observed on LPS voltammograms are in linear dependence on ν (ν is the potential sweep rate. They obey well-known relationships obtained for simple redox processes, provided that the concentration of oxidant is treated as total concentration of proton donors. Determination of surface concentrations as current density functions makes it possible to transform LPS voltammograms into linear Tafel plots normalized with respect to the surface concentration of hydronium ions. Similar kinetic parameters (α≈0.6 and i0≈ 10 μA cm−2 obtained at pH 3 for all OA solutions indicate that the nature of OA has no noticeable influence on the charge-transfer process.

  4. High energy efficiency and high power density proton exchange membrane fuel cells: Electrode kinetics and mass transport (United States)

    Srinivasan, Supramaniam; Velev, Omourtag A.; Parthasathy, Arvind; Manko, David J.; Appleby, A. John


    The development of proton exchange membrane (PEM) fuel cell power plants with high energy efficiencies and high power densities is gaining momentum because of the vital need of such high levels of performance for extraterrestrial (space, underwater) and terrestrial (power source for electric vehicles) applications. Since 1987, considerable progress has been made in achieving energy efficiencies of about 60 percent at a current density of 200 mA/sq cm and high power densities (greater than 1 W/sq cm) in PEM fuel cells with high (4 mg/sq cm) or low (0.4 mg/sq cm) platinum loadings in electrodes. The following areas are discussed: (1) methods to obtain these high levels of performance with low Pt loading electrodes - by proton conductor impregnation into electrodes, localization of Pt near front surface; (2) a novel microelectrode technique which yields electrode kinetic parameters for oxygen reduction and mass transport parameters; (3) demonstration of lack of water transport from anode to cathode; (4) modeling analysis of PEM fuel cell for comparison with experimental results and predicting further improvements in performance; and (5) recommendations of needed research and development for achieving the above goals.

  5. Water-mediated proton hopping on an iron oxide surface. (United States)

    Merte, Lindsay R; Peng, Guowen; Bechstein, Ralf; Rieboldt, Felix; Farberow, Carrie A; Grabow, Lars C; Kudernatsch, Wilhelmine; Wendt, Stefan; Lægsgaard, Erik; Mavrikakis, Manos; Besenbacher, Flemming


    The diffusion of hydrogen atoms across solid oxide surfaces is often assumed to be accelerated by the presence of water molecules. Here we present a high-resolution, high-speed scanning tunneling microscopy (STM) study of the diffusion of H atoms on an FeO thin film. STM movies directly reveal a water-mediated hydrogen diffusion mechanism on the oxide surface at temperatures between 100 and 300 kelvin. Density functional theory calculations and isotope-exchange experiments confirm the STM observations, and a proton-transfer mechanism that proceeds via an H(3)O(+)-like transition state is revealed. This mechanism differs from that observed previously for rutile TiO(2)(110), where water dissociation is a key step in proton diffusion.

  6. The kinetic energy spectrum of protons produced by the dissociative ionization of H2 by electron impact (United States)

    Khakoo, M. A.; Srivastava, S. K.


    The kinetic energy spectra of protons resulting from the dissociative ionization of H2 by electron impact have been measured for electron impact energies from threshold (approximately 17 eV) to 160 eV at 90 deg and 30 deg detection angles, using a crossed-beam experimental arrangement. To check reliability, two separate proton energy analysis methods have been employed, i.e., a time-of-flight proton energy analysis and an electrostatic hemispherical energy analyzer. The present results are compared with previous measurements.

  7. Collision-induced dissociation of protonated water clusters (United States)

    Berthias, F.; Buridon, V.; Abdoul-Carime, H.; Farizon, B.; Farizon, M.; Dinh, P. M.; Reinhard, P.-G.; Suraud, E.; Märk, T. D.


    Collision-induced dissociation (CID) has been studied for protonated water clusters H+(H2O)n, with n = 2-8, colliding with argon atoms at a laboratory energy of 8 keV. The experimental data have been taken with an apparatus (Device for Irradiation of Molecular Clusters, `Dispositif d'Irradiation d'Agrégats Moléculaire,' DIAM) that has been recently constructed at the Institut de Physique Nucléaire de Lyon. It includes an event-by-event mass spectrometry detection technique, COINTOF (correlated ion and neutral fragment time of flight). The latter device allows, for each collision event, to detect and identify in a correlated manner all produced neutral and charged fragments. For all the studied cluster ions, it has allowed us to identify branching ratios for the loss of i = 1 to i = n water molecules, leading to fragment ions ranging from H+(H2O)i=n-1 all the way down to the production of protons. Using a corresponding calibration technique we determine total charged fragment production cross sections for incident protonated water clusters H+(H2O)n, with n = 2-7. Observed trends for branching ratios and cross sections, and a comparison with earlier data on measured attenuation cross sections for water clusters colliding with other noble gases (He and Xe), give insight into the underlying dissociation mechanisms.

  8. Interfacial water molecules at biological membranes: Structural features and role for lateral proton diffusion. (United States)

    Nguyen, Trung Hai; Zhang, Chao; Weichselbaum, Ewald; Knyazev, Denis G; Pohl, Peter; Carloni, Paolo


    Proton transport at water/membrane interfaces plays a fundamental role for a myriad of bioenergetic processes. Here we have performed ab initio molecular dynamics simulations of proton transfer along two phosphatidylcholine bilayers. As found in previous theoretical studies, the excess proton is preferably located at the water/membrane interface. Further, our simulations indicate that it interacts not only with phosphate head groups, but also with water molecules at the interfaces. Interfacial water molecules turn out to be oriented relative to the lipid bilayers, consistently with experimental evidence. Hence, the specific water-proton interaction may help explain the proton mobility experimentally observed at the membrane interface.

  9. Microscopic models for proton transfer in water and strongly hydrogen-bonded complexes with a single-well proton potential

    DEFF Research Database (Denmark)

    Kuznetsov, A.M.; Ulstrup, Jens


    A new mechanism and formalism for proton transfer in donor-acceptor complexes with long hydrogen bonds introduced recently [1], is applied to a proton transfer in liquid water. "Structural diffusion" of hydroxonium ions is regarded as totally adiabatic process, with synchronous hindered translation...

  10. Energy loss measurement of protons in liquid water

    Energy Technology Data Exchange (ETDEWEB)

    Siiskonen, T; Peraejaervi, K; Turunen, J [STUK - Radiation and Nuclear Safety Authority, PO Box 14, FI-00881 Helsinki (Finland); Kettunen, H; Javanainen, A; Rossi, M; Trzaska, W H; Virtanen, A, E-mail: [Department of Physics, University of Jyvaeskylae, PO Box 35, FI-40014, Jyvaeskylae (Finland)


    The proton stopping power of liquid water was, for the first time, measured in the energy range 4.7-15.2 MeV. The proton energies were determined by the time-of-flight transmission technique with the microchannel plate detectors, which were especially developed for timing applications. The results are compared to the literature values (from ICRU Report 49 (1993) and Janni's tabulation (1982 At. Data Nucl. Data Tables 27 147-339)) which are based on Bethe's formula and an agreement is found within the experimental uncertainty of 4.6%. Thus, earlier reported discrepancy between the experimental and literature stopping power values at lower energies was not observed at the energies considered in this experiment.

  11. High order magnetic optics for high dynamic range proton radiography at a kinetic energy of 800 MeV

    Energy Technology Data Exchange (ETDEWEB)

    Sjue, S. K. L., E-mail:; Mariam, F. G.; Merrill, F. E.; Morris, C. L.; Saunders, A. [Physics Division, Los Alamos National Laboratory, Los Alamos, New Mexico 87545 (United States)


    Flash radiography with 800 MeV kinetic energy protons at Los Alamos National Laboratory is an important experimental tool for investigations of dynamic material behavior driven by high explosives or pulsed power. The extraction of quantitative information about density fields in a dynamic experiment from proton generated images requires a high fidelity model of the proton imaging process. It is shown that accurate calculations of the transmission through the magnetic lens system require terms beyond second order for protons far from the tune energy. The approach used integrates the correlated multiple Coulomb scattering distribution simultaneously over the collimator and the image plane. Comparison with a series of static calibration images demonstrates the model’s accurate reproduction of both the transmission and blur over a wide range of tune energies in an inverse identity lens that consists of four quadrupole electromagnets.

  12. Water-Free Proton-Conducting Membranes for Fuel Cells (United States)

    Narayanan, Sekharipuram; Yen, Shiao-Pin


    Poly-4-vinylpyridinebisulfate (P4VPBS) is a polymeric salt that has shown promise as a water-free proton-conducting material (solid electrolyte) suitable for use in membrane/electrode assemblies in fuel cells. Heretofore, proton-conducting membranes in fuel cells have been made from perfluorinated ionomers that cannot conduct protons in the absence of water and, consequently, cannot function at temperatures >100 C. In addition, the stability of perfluorinated ionomers at temperatures >100 C is questionable. However, the performances of fuel cells of the power systems of which they are parts could be improved if operating temperatures could be raised above 140 C. What is needed to make this possible is a solid-electrolyte material, such as P4VPBS, that can be cast into membranes and that both retains proton conductivity and remains stable in the desired higher operating temperature range. A family of solid-electrolyte materials different from P4VPBS was described in Anhydrous Proton-Conducting Membranes for Fuel Cells (NPO-30493), NASA Tech Briefs, Vol. 29, No. 8 (August 2005), page 48. Those materials notably include polymeric quaternized amine salts. If molecules of such a polymeric salt could be endowed with flexible chain structures, it would be possible to overcome the deficiencies of simple organic amine salts that must melt before being able to conduct protons. However, no polymeric quaternized amine salts have yet shown to be useful in this respect. The present solid electrolyte is made by quaternizing the linear polymer poly- 4-vinylpyridine (P4VP) to obtain P4VPBS. It is important to start with P4VP having a molecular weight of 160,000 daltons because P4VPBS made from lower-molecular-weight P4VP yields brittle membranes. In an experimental synthesis, P4VP was dissolved in methanol and then reacted with an excess of sulfuric acid to precipitate P4VPBS. The precipitate was recovered, washed several times with methanol to remove traces of acid, and dried to a

  13. Water Soluble Polymers as Proton Exchange Membranes for Fuel Cells

    Directory of Open Access Journals (Sweden)

    Bing-Joe Hwang


    Full Text Available The relentless increase in the demand for useable power from energy-hungry economies continues to drive energy-material related research. Fuel cells, as a future potential power source that provide clean-at-the-point-of-use power offer many advantages such as high efficiency, high energy density, quiet operation, and environmental friendliness. Critical to the operation of the fuel cell is the proton exchange membrane (polymer electrolyte membrane responsible for internal proton transport from the anode to the cathode. PEMs have the following requirements: high protonic conductivity, low electronic conductivity, impermeability to fuel gas or liquid, good mechanical toughness in both the dry and hydrated states, and high oxidative and hydrolytic stability in the actual fuel cell environment. Water soluble polymers represent an immensely diverse class of polymers. In this comprehensive review the initial focus is on those members of this group that have attracted publication interest, principally: chitosan, poly (ethylene glycol, poly (vinyl alcohol, poly (vinylpyrrolidone, poly (2-acrylamido-2-methyl-1-propanesulfonic acid and poly (styrene sulfonic acid. The paper then considers in detail the relationship of structure to functionality in the context of polymer blends and polymer based networks together with the effects of membrane crosslinking on IPN and semi IPN architectures. This is followed by a review of pore-filling and other impregnation approaches. Throughout the paper detailed numerical results are given for comparison to today’s state-of-the-art Nafion® based materials.

  14. Light induced oxidative water splitting in photosynthesis: energetics, kinetics and mechanism. (United States)

    Renger, Gernot


    The essential steps of photosynthetic water splitting take place in Photosystem II (PSII) and comprise three different reaction sequences: (i) light induced formation of the radical pair P680(+)Q(A)(-), (ii) P680(+) driven oxidative water splitting into O(2) and four protons, and (iii) two step plastoquinone reduction to plastoquinol by Q(A)(-). This mini-review briefly summarizes our state of knowledge on energetics, kinetics and mechanism of oxidative water splitting. Essential features of the two types of reactions involved are described: (a) P680(+) reduction by the redox active tyrosine Y(z) and (b) sequence of oxidation steps induced by Y(z)(ox) in the water-oxidizing complex (WOC). The rate of the former reaction is limited by the non-adiabatic electron transfer (NET) step and the multi-phase kinetics shown to originate from a sequence of relaxation processes. In marked contrast, the rate of the stepwise oxidation by Y(z)(ox) of the WOC up to the redox level S(3) is not limited by NET but by trigger reactions which probably comprise proton shifts and/or conformational changes. The overall rate of the final reaction sequence leading to formation and release of O(2) is assumed to be limited by the electron transfer step from the S(3) state of WOC to Y(z)(ox) due to involvement of an endergonic redox equilibrium. Currently discussed controversial ideas on possible pathways are briefly outlined. Several crucial points of the mechanism of oxidative water splitting, like O-O bond formation, role of local proton shift(s), details of hydrogen bonding, are still not clarified and remain a challenging topic of future research. Copyright © 2011 Elsevier B.V. All rights reserved.

  15. Proton nuclear magnetic resonance study of water + t-butyl alcohol ...

    African Journals Online (AJOL)

    Hydroxyl-proton chemical shifts for water and t-butyl alcohol in water + t-butyl alcohol mixtures with 8 mol% t-butyl alcohol, and the average hydroxyl and amino proton chemical shift for water + t-butylamine mixtures, have been determined at 200 MHz for four temperatures (263, 278, 298 and 313 K) as a function of ...

  16. On the mean kinetic energy of the proton in strong hydrogen bonded systems

    Energy Technology Data Exchange (ETDEWEB)

    Finkelstein, Y. [Nuclear Research Center–Negev, Beer-Sheva 84190 (Israel); Moreh, R. [Physics Department, Ben-Gurion University of the Negev, Beer-Sheva 84105 (Israel); Shang, S. L.; Wang, Y.; Liu, Z. K. [Department of Materials Science and Engineering, The Pennsylvania State University, University Park, Pennsylvania 16802 (United States); Shchur, Ya. [Institute for Condensed Matter Physics, 1 Svientsitskii str., L’viv 79011 (Ukraine)


    The mean atomic kinetic energies of the proton, Ke(H), and of the deuteron, Ke(D), were calculated in moderate and strongly hydrogen bonded (HB) systems, such as the ferro-electric crystals of the KDP type (XH{sub 2}PO{sub 4}, X = K, Cs, Rb, Tl), the DKDP (XD{sub 2}PO{sub 4}, X = K, Cs, Rb) type, and the X{sub 3}H(SO{sub 4}){sub 2} superprotonic conductors (X = K, Rb). All calculations utilized the simulated partial phonon density of states, deduced from density functional theory based first-principle calculations and from empirical lattice dynamics simulations in which the Coulomb, short range, covalent, and van der Waals interactions were accounted for. The presently calculated Ke(H) values for the two systems were found to be in excellent agreement with published values obtained by deep inelastic neutron scattering measurements carried out using the VESUVIO instrument of the Rutherford Laboratory, UK. The Ke(H) values of the M{sub 3}H(SO{sub 4}){sub 2} compounds, in which the hydrogen bonds are centro-symmetric, are much lower than those of the KDP type crystals, in direct consistency with the oxygen-oxygen distance R{sub OO}, being a measure of the HB strength.

  17. Luminescence imaging of water during proton-beam irradiation for range estimation

    Energy Technology Data Exchange (ETDEWEB)

    Yamamoto, Seiichi, E-mail:; Okumura, Satoshi; Komori, Masataka [Radiological and Medical Laboratory Sciences, Nagoya University Graduate School of Medicine, Nagoya 461-8673 (Japan); Toshito, Toshiyuki [Department of Proton Therapy Physics, Nagoya Proton Therapy Center, Nagoya City West Medical Center, Nagoya 462-8508 (Japan)


    Purpose: Proton therapy has the ability to selectively deliver a dose to the target tumor, so the dose distribution should be accurately measured by a precise and efficient method. The authors found that luminescence was emitted from water during proton irradiation and conjectured that this phenomenon could be used for estimating the dose distribution. Methods: To achieve more accurate dose distribution, the authors set water phantoms on a table with a spot scanning proton therapy system and measured the luminescence images of these phantoms with a high-sensitivity, cooled charge coupled device camera during proton-beam irradiation. The authors imaged the phantoms of pure water, fluorescein solution, and an acrylic block. Results: The luminescence images of water phantoms taken during proton-beam irradiation showed clear Bragg peaks, and the measured proton ranges from the images were almost the same as those obtained with an ionization chamber. Furthermore, the image of the pure-water phantom showed almost the same distribution as the tap-water phantom, indicating that the luminescence image was not related to impurities in the water. The luminescence image of the fluorescein solution had ∼3 times higher intensity than water, with the same proton range as that of water. The luminescence image of the acrylic phantom had a 14.5% shorter proton range than that of water; the proton range in the acrylic phantom generally matched the calculated value. The luminescence images of the tap-water phantom during proton irradiation could be obtained in less than 2 s. Conclusions: Luminescence imaging during proton-beam irradiation is promising as an effective method for range estimation in proton therapy.

  18. Kinetic studies of biogas generated from water hyacinth ( Eichhornia ...

    African Journals Online (AJOL)

    Abstract. This research work investigated the operational process of production of biogas by the leaves, stem and their mixtures of the water hyacinth (Eichhornia crassipes), during anaerobic digestion for a period of eight weeks, using locally constructed ... Keywords: Kinetic models, biomass, biogas, Water hyacinth, energy ...

  19. Photocatalytic Water-Splitting Reaction from Catalytic and Kinetic Perspectives

    KAUST Repository

    Hisatomi, Takashi


    Abstract: Some particulate semiconductors loaded with nanoparticulate catalysts exhibit photocatalytic activity for the water-splitting reaction. The photocatalysis is distinct from the thermal catalysis because photocatalysis involves photophysical processes in particulate semiconductors. This review article presents a brief introduction to photocatalysis, followed by kinetic aspects of the photocatalytic water-splitting reaction.Graphical Abstract: [Figure not available: see fulltext.

  20. Water in the physiology of plant: thermodynamics and kinetic

    Directory of Open Access Journals (Sweden)

    Maurizio Cocucci


    Full Text Available Molecular properties of water molecule determine its role in plant physiology. At molecular level the properties of water molecules determine the behaviour of other plant molecules; in particular its physic characteristics are important in the operativeness of macromolecules and in plant thermoregulation. Plant water supply primarily dependent on thermodynamics properties in particular water chemical potential and its components, more recently there are evidences that suggest an important role in the water kinetic characteristics, depending, at cell membrane level, in particular plasmalemma, on the presence of specific water channel, the aquaporines controlled in its activity by a number of physiological and biochemical factors. Thermodynamics and kinetic factors controlled by physiological, biochemical properties and molecular effectors, control water supply and level in plants to realize their survival, growth and differentiation and the consequent plant production.

  1. Comparison of basic features of proton and helium ion pencil beams in water using GATE. (United States)

    Ströbele, Julia; Schreiner, Thomas; Fuchs, Hermann; Georg, Dietmar


    The aim of this study was to investigate the basic features of helium ions for their possible application in advanced radiotherapy and to benchmark them against protons, the current particle of choice in the low linear energy transfer (LET) range. Geant4 Application for Emission Tomography (GATE) simulations were performed with beams of 1x10(7) monodirectional particles traversing a water phantom. Initial energies ranged from 50 to 250 MeV per nucleon (MeV/A). The following parameters were evaluated: particle range at the distal 80% of maximum energy deposition (E(max)), width of the Bragg peak (BP) at 60% of E(max), and dose fall-off width between 80% and 20% of E(max) for longitudinal spectra. In addition the fragmentation tail was quantified in terms of length, percental energy deposition, and contributing particles. For each energy lateral profiles were registered along the beam axis and the FWHM at four different depths was extracted. Besides the comparison of parameters between the two particle types, results were also compared to data in the literature. As expected, the position of the BP as a function of initial kinetic energy showed similar values for protons and helium ions, with deviations smaller than 1.3%. The quantitative results of the Monte Carlo (MC) study showed less range straggling effects and smaller lateral deflections for helium ions compared to protons for the investigated energy range. On average, an about 56% reduction of the width of the BP and a 48% reduction of the dose fall-off was observed for helium ions compared to protons. Both the width of the BP and the dose fall-off width as a function of particle range or energy showed an almost linear increase with increasing energy. The tail length increased from 55.9 mm to 592.7 mm and the deposited energy increased from 0.5% to 7.3% for energies between 90 and 250 MeV/A. Lateral profiles of helium ions were about 52% narrower than those of protons. Due to their mass and charge helium

  2. Towards a kinetic energy density functional for the water molecule (United States)

    Akin-Ojo, Omololu; Shittu, Doyin

    Development of an accurate kinetic energy kinetic energy density functional (KEDF) is a holy grail. In this work, local KEDFS are parameterized for the water molecule in order to reproduce Kohn-Sham density functional theory (KS-DFT) results. Energies, forces and dipole moments from these KEDFs are presented. Problems with the convergence of the self-consistent-field (SCF) calculations are discussed together with possible solutions. and: Theoretical and Applied Physics Dept. African Univ. of Science and Technology (AUST) Abuja, Nigeria.

  3. Experimental investigation of picosecond dynamics following interactions between laser accelerated protons and water (United States)

    Senje, L.; Coughlan, M.; Jung, D.; Taylor, M.; Nersisyan, G.; Riley, D.; Lewis, C. L. S.; Lundh, O.; Wahlström, C.-G.; Zepf, M.; Dromey, B.


    We report direct experimental measurements with picosecond time resolution of how high energy protons interact with water at extreme dose levels (kGy), delivered in a single pulse with the duration of less than 80 ps. The unique synchronisation possibilities of laser accelerated protons with an optical probe pulse were utilized to investigate the energy deposition of fast protons in water on a time scale down to only a few picoseconds. This was measured using absorbance changes in the water, induced by a population of solvated electrons created in the tracks of the high energy protons. Our results indicate that for sufficiently high doses delivered in short pulses, intertrack effects will affect the yield of solvated electrons. The experimental scheme allows for investigation of the ultrafast mechanisms occurring in proton water radiolysis, an area of physics especially important due to its relevance in biology and for proton therapy.

  4. Umbrella sampling of proton transfer in a creatine-water system (United States)

    Ivchenko, Olga; Bachert, Peter; Imhof, Petra


    Proton transfer reactions are among the most common processes in chemistry and biology. Proton transfer between creatine and surrounding solvent water is underlying the chemical exchange saturation transfer used as a contrast in magnetic resonance imaging. The free energy barrier, determined by first-principles umbrella sampling simulations (EaDFT 3 kcal/mol) is in the same order of magnitude as the experimentally obtained activation energy. The underlying mechanism is a first proton transfer from the guanidinium group to the water pool, followed by a second transition where a proton is "transferred back" from the nearest water molecule to the deprotonated nitrogen atom of creatine.

  5. Near-Infrared Spectroscopy of Small Protonated Water Clusters (United States)

    Wagner, J. Philipp; McDonald, David C., II; McCoy, Anne B.; Duncan, Michael A.


    Small protonated water clusters and their argon tagged analogues of the general formula H^{+}(H_{2}O)_{n}Ar_{m} have been generated in a pulsed electric discharge source. Clusters containing n=1-8 water molecules were mass-selected and their absorptions in the near-infrared were probed with a tunable Nd/colonYAG pumped OPA/OPA laser system in the region from 4850-7350 cm^{-1}. A doublet corresponding to overtones of the free O-H stretches of the external waters was observed around 7200 cm^{-1} that was continuously decreasing in intensity with increasing cluster size. Broad, mostly featureless absorptions were found around 5300 cm^{-1} associated with stretch/bend combinations and with the hydrogen bonded waters in the core of the clusters. Vibrational assignments were substantiated by comparison to anharmonic frequency computations via second-order vibrational perturbation theory (VPT2) at the MP2/aug-cc-pVTZ level of theory.

  6. Structure dynamics of the proton in liquid water probed with terahertz time-domain spectroscopy

    NARCIS (Netherlands)

    Tielrooij, K.J.; Timmer, R.L.A.; Bakker, H.J.; Bonn, M.


    We study the hydration of protons in liquid water using terahertz time-domain spectroscopy and polarization-resolved femtosecond midinfrared pump-probe spectroscopy. We observe that the addition of protons leads to a very strong decrease of the dielectric response of liquid water that corresponds to

  7. Ultrafast vibrational and structural dynamics of the proton in liquid water. (United States)

    Woutersen, Sander; Bakker, Huib J


    The dynamical behavior of excess protons in liquid water is investigated using femtosecond vibrational pump-probe spectroscopy. By resonantly exciting the O-H+-stretching mode of the H9O4(+) (Eigen) hydration structure of the proton and probing the subsequent absorption change over a broad frequency range, the dynamics of the proton is observed in real time. The lifetime of the protonic stretching mode is found to be approximately 120 fs, shorter than for any other vibration in liquid water. We also observe the interconversion between the H9O4(+) (Eigen) and H5O2(+) (Zundel) hydration structures of the proton. This interconversion, which constitutes an essential step of proton transport in water, is found to occur on an extremely fast (< 100 fs) time scale.

  8. Coarse-grained model of water diffusion and proton conductivity in hydrated polyelectrolyte membrane

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Ming-Tsung; Vishnyakov, Aleksey; Neimark, Alexander V., E-mail: [Department of Chemical and Biochemical Engineering, Rutgers, The State University of New Jersey, 98 Brett Road, Piscataway, New Jersey 08854-8058 (United States)


    Using dissipative particle dynamics (DPD), we simulate nanoscale segregation, water diffusion, and proton conductivity in hydrated sulfonated polystyrene (sPS). We employ a novel model [Lee et al. J. Chem. Theory Comput. 11(9), 4395-4403 (2015)] that incorporates protonation/deprotonation equilibria into DPD simulations. The polymer and water are modeled by coarse-grained beads interacting via short-range soft repulsion and smeared charge electrostatic potentials. The proton is introduced as a separate charged bead that forms dissociable Morse bonds with the base beads representing water and sulfonate anions. Morse bond formation and breakup artificially mimics the Grotthuss mechanism of proton hopping between the bases. The DPD model is parameterized by matching the proton mobility in bulk water, dissociation constant of benzenesulfonic acid, and liquid-liquid equilibrium of water-ethylbenzene solutions. The DPD simulations semi-quantitatively predict nanoscale segregation in the hydrated sPS into hydrophobic and hydrophilic subphases, water self-diffusion, and proton mobility. As the hydration level increases, the hydrophilic subphase exhibits a percolation transition from isolated water clusters to a 3D network. The analysis of hydrophilic subphase connectivity and water diffusion demonstrates the importance of the dynamic percolation effect of formation and breakup of temporary junctions between water clusters. The proposed DPD model qualitatively predicts the ratio of proton to water self-diffusion and its dependence on the hydration level that is in reasonable agreement with experiments.

  9. Kinetics of proton transport into influenza virions by the viral M2 channel.

    Directory of Open Access Journals (Sweden)

    Tijana Ivanovic

    Full Text Available M2 protein of influenza A viruses is a tetrameric transmembrane proton channel, which has essential functions both early and late in the virus infectious cycle. Previous studies of proton transport by M2 have been limited to measurements outside the context of the virus particle. We have developed an in vitro fluorescence-based assay to monitor internal acidification of individual virions triggered to undergo membrane fusion. We show that rimantadine, an inhibitor of M2 proton conductance, blocks the acidification-dependent dissipation of fluorescence from a pH-sensitive virus-content probe. Fusion-pore formation usually follows internal acidification but does not require it. The rate of internal virion acidification increases with external proton concentration and saturates with a pK(m of ∼4.7. The rate of proton transport through a single, fully protonated M2 channel is approximately 100 to 400 protons per second. The saturating proton-concentration dependence and the low rate of internal virion acidification derived from authentic virions support a transporter model for the mechanism of proton transfer.

  10. Kinetics of Ce and Nd scavenging in Black Sea waters

    NARCIS (Netherlands)

    Schijf, Johan; Baar, Hein J.W. de; Millero, Frank J.


    Mixing experiments were performed during Leg 5 of the 1988 Black Sea Expedition in order to learn more about the mechanism and kinetics of rare earth element (REE) scavenging at the oxic-anoxic interface of anoxic basins and, more specifically, in the suboxic zone of the Black Sea. Water from the

  11. Water and proton transport properties of hexafluorinated sulfonated poly(arylenethioethersulfone) copolymers for applications to proton exchange membrane fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Khalfan, Amish N.; Sanchez, Luz M.; Kodiweera, Chandana; Greenbaum, Steve G. [Hunter College of the City University of New York, Physics Department, 695 Park Avenue, New York, NY 10021 (United States); Bai, Zongwu [University of Dayton Research Institute, University of Dayton, 300 College Park Drive, Dayton, OH 45469 (United States); Dang, Thuy D. [Air Force Research Laboratory/MLBP, Material and Manufacturing Directorate, Wright-Patterson Air Force Base, OH 45433 (United States)


    In the present study, we examine the water and proton transport properties of hexafluorinated sulfonated poly(arylenethioethersulfone) (6F-SPTES) copolymer membranes for applications to proton exchange membrane fuel cells (PEMFCs). The 6F-SPTES copolymer membranes build upon the structures of previously studied sulfonated poly(arylenethioethersulfone) (SPTES) copolymer membranes to include CF{sub 3} functional groups in efforts to strengthen water retention and extend membrane performance at elevated temperatures (above 120 C). The 6F-SPTES copolymer membranes sustain higher water self-diffusion and greater proton conductivities than the commercial Nafion {sup registered} membrane. Water diffusion studies of the 6F-SPTES copolymer membranes using the pulsed-field gradient spin-echo NMR technique reveal, however, the fluorinated membranes to be somewhat unfavorable over their non-fluorinated counterparts as high temperature membranes. In addition, proton conductivity measurements of the fluorinated membranes up to 85 C show comparable results with the non-fluorinated SPTES membranes. (author)

  12. The excess proton at the air-water interface: The role of instantaneous liquid interfaces (United States)

    Giberti, Federico; Hassanali, Ali A.


    The magnitude of the pH of the surface of water continues to be a contentious topic in the physical chemistry of aqueous interfaces. Recent theoretical studies have shown little or no preference for the proton to be at the surface compared to the bulk. Using ab initio molecular dynamics simulations, we revisit the propensity of the excess proton for the air-water interface with a particular focus on the role of instantaneous liquid interfaces. We find a more pronounced presence for the proton to be at the air-water interface. The enhanced water structuring around the proton results in the presence of proton wires that run parallel to the surface as well as a hydrophobic environment made up of under-coordinated topological defect water molecules, both of which create favorable conditions for proton confinement at the surface. The Grotthuss mechanism within the structured water layer involves a mixture of both concerted and closely spaced stepwise proton hops. The proton makes excursions within the first solvation layer either in proximity to or along the instantaneous interface.

  13. Orientation of non-spherical protonated water clusters revealed by infrared absorption dichroism. (United States)

    Daldrop, Jan O; Saita, Mattia; Heyden, Matthias; Lorenz-Fonfria, Victor A; Heberle, Joachim; Netz, Roland R


    Infrared continuum bands that extend over a broad frequency range are a key spectral signature of protonated water clusters. They are observed for many membrane proteins that contain internal water molecules, but their microscopic mechanism has remained unclear. Here we compute infrared spectra for protonated and unprotonated water chains, discs, and droplets from ab initio molecular dynamics simulations. The continuum bands of the protonated clusters exhibit significant anisotropy for chains and discs, with increased absorption along the direction of maximal cluster extension. We show that the continuum band arises from the nuclei motion near the excess charge, with a long-ranged amplification due to the electronic polarizability. Our experimental, polarization-resolved light-dark difference spectrum of the light-driven proton pump bacteriorhodopsin exhibits a pronounced dichroic continuum band. Our results suggest that the protonated water cluster responsible for the continuum band of bacteriorhodopsin is oriented perpendicularly to the membrane normal.

  14. Nonlinear interaction of proton whistler with kinetic Alfvén wave to study solar wind turbulence

    Energy Technology Data Exchange (ETDEWEB)

    Goyal, R.; Sharma, R. P. [Centre for Energy Studies, Indian Institute of Technology, Delhi-110016 (India); Goldstein, M. L. [NASA Goddard Space Flight Centre, Code 673, Greenbelt, Maryland 20771 (United States); Dwivedi, N. K. [Austrian Academy of Sciences, Space Research Institute, Schmiedlstrasse 6, 8042 Graz (Austria)


    This paper presents the nonlinear interaction between small but finite amplitude kinetic Alfvén wave (KAW) and proton whistler wave using two-fluid model in intermediate beta plasma, applicable to solar wind. The nonlinearity is introduced by modification in the background density. This change in density is attributed to the nonlinear ponderomotive force due to KAW. The solutions of the model equations, governing the nonlinear interaction (and its effect on the formation of localized structures), have been obtained using semi-analytical method in solar wind at 1AU. It is concluded that the KAW properties significantly affect the threshold field required for the filament formation and their critical size (for proton whistler). The magnetic and electric field power spectra have been obtained and their relevance with the recent observations of solar wind turbulence by Cluster spacecraft has been pointed out.


    African Journals Online (AJOL)

    capable to initiate a photochemical reaction by absorbing photons upon exposition to light at visible wavelength. ... The free base TPPS (H2tpps4-), Figure 1, can be protonated by one or two protons on pyrrolinic ... the nature of this compound, a complete evaluation of its acid-base characteristics and their dependence on ...

  16. Intermediates and kinetics for phenol gasification in supercritical water. (United States)

    Huelsman, Chad M; Savage, Phillip E


    We processed phenol with supercritical water in a series of experiments, which systematically varied the temperature, water density, reactant concentration, and reaction time. Both the gas and liquid phases were analyzed post-reaction using gas chromatographic techniques, which identified and quantified the reaction intermediates and products, including H(2), CO, CH(4), and CO(2) in the gas phase and twenty different compounds--mainly polycyclic aromatic hydrocarbons--in the liquid phase. Many of these liquid phase compounds were identified for the first time and could pose environmental risks. Higher temperatures promoted gasification and resulted in a product gas rich in H(2) and CH(4) (33% and 29%, respectively, at 700 °C), but char yields increased as well. We implicated dibenzofuran and other identified phenolic dimers as precursor molecules for char formation pathways, which can be driven by free radical polymerization at high temperatures. Examination of the trends in conversion as a function of initial water and phenol concentrations revealed competing effects, and these informed the kinetic modeling of phenol disappearance. Two different reaction pathways emerged from the kinetic modeling: one in which rate ∝ [phenol](1.73)[water](-16.60) and the other in which rate ∝ [phenol](0.92)[water](1.39). These pathways may correspond to pyrolysis, which dominates when there is abundant phenol and little water, and hydrothermal reactions, which dominate in excess water. This result confirms that supercritical water gasification of phenol does not simply follow first-order kinetics, as previous efforts to model phenol disappearance had assumed.

  17. Kinetic isotope effects provide experimental evidence for proton tunneling in methylammonium lead triiodide perovskites. (United States)

    Chen, Yan-Fang; Tsai, Yu-Tang; Hirsch, Lionel; Bassani, Dario M


    The occurrence of proton tunneling in MAPbI3 hybrid organic inorganic perovskites is demonstrated through the effect of isotopic labeling of the methylammonium (MA) component on the dielectric permittivity response. Deuteration of the ammonium group results in the acceleration of proton migration (inverse primary isotope effect), whereas deuteration of the methyl group induces a normal secondary isotope effect. The activation energies for proton migration are calculated to be 50 and 27 meV for the tetragonal and orthorhombic phases, respectively, which decrease upon deuteration of the ammonium group. The low activation barrier, and the deviation from unity of the ratio of the pre-exponential factors (AH/AD = 0.3 - 0.4) are consistent with a tunneling mechanism for proton migration. Deuteration of the PEDOT:PSS hole transport layer results in a behavior that is intermediate between that of the deuterated and undeuterated perovskite, due to extrinsic ion migration between the two materials.

  18. Probing water micro-solvation in proteins by water catalysed proton-transfer tautomerism. (United States)

    Shen, Jiun-Yi; Chao, Wei-Chih; Liu, Chun; Pan, Hsiao-An; Yang, Hsiao-Ching; Chen, Chi-Lin; Lan, Yi-Kang; Lin, Li-Ju; Wang, Jinn-Shyan; Lu, Jyh-Feng; Chun-Wei Chou, Steven; Tang, Kuo-Chun; Chou, Pi-Tai


    Scientists have made tremendous efforts to gain understanding of the water molecules in proteins via indirect measurements such as molecular dynamic simulation and/or probing the polarity of the local environment. Here we present a tryptophan analogue that exhibits remarkable water catalysed proton-transfer properties. The resulting multiple emissions provide unique fingerprints that can be exploited for direct sensing of a site-specific water environment in a protein without disrupting its native structure. Replacing tryptophan with the newly developed tryptophan analogue we sense different water environments surrounding the five tryptophans in human thromboxane A₂ synthase. This development may lead to future research to probe how water molecules affect the folding, structures and activities of proteins.

  19. Compression Freezing Kinetics of Water to Ice VII (United States)

    Gleason, A. E.; Bolme, C. A.; Galtier, E.; Lee, H. J.; Granados, E.; Dolan, D. H.; Seagle, C. T.; Ao, T.; Ali, S.; Lazicki, A.; Swift, D.; Celliers, P.; Mao, W. L.


    Time-resolved x-ray diffraction (XRD) of compressed liquid water shows transformation to ice VII in 6 nsec, revealing crystallization rather than amorphous solidification during compression freezing. Application of classical nucleation theory indicates heterogeneous nucleation and one-dimensional (e.g., needlelike) growth. These first XRD data demonstrate rapid growth kinetics of ice VII with implications for fundamental physics of diffusion-mediated crystallization and thermodynamic modeling of collision or impact events on ice-rich planetary bodies.

  20. Anisotropy of the proton kinetic energy in CsH2PO4 and KH2PO4 (United States)

    Finkelstein, Y.; Moreh, R.; Shchur, Ya.


    The strong anisotropy of the proton mean kinetic energy, Ke(H), in a single crystal of KH2PO4 (KDP), measured by deep inelastic neutron scattering (DINS), is compared with that calculated for its Cs analogue, CsH2PO4 (CDP) in the ferroelectric (FE) and paraelectric (PE) phases. Empirical lattice dynamics (LD) calculations were used to simulate the partial vibrational density of states shared by the protons (H-VDOS), from which Ke(H) values were deduced. Good agreement was found between the measured and calculated Ke(H) values of the two samples despite the different hydrogen bond dynamics. However, the directional components of Ke(H) in the two samples were quite different. In both cases, the Ke(H) tensor is nearly an ellipsoid of rotation: in KDP the shape is oblate around the major axis while being prolate in CDP. By resolving the directional Ke(H) values of the two non-equivalent protons of CDP, a possible signature of competing quantum effects is indicated.

  1. Correlation between Morphology, Water Uptake, and Proton Conductivity in Radiation-Grafted Proton-Exchange Membranes

    DEFF Research Database (Denmark)

    Balog, Sandor; Gasser, Urs; Mortensen, Kell


    An SANS investigation of hydrated proton exchange membranes is presented. Our membranes were synthesized by radiation-induced grafting of ETFE with styrene in the presence of a crosslinker, followed by sulfonation of the styrene. The contrast variation method was used to understand the relationship...

  2. Protic Salt Polymer Membranes: High-Temperature Water-Free Proton-Conducting Membranes

    Energy Technology Data Exchange (ETDEWEB)

    Gervasio, Dominic Francis [Univ. of Arizona, Tucson, AZ (United States)


    This research on proton-containing (protic) salts directly addresses proton conduction at high and low temperatures. This research is unique, because no water is used for proton ionization nor conduction, so the properties of water do not limit proton fuel cells. A protic salt is all that is needed to give rise to ionized proton and to support proton mobility. A protic salt forms when proton transfers from an acid to a base. Protic salts were found to have proton conductivities that are as high as or higher than the best aqueous electrolytes at ambient pressures and comparable temperatures without or with water present. Proton conductivity of the protic salts occurs providing two conditions exist: i) the energy difference is about 0.8 eV between the protic-salt state versus the state in which the acid and base are separated and 2) the chemical constituents rotate freely. The physical state of these proton-conducting salts can be liquid, plastic crystal as well as solid organic and inorganic polymer membranes and their mixtures. Many acids and bases can be used to make a protic salt which allows tailoring of proton conductivity, as well as other properties that affect their use as electrolytes in fuel cells, such as, stability, adsorption on catalysts, environmental impact, etc. During this project, highly proton conducting (~ 0.1S/cm) protic salts were made that are stable under fuel-cell operating conditions and that gave highly efficient fuel cells. The high efficiency is attributed to an improved oxygen electroreduction process on Pt which was found to be virtually reversible in a number of liquid protic salts with low water activity (< 1% water). Solid flexible non-porous composite membranes, made from inorganic polymer (e.g., 10%indium 90%tin pyrophosphate, ITP) and organic polymer (e.g., polyvinyl pyridinium phosphate, PVPP), were found that give conductivity and fuel cell performances similar to phosphoric acid electrolyte with no need for hydration at

  3. Role of protons in the pump cycle of KdpFABC investigated by time-resolved kinetic experiments. (United States)

    Damnjanovic, Bojana; Apell, Hans-Jürgen


    The time-resolved kinetics of the KdpFABC complex solubilized in Aminoxide WS-35 was investigated by ATP concentration jump experiments. ATP was photoreleased from its inactive precursor, caged ATP, and charge movements in the membrane domain of the KdpFABC were detected by the electrochromic dye RH421. At low ATP concentrations, the ATP binding step became rate-limiting with an apparent, pH-independent ATP binding affinity of ~70 μM. At saturating ATP concentrations, the rate-limiting step is the conformational transition (E1-P → P-E2) with a rate constant of ~1.7 s(-1) at 20 °C that was independent of K(+) concentration. This observation together with the detected fluorescence decrease indicates that K(+) (or another positive ion) is bound in the membrane domain after enzyme phosphorylation and the conformational transition to the P-E2 state. pH dependence experiments revealed different roles of H(+) in the transport mechanism. Two different functions of protons for the ion pump must be distinguished. On one hand, there are electrogenically bound "functional" protons, which are not transported but prerequisite for the performance of the ATP-driven half-cycle. On the other hand, protons bind to the transport sites, acting as weak congeners of K(+). There possibly are noncompetitively bound protons, affecting the enzyme activity and/or coupling between KdpA and KdpB subunits. Finally, the recently proposed Post-Albers model for the KdpFABC complex was supplemented with stoichiometry factors of 2 for K(+) and 3 for H(+), and additional inhibitory side reactions controlled by H(+) were introduced, which are relevant at pH <6.5 and/or in the absence of K(+).

  4. Tracking the Structural and Electronic Configurations of a Cobalt Proton Reduction Catalyst in Water

    Energy Technology Data Exchange (ETDEWEB)

    Moonshiram, Dooshaye; Gimbert-Suriñach, Carolina [Institute; Guda, Alexander [International; Picon, Antonio; Lehmann, C. Stefan; Zhang, Xiaoyi; Doumy, Gilles; March, Anne Marie; Benet-Buchholz, Jordi [Institute; Soldatov, Alexander [International; Llobet, Antoni [Institute; Departament; Southworth, Stephen H.


    Time resolved X-ray absorption spectroscopy (X-TAS) has been used to study the light induced hydrogen evolution reaction catalyzed by a highly stable cobalt complex, [Ru(bpy)3]2+ photosensitizer and an equimolar mixture of sodium ascorbate/ascorbic acid electron donor in pure water. XANES and EXAFS analysis of a binary mixture of the octahedral Co(III) pre-catalyst and [Ru(bpy)3]2+ after illumination, revealed in-situ formation of a square pyramidal Co(II) intermediate, with electron transfer kinetics of 51 ns. On the other hand, X-TAS experiments of the complete photocatalytic system in the presence of the electron donor showed the formation of a square planar Co(I) intermediate species within a few nanoseconds followed by its decay in the microsecond timescales. The Co(I) structural assignment is supported by calculations based on density functional theory (DFT). At longer reaction times, we observe the formation of the initial Co(III) species concomitant to the decay of Co(I), thus closing the catalytic cycle. The experimental X-ray absorption spectra of the molecular species formed along the catalytic cycle are modeled using a combination of molecular orbital DFT calculations (DFT-MO) and Finite Difference Method (FDM). These findings allowed us to unequivocally assign the full mechanistic pathway followed by the catalyst as well as to determine the rate limiting step of the process, which consists in the protonation of the Co(I). This study provides a complete kinetics scheme for the hydrogen evolution reaction by a cobalt catalyst, revealing unique information for the development of better catalysts for the reductive side of hydrogen fuel cells.

  5. Aggregation kinetics of nanosilver in different water conditions (United States)

    Chen, Shao-Feng; Zhang, Hongyin


    In this study the effect of different water conditions on the aggregation kinetics of nanosilver (nAg) is evaluated. The obtained results show that the aggregation rate of nAg increases with increasing electrolyte concentration. Divalent cation (Ca2+) can more effectively induce aggregation than monovalent cation (Na+). Critical coagulation concentration of nAg in NaCl solution is about 40 times higher than that in CaCl2 solution. This study also indicates that aggregation rate of nAg in water condition containing high Ca2+ concentration in presence of humic acid is higher than that without humic acid due to the bridging effect of humic acid-Ca2+ complex. Finally, aggregation rate of nAg in seawater is higher than that in lake water.

  6. Kinetics and Mechanism of Deoxygenation Reactions over Proton-Form and Molybdenum-Modified Zeolite Catalysts (United States)

    Bedard, Jeremy William

    The depletion of fossil fuel resources and the environmental consequences of their use have dictated the development of new sources of energy that are both sustainable and economical. Biomass has emerged as a renewable carbon feedstock that can be used to produce chemicals and fuels traditionally obtained from petroleum. The oxygen content of biomass prohibits its use without modification because oxygenated hydrocarbons are non-volatile and have lower energy content. Chemical processes that eliminate oxygen and keep the carbon backbone intact are required for the development of biomass as a viable chemical feedstock. This dissertation reports on the kinetic and mechanistic studies conducted on high and low temperature catalytic processes for deoxygenation of biomass precursors to produce high-value chemicals and fuels. Low temperature, steady state reaction studies of acetic acid and ethanol were used to identify co-adsorbed acetic acid/ethanol dimers as surface intermediates within specific elementary steps involved in the esterification of acetic acid with ethanol on zeolites. A reaction mechanism involving two dominating surface species, an inactive ethanol dimeric species adsorbed on Bronsted sites inhibiting ester formation and a co-adsorbed complex of acetic acid and ethanol on the active site reacting to produce ethyl acetate, is shown to describe the reaction rate as a function of temperature (323 -- 383 K), acetic acid (0.5 -- 6.0 kPa), and ethanol (5.0 -- 13.0 kPa) partial pressure on proton-form BEA, FER, MFI, and MOR zeolites. Measured differences in rates as a function of zeolite structure and the rigorous interpretation of these differences in terms of esterification rate and equilibrium constants is presented to show that the intrinsic rate constant for the activation of the co-adsorbed complex increases in the order FER < MOR < MFI < BEA. High temperature co-processing of acetic acid, formic acid, or carbon dioxide with methane (CH3COOH/CH4 = 0

  7. Simulated solvation of organic ions: protonated methylamines in water nanodroplets. Convergence toward bulk properties and the absolute proton solvation enthalpy. (United States)

    Houriez, Céline; Meot-Ner Mautner, Michael; Masella, Michel


    We applied an alternative, purely theoretical route to estimate thermodynamical properties of organic ions in bulk solution. The method performs a large ensemble of simulations of ions solvated in water nanodroplets of different sizes, using a polarizable molecular dynamics approach. We consider protonated ammonia and methylamines, and K(+) for comparison, solvated in droplets of 50-1000 water molecules. The parameters of the model are assigned from high level quantum computations of small clusters. All the bulk phase results extrapolated from droplet simulations match, and confirm independently, the relative and absolute experiment-based ion solvation energies. Without using experiment-based parameters or assumptions, the results confirm independently the solvation enthalpy of the proton, as -270.3 ± 1.1 kcal mol(-1). The calculated relative solvation enthalpies of these ions are constant from small water clusters, where only the ionic headgroups are solvated, up to bulk solution. This agrees with experimental thermochemistry, that the relative solvation energies of alkylammonium ions by only four H2O molecules reproduce the relative bulk solvation energies, although the small clusters lack major bulk solvation factors. The droplet results also show a slow convergence of ion solvation properties toward their bulk limit, and predict that the stepwise solvation enthalpies of ion/water droplets are very close to those of pure neutral water droplets already after 50 water molecules. Both the ionic and neutral clusters approach the bulk condensation energy very gradually up to 10,000 water molecules, consistent with the macroscopic liquid drop model for pure water droplets. Compared to standard computational methods based on infinite periodic systems, our protocol represents a new purely theoretical approach to investigate the solvation properties of ions. It is applicable to the solvation of organic ions, which are pivotal in environmental, industrial, and

  8. Kinetics of zero valent iron nanoparticle oxidation in oxygenated water. (United States)

    Greenlee, Lauren F; Torrey, Jessica D; Amaro, Robert L; Shaw, Justin M


    Zero valent iron (ZVI) nanoparticles are versatile in their ability to remove a wide variety of water contaminants, and ZVI-based bimetallic nanoparticles show increased reactivity above that of ZVI alone. ZVI nanoparticles degrade contaminants through the reactive species (e.g., OH*, H(2(g)), H(2)O(2)) that are produced during iron oxidation. Measurement and modeling of aqueous ZVI nanoparticle oxidation kinetics are therefore necessary to optimize nanoparticle design. Stabilized ZVI and iron-nickel nanoparticles of approximately 150 nm in diameter were synthesized through solution chemistry, and nanoparticle oxidation kinetics were determined via measured mass change using a quartz crystal microbalance (QCM). Under flowing aerated water, ZVI nanoparticles had an initial exponential growth behavior indicating surface-dominated oxidation controlled by migration of species (H(2)O and O(2)) to the surface. A region of logarithmic growth followed the exponential growth which, based on the Mott-Cabrera model of thin oxide film growth, suggests a reaction dominated by movement of species (e.g., iron cations and oxygen anions) through the oxide layer. The presence of ethanol or a nickel shell on the ZVI nanoparticles delayed the onset of iron oxidation and reduced the extent of oxidation. In oxygenated water, ZVI nanoparticles oxidized primarily to the iron oxide-hydroxide lepidocrocite.

  9. Study of water vapour adsorption kinetics on aluminium oxide materials (United States)

    Livanova, Alesya; Meshcheryakov, Evgeniy; Reshetnikov, Sergey; Kurzina, Irina


    Adsorbents on the basis of active aluminum oxide are still of demand on the adsorbent-driers market. Despite comprehensive research of alumina adsorbents, and currently is an urgent task to improve their various characteristics, and especially the task of increasing the sorption capacity. In the present work kinetics of the processes of water vapours' adsorption at room temperature on the surface of desiccant samples has been studied. It was obtained on the basis of bayerite and pseudoboehmite experimentally. The samples of pseudoboehmite modified with sodium and potassium ions were taken as study objects. The influence of an adsorbent's grain size on the kinetics of water vapours' adsorption was studied. The 0.125-0.25 mm and 0.5-1.0 mm fractions of this sample were used. It has been revealed that the saturation water vapor fine powder (0.125-0.25 mm) is almost twofold faster in comparison with the sample of fraction 0.5-1.0 mm due to the decrease in diffusion resistance in the pores of the samples when moving from the sample of larger fraction to the fine-dispersed sample. It has been established that the adsorption capacity of the pseudoboehmite samples, modified by alkaline ions, is higher by ˜40 %, than for the original samples on the basis of bayerite and pseudoboehmite.

  10. Influence of water and membrane microstructure on the transport properties of proton exchange membrane fuel cells (United States)

    Siu, Ana Rosa

    Proton transport in proton exchange membranes (PEMs) depends on interaction between water and acid groups covalently bound to the polymer. Although the presence of water is important in maintaining the PEM's functions, a thorough understanding of this topic is still lacking. The objective of this work is to provide a better understanding of how the nature water, confined to ionic domains of the polymer, influences the membrane's ability to transport protons, methanol and water. Understanding this topic will facilitate development of new materials with favorable transport properties for fuel cells use. Five classes of polymer membranes were used in this work: polyacrylonitrile-graft-poly(styrenesulfonic) acid (PAN-g-macPSSA); poly(vinylidene difluoride) irradiation-graft-poly(styrenesulfonic) acid (PVDF-g-PSSA); poly(ethylenetetrafluoroethylene) irradiation-graft-poly(styrenesulfonic) acid (ETFE-gPSSA); PVDF-g-PSSA with hydroxyethylmethacrylate (HEMA); and perfluorosulfonic acid membrane (Nafion). The nature of water within the polymers (freezable versus non-freezable states) was measured by systematically freezing samples, and observing the temperature at which water freezes and the amount of heat released in the process. Freezing water-swollen membranes resulted in a 4-fold decrease in the proton conductivity of the PEM. Activation energies of proton transport before and after freezing were ˜ 0.15 eV and 0.5 eV, consistent with proton transport through liquid water and bound water, respectively. Reducing the content of water in membrane samples decreased the amount of freezable and non-freezable water. Calorimetric measurements of membranes in various degrees of hydration showed that water molecules became non-freezable when lambda, (water molecules per sulfonic acid group) was less than ˜14. Proton conduction through membranes containing only non-freezable water was demonstrated to be feasible. Diffusion experiments showed that the permeability of methanol

  11. Unstirred Water Layers and the Kinetics of Organic Cation Transport (United States)

    Shibayama, Takahiro; Morales, Mark; Zhang, Xiaohong; Martinez, Lucy; Berteloot, Alfred; Secomb, Timothy W.; Wright, Stephen H.


    Purpose Unstirred water layers (UWLs) present an unavoidable complication in the measurement of transport kinetics in cultured cells and the high rates of transport achieved by overexpressing heterologous transporters exacerbate the UWL effect. This study examined the correlation between measured Jmax and Kt values and the effect of manipulating UWL thickness or transport Jmax on the accuracy of experimentally determined kinetics of the multidrug transporters, OCT2 and MATE1. Methods Transport of TEA and MPP was measured in CHO cells that stably expressed human OCT2 or MATE1. UWL thickness was manipulated by vigorous reciprocal shaking. Several methods were used to manipulate maximal transport rates. Results Vigorous stirring stimulated uptake of OCT2-mediated transport by decreasing apparent Kt (Ktapp) values. Systematic reduction in transport rates was correlated with reduction in Ktapp values. The slope of these relationships indicated a 1500 µm UWL in multiwell plates. Reducing the influence of UWLs (by decreasing either their thickness or the Jmax of substrate transport) reduced Ktapp by 2-fold to >10-fold. Conclusions Failure to take into account the presence of UWLs in experiments using cultured cells to measure transport kinetics can result in significant underestimates of the affinity of multidrug transporters for substrates. PMID:25791216

  12. Proton energy determinations in water and in tissue-like material

    Energy Technology Data Exchange (ETDEWEB)

    Laitano, R.F. [Ist. Nazionale di Metrologia delle Radiazioni Ionizzanti, ENEA, Roma (Italy); Rosetti, M. [Div. di Fisica Applicata, ENEA, Bologna (Italy)


    The mean energy of proton beams in water and in a tissue substitute, respectively, were determined as a function of SOBP width, beam size and initial energy spread. Then an analytical expression to obtain the proton mean energy as a function of phantom depth and initial energy was established. This expression differs from the analogous ones reported in some current dosimetry protocols in that it accounts for the nuclear interaction effects in determining the mean energy. The preliminary results of the calculations referred to above are reported together with some comments on the specification of the proton beam quality for clinical dosimetry. (orig.)

  13. A kinetic study on decomposition of proton-bound dimer using data obtained by ion mobility spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Jazan, Elham, E-mail:; Ghazali Khoob, Abdolhosein S.


    Graphical abstract: - Highlights: • The capability of corona discharge-IMS for easy study of kinetic properties was confirmed. • An equation for measuring the rate constant of the proton-bound dimer decomposition reaction was derived. • The effects of temperatures and sample concentration were investigated for monomer–dimer tail. - Abstract: In this study, an equation for measuring the rate constant of the proton-bound dimer decomposition reaction was derived using the data obtained by ion mobility spectrometry (IMS) technique. The ion mobility spectra of cyclohexanone (as the test compound) were obtained at various temperatures and different electric fields. The applied electric field for each temperature was varied between 375 and 500 V cm{sup −1} and the rate constant values of 188.24, 180.54, 280.64, 288.34 and 379.60 s{sup −1} were obtained at different temperatures of 463, 468, 473, 478 and 483 K, respectively. Subsequently, the activation energy and pre-exponential factor were calculated to be 69.5 kJ mol{sup −1} and 1.2 × 10{sup 10} s{sup −1}, respectively. In addition, the standard enthalpy changes were calculated for the dimer decomposition reaction of cyclohexanone at the above-mentioned temperatures.

  14. Size effect of water cluster on the excited-state proton transfer in aqueous solvent (United States)

    Liu, Yu-Hui; Chu, Tian-Shu


    Time-dependent density functional theory (TDDFT) was used to investigate the excited-state proton transfer (ESPT) dynamics of 6-hydroxyquinolinium (6HQc) in aqueous solvent, resulting in the excited zwitterionic form (6HQz). The optimized excited-state energy profiles of 6HQc:(H 2O) n complexes have been calculated along the phenolic O sbnd H bond to simulate the minimum energy pathway (MEP) in the excited state. The results suggested that the threshold of the size of the water cluster is 3 for the excited-state proton transfer of 6HQc in aqueous solvent, since the conformation of the stable hydrated proton requires proton transferring to the second or deeper shell of water solvent. Moreover, the stability of the hydrated proton can be improved significantly by adding one more H 2O molecule to form an Eigen cation in the excited-state 6HQz:H 9O 4+. The effect of the size of water cluster on the proton transfer is investigated theoretically in the excited state for the first time.

  15. Isothermal ice crystallization kinetics in the gas-diffusion layer of a proton-exchange-membrane fuel cell. (United States)

    Dursch, T J; Ciontea, M A; Radke, C J; Weber, A Z


    Nucleation and growth of ice in the fibrous gas-diffusion layer (GDL) of a proton-exchange membrane fuel cell (PEMFC) are investigated using isothermal differential scanning calorimetry (DSC). Isothermal crystallization rates and pseudo-steady-state nucleation rates are obtained as a function of subcooling from heat-flow and induction-time measurements. Kinetics of ice nucleation and growth are studied at two polytetrafluoroethylene (PTFE) loadings (0 and 10 wt %) in a commercial GDL for temperatures between 240 and 273 K. A nonlinear ice-crystallization rate expression is developed using Johnson-Mehl-Avrami-Kolmogorov (JMAK) theory, in which the heat-transfer-limited growth rate is determined from the moving-boundary Stefan problem. Induction times follow a Poisson distribution and increase upon addition of PTFE, indicating that nucleation occurs more slowly on a hydrophobic fiber than on a hydrophilic fiber. The determined nucleation rates and induction times follow expected trends from classical nucleation theory. A validated rate expression is now available for predicting ice-crystallization kinetics in GDLs. © 2011 American Chemical Society

  16. Catalytic role of calix[4]hydroquinone in acetone-water proton exchange: a quantum chemical study of proton transfer via keto-enol tautomerism. (United States)

    Zakharov, M; Masunov, A E; Dreuw, A


    Calix[4]hydroquinone has recently attracted considerable interest since it forms stable tubular aggregates mediated solely by hydrogen bonding and pi-pi-stacking interactions. These aggregates trap specifically various small organic molecules and, in particular, catalyze the proton exchange of water with acetone. Using correlated quantum chemical methods, the mechanism of the observed proton exchange mediated by keto-enol tautomerism of acetone is investigated in detail. Starting with an investigation of keto-enol tautomerism of acetone-water clusters, it appears that four catalytic water molecules are optimal for the catalysis and that additional solvent water molecules lead to a decrease in efficiency. Analyses of the partial charges revealed a decrease of the polarization of the reactive hydrogen bonds due to the additional water molecules. As a next step, hydroquinone-acetone-water complexes were studied as models for the situation in the CHQ moieties. However, the computations revealed that the proton transfer reaction becomes less efficient when one catalytic water molecule is replaced by hydroquinone. Although concerted proton transfer via keto-enol tautomerism of acetone seems to be the predominant mechanism in supercritical water, it is no longer the rate-determining reaction mechanism for the catalyzed acetone-water proton exchange observed in tubular CHQ. Nevertheless, a key feature of the catalytic function of tubular CHQ has been identified to be the stiff hydrogen bonding network and the exclusion of additional solvent water molecules.

  17. Very Tiny Rocks: Site-Specific, Size-Dependent Reaction Kinetics at Nanoparticle-Water Interfaces (United States)

    Rustad, J. R.


    One of the most fundamental challenges in geochemistry is to be able to understand the rates and mechanisms of elementary reactions that describe chemical processes occurring at mineral-water interfaces. One of the reasons for the primitive conceptual state of reaction kinetics in solid earth geochemistry is that it is very difficult to identify defensible elementary reactions where theoretical predictions can be made and the results can tested experimentally at the same length and time scale of the prediction. For example, the most fundamental predictor of complexation kinetics in aqueous solution is the characteristic water exchange rate, which are well known for the aquo ions and vary by 20 orders of magnitude even for simple trivalent ions. In contrast, for interfacial reactions, it was not even known whether water exchange rates were faster or slower than equivalent metal sites in solution, prohibiting any quantitive understanding of mineral reaction kinetics at the molecular level. Recent advances in synthesis and characterization of materials at nanometer length scales has been able to bridge the gap in scale, and nanometer-sized minerals have given us our first quantitative understanding of elementary reaction rates for fundamental processes involving water and hydroxide exchange reactions. I describe the results of molecular dynamics calculation and experimental measurement of the rates of water, hydroxide, and proton exchange reactions on nanoparticle surfaces. The calculations already show that transition state theory is completely inadequate to understand the rates of even the simplest elementary reactions. Furthermore, the mechanistic implications of rate parameters such as activation volume and activation enthalpy may be different in moving from aquo ions to interfaces. Is a molecular understanding of geochemical processes really needed? One might have asked a biologist at the turn of the century whether studying the structure of proteins would ever

  18. Highly Water-Stable Lanthanide-Oxalate MOFs with Remarkable Proton Conductivity and Tunable Luminescence. (United States)

    Zhang, Kun; Xie, Xiaoji; Li, Hongyu; Gao, Jiaxin; Nie, Li; Pan, Yue; Xie, Juan; Tian, Dan; Liu, Wenlong; Fan, Quli; Su, Haiquan; Huang, Ling; Huang, Wei


    Although proton conductors derived from metal-organic frameworks (MOFs) are highly anticipated for various applications including solid-state electrolytes, H2 sensors, and ammonia synthesis, they are facing serious challenges such as poor water stability, fastidious working conditions, and low proton conductivity. Herein, we report two lanthanide-oxalate MOFs that are highly water stable, with so far the highest room-temperature proton conductivity (3.42 × 10-3 S cm-1 ) under 100% relative humidity (RH) among lanthanide-based MOFs and, most importantly, luminescent. Moreover, the simultaneous response of both the proton conductivity and luminescence intensity to RH allows the linkage of proton conductivity with luminescence intensity. This way, the electric signal of proton conductivity variation versus RH will be readily translated to optical signal of luminescence intensity, which can be directly visualized by the naked eye. If proper lanthanide ions or even transition-metal ions are used, the working wavelengths of luminescence emissions can be further extended from visible to near infrared light for even wider-range applications. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. Modeling of Kinetics of Air Entrainment in Water Produced by Vertically Falling Water Flow

    Directory of Open Access Journals (Sweden)



    Full Text Available This study analyzes the process of air entrainment in water caused by vertically falling water flow in the free water surface. The new kinetic model of air entrainment in water was developed. This model includes the process of air entrapment, as well as air removal, water sputtering and resorption. For the experimental part of this study a new method based on digital image processing was developed. Theoretical and experimental methods were used for determining air concentration and its distribution in water below the air-water interface. A new presented mathematical model of air entrainment process allows determining of air bubbles and water droplets concentrations distribution. The obtained theoretical and experimental results were in good agreement. DOI:

  20. Investigation of the kinetics of water uptake into partially saturated shales

    National Research Council Canada - National Science Library

    Roshan, H; Andersen, M. S; Rutlidge, H; Marjo, C. E; Acworth, R. I


    .... This study describes novel hydraulic experiments to quantitatively investigate the kinetics of water uptake into partially saturated shale through investigating the pressure response of injecting fluids...

  1. Hydrolysis kinetics of tulip tree xylan in hot compressed water. (United States)

    Yoon, Junho; Lee, Hun Wook; Sim, Seungjae; Myint, Aye Aye; Park, Hee Jeong; Lee, Youn-Woo


    Lignocellulosic biomass, a promising renewable resource, can be converted into numerous valuable chemicals post enzymatic saccharification. However, the efficacy of enzymatic saccharification of lignocellulosic biomass is low; therefore, pretreatment is necessary to improve the efficiency. Here, a kinetic analysis was carried out on xylan hydrolysis, after hot compressed water pretreatment of the lignocellulosic biomass conducted at 180-220°C for 5-30min, and on subsequent xylooligosaccharide hydrolysis. The weight ratio of fast-reacting xylan to slow-reacting xylan was 5.25 in tulip tree. Our kinetic results were applied to three different reaction systems to improve the pretreatment efficiency. We found that semi-continuous reactor is promising. Lower reaction temperatures and shorter space times in semi-continuous reactor are recommended for improving xylan conversion and xylooligosaccharide yield. In the theoretical calculation, 95% of xylooligosaccharide yield and xylan conversion were achieved simultaneously with high selectivity (desired product/undesired product) of 100 or more. Copyright © 2016. Published by Elsevier Ltd.

  2. A combined INS and DINS study of proton quantum dynamics of ice and water across the triple point and in the supercritical phase (United States)

    Andreani, C.; Romanelli, G.; Senesi, R.


    We report new results of a combined analysis of previous Inelastic Neutron Scattering (INS) and Deep Inelastic Neutron Scattering (DINS) experiments on ice at T = 271 K and water at T = 285 K and T = 673 K. Proton quantum dynamics is discussed in terms of the total mean kinetic energy, , and its three principal direction components, α (with α=x,y,z), the lineshape momentum distribution, n(p), and its harmonic lineshape components, nh(p). The results show that the single proton dynamics is ground-state dominated and that x,y and z consist mainly of weighted averages of a mix of bending and librational, librational and stretching mean kinetic energy components, respectively. The stretching component z is redshifted respect to its harmonic component due to additional network mode contributions and softening caused by anharmonicity. The n(p) lineshapes derived at the investigated temperature reflect the anisotropy and quasi-harmonic nature of proton motion in ice and water.

  3. Atomistic simulation of water percolation and proton hopping in Nafion fuel cell membrane. (United States)

    Devanathan, Ram; Venkatnathan, Arun; Rousseau, Roger; Dupuis, Michel; Frigato, Tomaso; Gu, Wei; Helms, Volkhard


    We have performed a detailed analysis of water clustering and percolation in hydrated Nafion configurations generated by classical molecular dynamics simulations. Our results show that at low hydration levels H(2)O molecules are isolated and a continuous hydrogen-bonded network forms as the hydration level is increased. Our quantitative analysis has established a hydration level (λ) between 5 and 6 H(2)O/SO(3)(-) as the percolation threshold of Nafion. We have also examined the effect of such a network on proton transport by studying the structural diffusion of protons using the quantum hopping molecular dynamics method. The mean residence time of the proton on a water molecule decreases by 2 orders of magnitude when the λ value is increased from 5 to 15. The proton diffusion coefficient in Nafion at a λ value of 15 is about 1.1 × 10(-5) cm(2)/s in agreement with experiment. The results provide quantitative atomic-level evidence of water network percolation in Nafion and its effect on proton conductivity.

  4. Kinetic modeling of water sorption by roasted and ground coffee

    Directory of Open Access Journals (Sweden)

    Fernanda Machado Baptestini


    Full Text Available The objective of this study was to model the kinetics of water sorption in roasted and ground coffee. Crude Arabica coffee beans with an initial moisture content of 0.1234 kgwkgdm-1 were used. These beans were roasted to a medium roast level (SCCA # 55 and ground at three particle sizes: coarse (1.19 mm, medium (0.84 mm and fine (0.59 mm. To obtain the water sorption isotherms and the isosteric heat, different conditions of temperature and relative humidity were analyzed using the dynamic method at 25ºC (0.50, 0.60, 0.70, and 0.80 of RH and 30°C (0.30, 0.40, 0.50, 0.60, 0.70, and 0.80 of RH and using the static method at 25ºC (0.332 and 0.438 of RH. The GAB model best represented the hygroscopic equilibrium of roasted coffee at every particle size. Isosteric heat of sorption for the fine particle size increased with increments of equilibrium moisture content, indicating a strong bond energy between water molecules and the product components. The Gibbs free energy decreased with the increase in equilibrium moisture content and with temperature.

  5. Effects of external electric fields on double proton transfer kinetics in the formic acid dimer. (United States)

    Arabi, Alya A; Matta, Chérif F


    Molecules can be exposed to strong local electric fields of the order of 10(8)-10(10) V m(-1) in the biological milieu. The effects of such fields on the rate constant (k) of a model reaction, the double-proton transfer reaction in the formic acid dimer (FAD), are investigated. The barrier heights and shapes are calculated in the absence and presence of several static homogenous external fields ranging from 5.14 × 10(8) to 5.14 × 10(9) V m(-1) using density functional theory (DFT/B3LYP) and second order Møller-Plesset perturbation theory (MP2) in conjunction with the 6-311++G(d,p) Pople basis set. Conventional transition state theory (CTST) followed by Wigner tunneling correction is then applied to estimate the rate constants at 25 °C. It is found that electric fields parallel to the long axis of the dimer (the line joining the two carbon atoms) lower the uncorrected barrier height, and hence increase the raw k. These fields also flatten the potential energy surface near the transition state region and, hence, decrease the multiplicative tunneling correction factor. The net result of these two opposing effects is that fields increase k(corrected) by a factor of ca. 3-4 (DFT-MP2, respectively) compared to the field-free k. Field strengths of ∼3 × 10(9) V m(-1) are found to be sufficient to double the tunneling-corrected double proton transfer rate constant at 25 °C. Field strengths of similar orders of magnitudes are encountered in the scanning tunneling microscope (STM), in the microenvironment of a DNA base-pair, in an enzyme active site, and in intense laser radiation fields. It is shown that the net (tunneling corrected) effect of the field on k can be closely fitted to an exponential relationship of the form k = aexp(bE), where a and b are constants and E the electric field strength.

  6. A statistical mechanical theory of proton transport kinetics in hydrogen-bonded networks based on population correlation functions with applications to acids and bases. (United States)

    Tuckerman, Mark E; Chandra, Amalendu; Marx, Dominik


    Extraction of relaxation times, lifetimes, and rates associated with the transport of topological charge defects in hydrogen-bonded networks from molecular dynamics simulations is a challenge because proton transfer reactions continually change the identity of the defect core. In this paper, we present a statistical mechanical theory that allows these quantities to be computed in an unbiased manner. The theory employs a set of suitably defined indicator or population functions for locating a defect structure and their associated correlation functions. These functions are then used to develop a chemical master equation framework from which the rates and lifetimes can be determined. Furthermore, we develop an integral equation formalism for connecting various types of population correlation functions and derive an iterative solution to the equation, which is given a graphical interpretation. The chemical master equation framework is applied to the problems of both hydronium and hydroxide transport in bulk water. For each case it is shown that the theory establishes direct links between the defect's dominant solvation structures, the kinetics of charge transfer, and the mechanism of structural diffusion. A detailed analysis is presented for aqueous hydroxide, examining both reorientational time scales and relaxation of the rotational anisotropy, which is correlated with recent experimental results for these quantities. Finally, for OH(-)(aq) it is demonstrated that the "dynamical hypercoordination mechanism" is consistent with available experimental data while other mechanistic proposals are shown to fail. As a means of going beyond the linear rate theory valid from short up to intermediate time scales, a fractional kinetic model is introduced in the Appendix in order to describe the nonexponential long-time behavior of time-correlation functions. Within the mathematical framework of fractional calculus the power law decay ∼t(-σ), where σ is a parameter of the

  7. Water adsorption and proton conduction in metal-organic frameworks: Insights from molecular simulations (United States)

    Paesani, Francesco


    Metal-organic frameworks (MOFs) are a relatively new class of porous materials that hold great potential for a wide range of applications in chemistry, materials science, and nanoengineering. Compared to other porous materials such as zeolites, MOF properties are highly tunable. In particular, it has been shown that both size and shape of the MOF pores can be rationally designed for specific applications. For example, the ability to modify the framework properties with respect to hydrophilicity/hydrophobicity and acidity/basicity can enable the direct control of proton conduction through carrier molecules adsorbed inside the pores. Here, I report on our current efforts aimed at providing a molecular-level characterization of water-mediated proton conduction through the MOF pores. Particular emphasis will be put on correlation between proton conduction and both structural and chemical properties of the frameworks as well as on the dynamical behavior of water confined in the MOF pores. NSF award number: DMR-130510

  8. Proton-conductive nano zeolite-PVA composite film as a new water-absorbing electrolyte for water electrolysis

    Directory of Open Access Journals (Sweden)

    M. Nishihara


    Full Text Available In this study, organic-inorganic composite electrolyte membranes are developed for a novel water-absorbing porous electrolyte water electrolysis cell. As the materials of the composite electrolyte membrane, 80 wt% of a proton-conducting nano zeolite (H-MFI as an electrolyte and 20 wt% of poly(vinyl alcohol (PVA as a cross-linkable matrix are used. The nano zeolite is prepared by a milling process. The nano zeolite-PVA composite membrane precursors are prepared by spraying onto a substrate, followed by cross-linking. The resulting nano zeolite-cross-linked PVA composite films are then evaluated for their properties such as proton conductivity as electrolyte membranes for the water-absorbing porous electrolyte water electrolysis cell. It is confirmed that conventional materials such as zeolites and PVA can be used for the water electrolysis as an electrolyte.

  9. Hydration and translocation of an excess proton in water clusters: An ...

    Indian Academy of Sciences (India)

    The hydration structure and translocation of an excess proton in hydrogen bonded water clusters of two different sizes are investigated by means of finite temperature quantum simulations. The simulations are performed by employing the method of Car–Parrinello molecular dynamics where the forces on the nuclei are ...

  10. Proton affinities in water of maingroup-element Hydrides - Effects of hydration and methyl substitution

    NARCIS (Netherlands)

    Swart, M.; Rosler, E.; Bickelhaupt, F.M.


    We have computed the proton affinities in water of archetypal anionic and neutral bases across the periodic table using the generalized gradient approximation (GGA) of density functional theory (DFT) at BP86/QZ4P//BP86/TZ2P. The main purpose of this work is to provide an intrinsically consistent set

  11. Energetic protons at Mars: interpretation of SLED/Phobos-2 observations by a kinetic model

    Directory of Open Access Journals (Sweden)

    E. Kallio


    Full Text Available Mars has neither a significant global intrinsic magnetic field nor a dense atmosphere. Therefore, solar energetic particles (SEPs from the Sun can penetrate close to the planet (under some circumstances reaching the surface. On 13 March 1989 the SLED instrument aboard the Phobos-2 spacecraft recorded the presence of SEPs near Mars while traversing a circular orbit (at 2.8 RM. In the present study the response of the Martian plasma environment to SEP impingement on 13 March was simulated using a kinetic model. The electric and magnetic fields were derived using a 3-D self-consistent hybrid model (HYB-Mars where ions are modelled as particles while electrons form a massless charge neutralizing fluid. The case study shows that the model successfully reproduced several of the observed features of the in situ observations: (1 a flux enhancement near the inbound bow shock, (2 the formation of a magnetic shadow where the energetic particle flux was decreased relative to its solar wind values, (3 the energy dependency of the flux enhancement near the bow shock and (4 how the size of the magnetic shadow depends on the incident particle energy. Overall, it is demonstrated that the Martian magnetic field environment resulting from the Mars–solar wind interaction significantly modulated the Martian energetic particle environment.

  12. Concerted proton-coupled electron transfers in aquo/hydroxo/oxo metal complexes: Electrochemistry of [OsII(bpy)2py(OH2)]2+ in water


    Costentin, Cyrille; Robert, Marc; Savéant, Jean-Michel; Teillout, Anne-Lucie


    Kinetic analysis of the successive oxidative cyclic voltammetric responses of [OsII(bpy)2py(OH2)]2+ in buffered water, together with determination of H/D isotope effects, has allowed the determination of the mechanisms of the successive proton-coupled electron transfers that convert the OsII-aquo complex into the OsIII-hydroxo complex and the later into the OsIV-oxo complex. The stepwise pathways prevail over the concerted pathway in the first case. However, very large concentrations of a bas...

  13. Antimony doped tin oxides and their composites with tin pyrophosphates as catalyst supports for oxygen evolution reaction in proton exchange membrane water electrolysis

    DEFF Research Database (Denmark)

    Xu, Junyuan; Li, Qingfeng; Hansen, Martin Kalmar


    based on tin pyrophosphates as the catalyst support. The materials showed an overall conductivity of 0.57 S cm−1 at 130 °C under the water vapor atmosphere with a contribution of the proton conduction. Using this composite support, iridium oxide nanoparticle catalysts were prepared and characterized...... in sulfuric and phosphoric acid electrolytes, showing much enhanced catalytic activity. Electrolyzer tests were conducted at both 80 °C with an Aquivion™ membrane and at 130 °C with a phosphoric acid doped Aquivion™ membrane. Significant improvement in the anodic kinetics was achieved on the composite...

  14. Biophysical comparison of ATP-driven proton pumping mechanisms suggests a kinetic advantage for the rotary process depending on coupling ratio


    Anandakrishnan, Ramu; Zuckerman, Daniel M.


    ATP-driven proton pumps, which are critical to the operation of a cell, maintain cytosolic and organellar pH levels within a narrow functional range. These pumps employ two very different mechanisms: an elaborate rotary mechanism used by V-ATPase H+ pumps, and a simpler alternating access mechanism used by P-ATPase H+ pumps. Why are two different mechanisms used to perform the same function? Systematic analysis, without parameter fitting, of kinetic models of the rotary, alternating access an...

  15. Coarse-grained model of nanoscale segregation, water diffusion, and proton transport in Nafion membranes. (United States)

    Vishnyakov, Aleksey; Mao, Runfang; Lee, Ming-Tsung; Neimark, Alexander V


    We present a coarse-grained model of the acid form of Nafion membrane that explicitly includes proton transport. This model is based on a soft-core bead representation of the polymer implemented into the dissipative particle dynamics (DPD) simulation framework. The proton is introduced as a separate charged bead that forms dissociable Morse bonds with water beads. Morse bond formation and breakup artificially mimics the Grotthuss hopping mechanism of proton transport. The proposed DPD model is parameterized to account for the specifics of the conformations and flexibility of the Nafion backbone and sidechains; it treats electrostatic interactions in the smeared charge approximation. The simulation results qualitatively, and in many respects quantitatively, predict the specifics of nanoscale segregation in the hydrated Nafion membrane into hydrophobic and hydrophilic subphases, water diffusion, and proton mobility. As the hydration level increases, the hydrophilic subphase exhibits a percolation transition from a collection of isolated water clusters to a 3D network of pores filled with water embedded in the hydrophobic matrix. The segregated morphology is characterized in terms of the pore size distribution with the average size growing with hydration from ∼1 to ∼4 nm. Comparison of the predicted water diffusivity with the experimental data taken from different sources shows good agreement at high and moderate hydration and substantial deviation at low hydration, around and below the percolation threshold. This discrepancy is attributed to the dynamic percolation effects of formation and rupture of merging bridges between the water clusters, which become progressively important at low hydration, when the coarse-grained model is unable to mimic the fine structure of water network that includes singe molecule bridges. Selected simulations of water diffusion are performed for the alkali metal substituted membrane which demonstrate the effects of the counter

  16. Coarse-grained model of nanoscale segregation, water diffusion, and proton transport in Nafion membranes (United States)

    Vishnyakov, Aleksey; Mao, Runfang; Lee, Ming-Tsung; Neimark, Alexander V.


    We present a coarse-grained model of the acid form of Nafion membrane that explicitly includes proton transport. This model is based on a soft-core bead representation of the polymer implemented into the dissipative particle dynamics (DPD) simulation framework. The proton is introduced as a separate charged bead that forms dissociable Morse bonds with water beads. Morse bond formation and breakup artificially mimics the Grotthuss hopping mechanism of proton transport. The proposed DPD model is parameterized to account for the specifics of the conformations and flexibility of the Nafion backbone and sidechains; it treats electrostatic interactions in the smeared charge approximation. The simulation results qualitatively, and in many respects quantitatively, predict the specifics of nanoscale segregation in the hydrated Nafion membrane into hydrophobic and hydrophilic subphases, water diffusion, and proton mobility. As the hydration level increases, the hydrophilic subphase exhibits a percolation transition from a collection of isolated water clusters to a 3D network of pores filled with water embedded in the hydrophobic matrix. The segregated morphology is characterized in terms of the pore size distribution with the average size growing with hydration from ˜1 to ˜4 nm. Comparison of the predicted water diffusivity with the experimental data taken from different sources shows good agreement at high and moderate hydration and substantial deviation at low hydration, around and below the percolation threshold. This discrepancy is attributed to the dynamic percolation effects of formation and rupture of merging bridges between the water clusters, which become progressively important at low hydration, when the coarse-grained model is unable to mimic the fine structure of water network that includes singe molecule bridges. Selected simulations of water diffusion are performed for the alkali metal substituted membrane which demonstrate the effects of the counter-ions on

  17. Proton magnetic relaxation in aromatic polyamides during water vapor sorption (United States)

    Smotrina, T. V.; Chulkova, Yu. S.; Karasev, D. V.; Lebedeva, N. P.; Perepelkin, K. E.; Grebennikov, S. F.


    The state of the components in the aromatic polyamide-water system was studied by NMR and sorption. A comparative analysis of spin-lattice and spin-spin relaxation in aromatic para-polyamide ( para-aramid) technical fibers Rusar, Kevlar, and Technora was performed depending on the sorption value. The NMR results correlated with the supramolecular structure of polymers and quasi-chemical equation parameters for water vapor sorption.

  18. Parametrized energy spectrum of cosmic-ray protons with kinetic energies down to 1 GeV (United States)

    Tan, L. C.


    A new estimation of the interstellar proton spectrum is made in which the source term of primary protons is taken from shock acceleration theory and the cosmic ray propagation calculation is based on a proposed nonuniform galactic disk model.

  19. Radiation tests of the EMU spacesuit for the International Space Station using energetic protons


    Zeitlin, C.; Heilbronn, L.; Miller, J; Shavers, M.


    Measurements using silicon detectors to characterize the radiation transmitted through the EMU spacesuit and a human phantom have been performed using 155 and 250 MeV proton beams at the Loma Linda University Medical Center (LLUMC). The beams simulate radiation encountered in space, where trapped protons having kinetic energies on the order of 100 MeV are copious. Protons with 100 MeV kinetic energy and above can penetrate many centimeters of water of other light materials, so that astro...

  20. Submillimeter ionoacoustic range determination for protons in water at a clinical synchrocyclotron (United States)

    Lehrack, Sebastian; Assmann, Walter; Bertrand, Damien; Henrotin, Sebastien; Herault, Joel; Heymans, Vincent; Vander Stappen, Francois; Thirolf, Peter G.; Vidal, Marie; Van de Walle, Jarno; Parodi, Katia


    Proton ranges in water between 145 MeV to 227 MeV initial energy have been measured at a clinical superconducting synchrocyclotron using the acoustic signal induced by the ion dose deposition (ionoacoustic effect). Detection of ultrasound waves was performed by a very sensitive hydrophone and signals were stored in a digital oscilloscope triggered by secondary prompt gammas. The ionoacoustic range measurements were compared to existing range data from a calibrated range detector setup on-site and agreement of better than 1 mm was found at a Bragg peak dose of about 10 Gy for 220 MeV initial proton energy, compatible with the experimental errors. Ionoacoustics has thus the potential to measure the Bragg peak position with submillimeter accuracy during proton therapy, possibly correlated with ultrasound tissue imaging.

  1. Dose to water versus dose to medium in proton beam therapy (United States)

    Paganetti, Harald


    Dose in radiation therapy is traditionally reported as the water-equivalent dose, or dose to water. Monte Carlo dose calculations report dose to medium and thus a methodology is needed to convert dose to medium into dose to water (or vice versa) for comparison of Monte Carlo results with results from planning systems. This paper describes the development of a formalism to convert dose to medium into dose to water for proton fields when simulating the dose with Monte Carlo techniques. The conversion is based on relative stopping power but also considers energy transferred via nuclear interactions. The influence of different interaction mechanisms of proton beams (electromagnetic versus nuclear) is demonstrated. Further, an approximate method for converting doses retroactively is presented. Based on the outlined formalism, five proton therapy patients with a total of 33 fields were analyzed. Dose distributions, dose volume histograms and absolute doses to assess the clinical significance of differences between dose to medium and dose to water are presented. We found that the difference between the two dose reporting definitions can be up to 10% for high CT numbers if analyzing the mean dose to the target. The difference is clinically insignificant for soft tissues. For the structures analyzed, the mean dose to water could be converted to dose to medium by applying a correction factor increasing linearly with increasing average CT number in the volume. We determined that an approximate conversion method, done retroactively with an energy-independent stopping power ratio and without considering nuclear interaction events separately (as compared to on-the-fly conversion during simulation), is sufficiently accurate to compute mean doses. It is insufficient, however, when analyzing the beam range. For proton beams stopping in bony anatomy, the predicted beam range can differ by 2-3 mm when comparing dose to tissue and dose to water.

  2. Kinetic and theoretical studies on the protonation of [Ni(2-SC6H4N){PhP(CH2CH2PPh2)2}]+: nitrogen versus sulfur as the protonation site. (United States)

    Petrou, Athinoula L; Koutselos, Andreas D; Wahab, Hilal S; Clegg, William; Harrington, Ross W; Henderson, Richard A


    The complexes [Ni(4-Spy)(triphos)]BPh(4) and [Ni(2-Spy)(triphos)]BPh(4) {triphos = PhP(CH(2)CH(2)PPh(2))(2), 4-Spy = 4-pyridinethiolate, 2-Spy = 2-pyridinethiolate} have been prepared and characterized both spectroscopically and using X-ray crystallography. In both complexes the triphos is a tridentate ligand. However, [Ni(4-Spy)(triphos)](+) comprises a 4-coordinate, square-planar nickel with the 4-Spy ligand bound to the nickel through the sulfur while [Ni(2-Spy)(triphos)](+) contains a 5-coordinate, trigonal-bipyramidal nickel with a bidentate 2-Spy ligand bound to the nickel through both sulfur and nitrogen. The kinetics of the reactions of [Ni(4-Spy)(triphos)](+) and [Ni(2-Spy)(triphos)](+) with lutH(+) (lut = 2,6-dimethylpyridine) in MeCN have been studied using stopped-flow spectrophotometry, and the two complexes show very different reactivities. The reaction of [Ni(4-Spy)(triphos)](+) with lutH(+) is complete within the deadtime of the stopped-flow apparatus (2 ms) and corresponds to protonation of the nitrogen. However, upon mixing [Ni(2-Spy)(triphos)](+) and lutH(+) a reaction is observed (on the seconds time scale) to produce an equilibrium mixture. The mechanistic interpretation of the rate law has been aided by the application of MSINDO semiempirical and ADF calculations. The kinetics and calculations are consistent with the reaction between [Ni(2-Spy)(triphos)](+) and lutH(+) involving initial protonation of the sulfur followed by dissociation of the nitrogen and subsequent transfer of the proton from sulfur to nitrogen. The factors affecting the position of protonation and the coupling of the coordination state of the 2-pyridinethiolate ligand to the site of protonation are discussed.

  3. Polaronic exciton in self-organized assemblies of protonated meso-tetraphenylporphine dimers and water at room temperature (United States)

    Udal'tsov, Alexander V.


    Assemblies consisting of protonated meso-tetraphenylporphine (TPP) dimers and water have been investigated by UV-vis and infrared (IR) spectroscopy and by atomic force microscopy (AFM) in thin layers. Features of electronic absorption spectra of the assemblies are interpreted in terms of hole polaron combined with exciton theory using quantum well with parameters obtained from the dimer structure. It appears to be hole polaron moving defines kinetic energy of polaronic exciton confined in a quantum well when the electron absorbs photon. Hole polaron characteristics such as polaron self-energy, energy of Frank-Condon transitions, and radius of hole polaron moving through water are found to be 1.38 eV, 0.2445 eV, and 0.246 Å, respectively. A doublet at 1944, 1960 cm-1 (0.2412, 0.2432 eV) observed in IR spectra matches the energy of Frank-Condon transitions. Excitation energies estimated using molecular parameters for polaronic excitons in pure water and in the TPP dimers are found in a good agreement with the experimental data.

  4. Molecular dynamics simulations of electrosprayed water nanodroplets: internal potential gradients, location of excess charge centers, and "hopping" protons. (United States)

    Ahadi, Elias; Konermann, Lars


    Water nanodroplets charged with excess protons play a central role during electrospray ionization (ESI). In the current study molecular dynamics (MD) simulations were used for gaining insights into the nanodroplet behavior based on classical mechanics. The SPC/E water model was modified to permit the inclusion of protons as highly mobile point charges at minimum computational cost. A spherical trapping potential was assigned to every SPC/E oxygen, thereby allowing the formation of protonated water molecules. Within a tightly packed nanodroplet the individual potential wells merge to form a three-dimensional energy landscape that facilitates rapid proton hopping between water molecules. This approach requires short-range modifications to the standard Coulomb potential for modeling electrostatic proton-water interactions. Simulations on nanodroplets consisting of 1248 water molecules and 10 protons (radius, ca. 21 A) result in a proton diffusion coefficient that is in agreement with the value measured in bulk solution. Radial proton distributions extracted from 1 ns MD runs exhibit a large peak around 14 A, in addition to substantial population density closer to the droplet center. Similar radial distributions were found for nanodroplets charged with Na+ ions. This behavior is dramatically different from that expected on the basis of continuum electrostatic theory, which predicts that excess charge should be confined to a thin layer on the droplet surface. One important contributor to this effect seems to be the ordering of water molecules at the liquid/vacuum interface. This ordering results in an electrical double layer, generating a potential gradient that tends to pull positive charge carriers (such as protons, but also others such as Na+ ions) toward the droplet interior. This deviation from the widely assumed surface charge paradigm could have implications for the mechanism by which protonated analyte ions are formed during ESI.

  5. Water removal characteristics of proton exchange membrane fuel cells using a dry gas purging method

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Sang-Yeop; Kim, Hyoung-Juhn; Jang, Jong Hyun; Oh, In-Hwan; Cho, Eun Ae; Hong, Seong-Ahn; Lim, Tae-Hoon [Center for Fuel Cell Research, Korea Institute of Science and Technology, 39-1 Hawolgok-dong, Sungbuk-gu, Seoul 136-791 (Korea); Kim, Sang-Uk [Center for Fuel Cell Research, Korea Institute of Science and Technology, 39-1 Hawolgok-dong, Sungbuk-gu, Seoul 136-791 (Korea); Department of Chemical Engineering, Korea University, Anam-dong, Sungbuk-gu, Seoul 136-701 (Korea); Ko, Jaejun; Lim, Tae-Won [Fuel Cell Vehicle Team 1, Hyundai-Kia Corporate Research and Development Division, 104 Mabuk-Dong, Giheung-Gu, Yongin-Si, Gyeonggi-do 446-912 (Korea); Lee, Kwan-Young [Department of Chemical Engineering, Korea University, Anam-dong, Sungbuk-gu, Seoul 136-701 (Korea)


    Water removal from proton exchange membrane fuel cells (PEMFC) is of great importance to improve start-up ability and mitigate cell degradation when the fuel cell operates at subfreezing temperatures. In this study, we report water removal characteristics under various shut down conditions including a dry gas-purging step. In order to estimate the dehydration level of the electrolyte membrane, the high frequency resistance of the fuel cell stack was observed. Also, a novel method for measuring the amount of residual water in the fuel cell was developed to determine the amount of water removal. The method used the phase change of liquid water and was successfully applied to examine the water removal characteristics. Based on these works, the effects of several parameters such as purging time, flow rate of purging gas, operation current, and stack temperature on the amount of residual water were investigated. (author)

  6. Biophysical comparison of ATP-driven proton pumping mechanisms suggests a kinetic advantage for the rotary process depending on coupling ratio. (United States)

    Anandakrishnan, Ramu; Zuckerman, Daniel M


    ATP-driven proton pumps, which are critical to the operation of a cell, maintain cytosolic and organellar pH levels within a narrow functional range. These pumps employ two very different mechanisms: an elaborate rotary mechanism used by V-ATPase H+ pumps, and a simpler alternating access mechanism used by P-ATPase H+ pumps. Why are two different mechanisms used to perform the same function? Systematic analysis, without parameter fitting, of kinetic models of the rotary, alternating access and other possible mechanisms suggest that, when the ratio of protons transported per ATP hydrolyzed exceeds one, the one-at-a-time proton transport by the rotary mechanism is faster than other possible mechanisms across a wide range of driving conditions. When the ratio is one, there is no intrinsic difference in the free energy landscape between mechanisms, and therefore all mechanisms can exhibit the same kinetic performance. To our knowledge all known rotary pumps have an H+:ATP ratio greater than one, and all known alternating access ATP-driven proton pumps have a ratio of one. Our analysis suggests a possible explanation for this apparent relationship between coupling ratio and mechanism. When the conditions under which the pump must operate permit a coupling ratio greater than one, the rotary mechanism may have been selected for its kinetic advantage. On the other hand, when conditions require a coupling ratio of one or less, the alternating access mechanism may have been selected for other possible advantages resulting from its structural and functional simplicity.

  7. The kinetics of chromium(VI) adsorption from water on some natural materials


    Šćiban Marina B.; Klašnja Mile T.


    This paper is concerned with the kinetics of chromium(VI) adsorption by wood sawdust, pulp, and Kraft lignin. In our previous works we determined adsorption efficiency of these adsorbents. In this paper we focused our attention on the influence of contact time on chromium(VI) adsorption from water by the same adsorbents. The analytical data were approached from the following kinetic models: First-order kinetic model, Parabolic diffusion model, Elovich model, and Modified Freundlich model. Elo...

  8. Kinetic description of electron-proton instability in high-intensity proton linacs and storage rings based on the Vlasov-Maxwell equations

    Directory of Open Access Journals (Sweden)

    Ronald C. Davidson


    Full Text Available The present analysis makes use of the Vlasov-Maxwell equations to develop a fully kinetic description of the electrostatic, electron-ion two-stream instability driven by the directed axial motion of a high-intensity ion beam propagating in the z direction with average axial momentum γ_{b}m_{b}β_{b}c through a stationary population of background electrons. The ion beam has characteristic radius r_{b} and is treated as continuous in the z direction, and the applied transverse focusing force on the beam ions is modeled by F_{foc}^{b}=-γ_{b}m_{b}ω_{βb}^{0^{2}}x_{⊥} in the smooth-focusing approximation. Here, ω_{βb}^{0}=const is the effective betatron frequency associated with the applied focusing field, x_{⊥} is the transverse displacement from the beam axis, (γ_{b}-1m_{b}c^{2} is the ion kinetic energy, and V_{b}=β_{b}c is the average axial velocity, where γ_{b}=(1-β_{b}^{2}^{-1/2}. Furthermore, the ion motion in the beam frame is assumed to be nonrelativistic, and the electron motion in the laboratory frame is assumed to be nonrelativistic. The ion charge and number density are denoted by +Z_{b}e and n_{b}, and the electron charge and number density by -e and n_{e}. For Z_{b}n_{b}>n_{e}, the electrons are electrostatically confined in the transverse direction by the space-charge potential φ produced by the excess ion charge. The equilibrium and stability analysis retains the effects of finite radial geometry transverse to the beam propagation direction, including the presence of a perfectly conducting cylindrical wall located at radius r=r_{w}. In addition, the analysis assumes perturbations with long axial wavelength, k_{z}^{2}r_{b}^{2}≪1, and sufficiently high frequency that |ω/k_{z}|≫v_{Tez} and |ω/k_{z}-V_{b}|≫v_{Tbz}, where v_{Tez} and v_{Tbz} are the characteristic axial thermal speeds of the background electrons and beam ions. In this regime, Landau damping (in axial velocity space v_{z} by resonant ions and

  9. A model for the accurate computation of the lateral scattering of protons in water. (United States)

    Bellinzona, E V; Ciocca, M; Embriaco, A; Ferrari, A; Fontana, A; Mairani, A; Parodi, K; Rotondi, A; Sala, P; Tessonnier, T


    A pencil beam model for the calculation of the lateral scattering in water of protons for any therapeutic energy and depth is presented. It is based on the full Molière theory, taking into account the energy loss and the effects of mixtures and compounds. Concerning the electromagnetic part, the model has no free parameters and is in very good agreement with the FLUKA Monte Carlo (MC) code. The effects of the nuclear interactions are parametrized with a two-parameter tail function, adjusted on MC data calculated with FLUKA. The model, after the convolution with the beam and the detector response, is in agreement with recent proton data in water from HIT. The model gives results with the same accuracy of the MC codes based on Molière theory, with a much shorter computing time.

  10. submitter A model for the accurate computation of the lateral scattering of protons in water

    CERN Document Server

    Bellinzona, EV; Embriaco, A; Ferrari, A; Fontana, A; Mairani, A; Parodi, K; Rotondi, A; Sala, P; Tessonnier, T


    A pencil beam model for the calculation of the lateral scattering in water of protons for any therapeutic energy and depth is presented. It is based on the full Molière theory, taking into account the energy loss and the effects of mixtures and compounds. Concerning the electromagnetic part, the model has no free parameters and is in very good agreement with the FLUKA Monte Carlo (MC) code. The effects of the nuclear interactions are parametrized with a two-parameter tail function, adjusted on MC data calculated with FLUKA. The model, after the convolution with the beam and the detector response, is in agreement with recent proton data in water from HIT. The model gives results with the same accuracy of the MC codes based on Molière theory, with a much shorter computing time.

  11. Monovalent counterion distributions at highly charged water interfaces: proton-transfer and Poisson-Boltzmann theory. (United States)

    Bu, Wei; Vaknin, David; Travesset, Alex


    Surface sensitive synchrotron-x-ray scattering studies reveal the distributions of monovalent ions next to highly charged interfaces. A lipid phosphate (dihexadecyl hydrogen phosphate) was spread as a monolayer at the air-water interface, containing CsI at various concentrations. Using anomalous reflectivity off and at the L3 Cs+ resonance, we provide spatial counterion distributions (Cs+) next to the negatively charged interface over a wide range of ionic concentrations. We argue that at low salt concentrations and for pure water the enhanced concentration of hydroniums H3O+ at the interface leads to proton transfer back to the phosphate group by a high contact potential, whereas high salt concentrations lower the contact potential resulting in proton release and increased surface charge density. The experimental ionic distributions are in excellent agreement with a renormalized-surface-charge Poisson-Boltzmann theory without fitting parameters or additional assumptions.

  12. Kinetics of reactions of aquacobalamin with aspartic and glutamic acids and their amides in water solutions (United States)

    Bui, T. T. T.; Sal'nikov, D. S.; Dereven'kov, I. A.; Makarov, S. V.


    The kinetics of aquacobalamin reaction with aspartic and glutamic acids, and with their amides in water solutions, is studied via spectrophotometry. The kinetic and activation parameters of the process are determined. It is shown that the reaction product is cobalamin-amino acid complex. The data are compared to results on the reaction between aquacobalamin and primary amines.



    Mounir Bennajah; Mostafa Maalmi; Yassine Darmane; Mohammed Ebn Touhami


    A variable order kinetic (VOK) model derived from the langmuir-freundlish equation was applied to determine the kinetics of fluoride removal reaction by electrocoagulation (EC). Synthetic solutions were employed to elucidate the effects of the initial fluoride concentration, the applied current and the initial acidity on the simulation results of the model. The proposed model successfully describes the fluoride removal in Airlift reactor in comparison with the experimental results. In this st...

  14. Proton-Transfer-Driven Water Exchange Mechanism in the Na+ Solvation Shell. (United States)

    Hellström, Matti; Behler, Jörg


    Ligand exchange plays an important role for organic and inorganic chemical reactions. We demonstrate the existence of a novel water exchange mechanism, the "proton transfer pathway" (PTP), around Na+(aq) in basic (high pH) solution, using reactive molecular dynamics simulations employing a high-dimensional neural network potential. An aqua ligand in the first solvation (hydration) shell around a sodium ion is only very weakly acidic, but if a hydroxide ion is present in the second solvation shell, thermal fluctuations can cause the aqua ligand to transfer a proton to the neighboring OH-, resulting in a transient direct-contact ion pair, Na+-OH-, which is only weakly bound and easily dissociates. The extent to which water exchange events follow the PTP is pH-dependent: in dilute NaOH(aq) solutions, only very few exchanges occur, whereas in saturated NaOH(aq) solutions up to a third of water self-exchange events are induced by proton transfer. The principles and results outlined here are expected to be relevant for chemical synthesis involving bases and alkali metal cations.

  15. MR-visible water content in human brain: a proton MRS study

    DEFF Research Database (Denmark)

    Christiansen, P; Toft, P B; Gideon, P


    In vivo measurement of metabolite concentrations in the human brain by means of proton-MRS contributes significantly to the clinical evaluation of patients with diseases of the brain. The fully relaxed water signal has been proposed as an internal standard for calibration of the MRS measurements....... and biochemical data published, suggest that only a small fraction (water may be MR-invisible.(ABSTRACT TRUNCATED AT 250 WORDS)......In vivo measurement of metabolite concentrations in the human brain by means of proton-MRS contributes significantly to the clinical evaluation of patients with diseases of the brain. The fully relaxed water signal has been proposed as an internal standard for calibration of the MRS measurements....... The major drawbacks are the necessity to make the assumptions that the water concentrations in the brain and that all tissue water is MR-visible. A number of in vivo measurements were carried out to estimate the concentration of MR-visible water in the brain of healthy volunteers divided into four age...

  16. Quantification of the types of water in Eudragit RLPO polymer and the kinetics of water loss using FTIR

    DEFF Research Database (Denmark)

    Pirayavaraporn, Chompak; Rades, Thomas; Gordon, Keith C


    . Using a curve fitting procedure, the water region (3100-3,700 cm(-1)) of the spectra was analyzed, and used to identify water present in differing environments in the polymer and to determine the water loss kinetics upon purging the sample with dry compressed air. It was found that four environments can...

  17. Analyzing the Molecular Kinetics of Water Spreading on Hydrophobic Surfaces via Molecular Dynamics Simulation

    National Research Council Canada - National Science Library

    Lei Zhao; Jiangtao Cheng


    (ProQuest: ... denotes formulae and/or non-USASCII text omitted; see image) In this paper, we report molecular kinetic analyses of water spreading on hydrophobic surfaces via molecular dynamics simulation...

  18. Separation kinetics of an oil-in-water emulsion under enhanced gravity

    NARCIS (Netherlands)

    Krebs, T.; Schroën, C.G.P.H.; Boom, R.M.


    The breakup of crude oil emulsions to produce clean oil and water phases is an important task in crude oil processing. We have investigated the demulsification kinetics of a model oil-in-water emulsion in a centrifugal field to mimic the forces acting on emulsion droplets in oil/water separators

  19. Parity Nonconservation in Proton-water Scattering at 800 MeV (United States)

    Nagle, D. E.; Bowman, J. D.; Carlini, R.; Mischke, R. E.; Frauenfelder, H.; Harper, R. W.; Yuan, V.; McDonald, A. B.; Talaga, R.


    A search has been made for parity nonconservation in the scattering of 800 MeV polarized protons from an unpolarized water target. The result is for the longitudinal asymmetry, A{sub L} = +(6.6 +- 3.2) x 10{sup -7}. Control runs with Pb, using a thickness which gave equivalent beam broadening from Coulomb multiple scattering, but a factor of ten less nuclear interactions than the water target, gave A{sub L} = -(0.5 +- 6.0) x 10{sup -7}.

  20. Perspectives for sensitivity enhancement in proton-detected solid-state NMR of highly deuterated proteins by preserving water magnetization

    Energy Technology Data Exchange (ETDEWEB)

    Chevelkov, Veniamin, E-mail:; Xiang, ShengQi; Giller, Karin; Becker, Stefan; Lange, Adam [Max-Planck-Institut für biophysikalische Chemie (MPI-bpc) (Germany); Reif, Bernd [Technische Universität München (TUM), Munich Center for Integrated Protein Science (CIPS-M), Department Chemie (Germany)


    In this work, we show how the water flip-back approach that is widely employed in solution-state NMR can be adapted to proton-detected MAS solid-state NMR of highly deuterated proteins. The scheme allows to enhance the sensitivity of the experiment by decreasing the recovery time of the proton longitudinal magnetization. The method relies on polarization transfer from non-saturated water to the protein during the inter-scan delay.

  1. Ab Initio Studies on the Preferred Site of Protonation in Cytisine in the Gas Phase and Water

    Directory of Open Access Journals (Sweden)

    Małgorzata Darowska


    Full Text Available Abstract: Ab initio calculations (HF, MP2, DFT for isolated and PCM for solvated molecules were performed for cytisine (1 and its model compounds: N-methyl-2-pyridone (2 and piperidine (3. Among three heteroatomic functions (carbonyl oxygen, pyridone and piperidine nitrogens considered as the possible sites of protonation in 1, surprisingly the carbonyl oxygen takes preferentially the proton in the gas phase whereas in water the piperidine nitrogen is firstly protonated. For model compounds, the piperidine nitrogen in 3 is more basic than the carbonyl oxygen in 2 in both, the gas phase and water.

  2. kinetics

    Directory of Open Access Journals (Sweden)

    D. E. Panayotounakos


    Full Text Available We present the construction of the general solutions concerning the one-dimensional (1D fully dynamic nonlinear partial differential equations (PDEs, for the erosion kinetics. After an uncoupling procedure of the above mentioned equations a second–order nonlinear PDE of the Monge type governing the porosity is derived, the general solution of which is constructed in the sense that a full complement of arbitrary functions (as many as the order is introduced. Afterwards, we specify the above solution according to convenient initial conditions.

  3. Microbial Species Diversity, Community Dynamics, and Metabolite Kinetics of Water Kefir Fermentation


    Laureys, David; De Vuyst, Luc


    Water kefir is a sour, alcoholic, and fruity fermented beverage of which the fermentation is started with water kefir grains. These water kefir grains consist of polysaccharide and contain the microorganisms responsible for the water kefir fermentation. In this work, a water kefir fermentation process was followed as a function of time during 192 h to unravel the community dynamics, the species diversity, and the kinetics of substrate consumption and metabolite production. The majority of the...

  4. Potential of mean force of water-proton bath and molecular dynamic simulation of proteins at constant pH. (United States)

    Vorobjev, Yury N


    An advanced implicit solvent model of water-proton bath for protein simulations at constant pH is presented. The implicit water-proton bath model approximates the potential of mean force of a protein in water solvent in a presence of hydrogen ions. Accurate and fast computational implementation of the implicit water-proton bath model is developed using the continuum electrostatic Poisson equation model for calculation of ionization equilibrium and the corrected MSR6 generalized Born model for calculation of the electrostatic atom-atom interactions and forces. Molecular dynamics (MD) method for protein simulation in the potential of mean force of water-proton bath is developed and tested on three proteins. The model allows to run MD simulations of proteins at constant pH, to calculate pH-dependent properties and free energies of protein conformations. The obtained results indicate that the developed implicit model of water-proton bath provides an efficient way to study thermodynamics of biomolecular systems as a function of pH, pH-dependent ionization-conformation coupling, and proton transfer events. Copyright © 2012 Wiley Periodicals, Inc.

  5. Modeling proton and alpha elastic scattering in liquid water in Geant4-DNA

    Energy Technology Data Exchange (ETDEWEB)

    Tran, H.N., E-mail: [Division of Nuclear Physics, Ton Duc Thang University, Tan Phong Ward, District 7, Ho Chi Minh City (Viet Nam); Faculty of Applied Sciences, Ton Duc Thang University, Tan Phong Ward, District 7, Ho Chi Minh City (Viet Nam); El Bitar, Z. [Institut Pluridisciplinaire Hubert Curien/IN2P3/CNRS, Strasbourg (France); Champion, C. [Univ. Bordeaux, CENBG, UMR 5797, F-33170 Gradignan (France); CNRS, IN2P3, CENBG, UMR 5797, F-33170 Gradignan (France); Karamitros, M. [Univ. Bordeaux, CENBG, UMR 5797, F-33170 Gradignan (France); CNRS, IN2P3, CENBG, UMR 5797, F-33170 Gradignan (France); CNRS, INCIA, UMR 5287, F-33400 Talence (France); Bernal, M.A. [Instituto de FísicaGleb Wataghin, Universida de Estadual de Campinas, SP (Brazil); Francis, Z. [Université Saint Joseph, Faculty of Science, Department of Physics, Beirut (Lebanon); The Open University, Faculty of Science, Department of Physical Sciences, Walton Hall, MK7 6AA Milton Keynes (United Kingdom); Ivantchenko, V. [Ecoanalytica, 119899 Moscow (Russian Federation); Lee, S.B.; Shin, J.I. [Proton Therapy Center, National Cancer Center, 323 Ilsan-ro, Ilsandong-gu, Goyang-si, Gyeonggi-do 410-769 (Korea, Republic of); Incerti, S. [Univ. Bordeaux, CENBG, UMR 5797, F-33170 Gradignan (France); CNRS, IN2P3, CENBG, UMR 5797, F-33170 Gradignan (France)


    Elastic scattering of protons and alpha (α) particles by water molecules cannot be neglected at low incident energies. However, this physical process is currently not available in the “Geant4-DNA” extension of the Geant4 Monte Carlo simulation toolkit. In this work, we report on theoretical differential and integral cross sections of the elastic scattering process for 100 eV–1 MeV incident protons and for 100 eV–10 MeV incident α particles in liquid water. The calculations are performed within the classical framework described by Everhart et al., Ziegler et al. and by the ICRU 49 Report. Then, we propose an implementation of the corresponding classes into the Geant4-DNA toolkit for modeling the elastic scattering of protons and α particles. Stopping powers as well as ranges are also reported. Then, it clearly appears that the account of the elastic scattering process in the slowing-down of the charged particle improves the agreement with the existing data in particular with the ICRU recommendations.

  6. Silicon hydride nanocrystals as catalysts for proton production in water-organic liquid mixtures

    KAUST Repository

    Chaieb, Sahraoui


    Embodiments of the present methods may be used to produce energy in the form of an electrical current from water without the use of fossil fuel. Silicon hydride is very easy to make. This procedure in conjunction with an enzyme to produce hydrogen gas for fuel cells and other small devices. In fuel cells the production of protons may be bypassed, and an oxidant such as permanganate or oxygen from air may be used to drive the fuel cells. In such an embodiment, an intermediate reaction may not be needed to produce protons. In one embodiment, membrane-less laminar flow fuel cells with an external grid for oxygen supply from the air may be used.

  7. Is there a change in water proton density associated with functional magnetic resonance imaging? (United States)

    Jochimsen, Thies H; Norris, David G; Möller, Harald E


    In a recent series of studies (see, for example, Stroman et al. Magn Reson Imag 2001; 19:827-831), an increase of water proton density has been suggested to correlate with neuronal activity. Owing to the significant implications of such a mechanism for other functional experiments, the functional signal changes in humans at very short echo times were re-examined by spin-echo EPI at 3 T. The results do not confirm the previous hypothesis of a significant increase in extravascular proton density at TE = 0. Instead, an alternative explanation of the effect is offered: The use of a low threshold to identify activated voxels may generate an artificial offset in functional contrast due to the inclusion of false-positives in the analysis.

  8. The kinetics of crossflow dynamic membrane bioreactor | Li | Water SA

    African Journals Online (AJOL)

    Crossflow dynamic membrane bioreactor (CDMBR) kinetics was investigated by treating caprolactam wastewater over a period of 180 d. The removal efficiencies of organic substances and nitrogen averaged over 99% and 80%, respectively. The observed sludge yield was only 0.14 g SS·g-1 COD·d-1 at an SRT of 30 d ...

  9. Drying kinetics of pre-osmosed fresh water frog ( Dicroglossus ...

    African Journals Online (AJOL)

    The drying kinetics of frog (Dicroglossus occipitalis) was conducted using convective oven dryer. The results were fitted into three thin-layer models; Lewis, Henderson and Page models. The constants and coefficients of the various models used were evaluated using non-linear regression methods, and the results show that ...

  10. Kinetics of aluminum-fulvic acid complexation in acidic waters

    Energy Technology Data Exchange (ETDEWEB)

    Plankey, B.J.; Patterson, H.H.


    A fluorescence technique has been used to study the complex formation kinetics of aluminum with a single metal-free fulvic acid isolated from an Adirondack Mountain forest soil. In the pH range of 3.0-4.5, two kinetically distinguishable components of the fulvic acid mixture have been identified, which define two types of average aluminum binding sites. Both fulvic acid average sites conform to a bidentate chelating binding site kinetic analysis, from which rate and equilibrium parameters have been obtained. From comparison of rate and equilibrium constants of aluminum-salicyclic acid complexation, the authors conclude that the faster reacting component of fulvic acid probably contains salicyclic acid type aluminum binding sites. Results are also compared with those of an aluminum-fluoride kinetic study. Fulvic acid and fluoride react with aluminum by the same mechanism and therefore have the same pH dependence. The dependence of the rate on temperature is, however, quite different for the two reactions. The environmental implications of these findings are discussed. 45 references, 5 figures, 6 tables.

  11. Proton exchange membrane fuel cells

    CERN Document Server

    Qi, Zhigang


    Preface Proton Exchange Membrane Fuel CellsFuel CellsTypes of Fuel CellsAdvantages of Fuel CellsProton Exchange Membrane Fuel CellsMembraneCatalystCatalyst LayerGas Diffusion MediumMicroporous LayerMembrane Electrode AssemblyPlateSingle CellStackSystemCell Voltage Monitoring Module (CVM)Fuel Supply Module (FSM)Air Supply Module (ASM)Exhaust Management Module (EMM)Heat Management Module (HMM)Water Management Module (WMM)Internal Power Supply Module (IPM)Power Conditioning Module (PCM)Communications Module (COM)Controls Module (CM)SummaryThermodynamics and KineticsTheoretical EfficiencyVoltagePo

  12. Excited state proton transfer in 9-aminoacridine carboxamides in water and in DNA

    Energy Technology Data Exchange (ETDEWEB)

    Smith, Charles A. [Iowa State Univ., Ames, IA (United States)


    The 9-aminoacridine molecule is important in several different fields of chemistry. The absorption and fluorescence spectra of this compound are pH sensitive and it is this property that allowed it to be used as a pH probe in different chemical environments. The compound exhibits proton transfer reactions which are among the most fundamental of chemical reactions. The planarity of 9-aminoacridine allows it to intercalate into DNA. Intercalation is a process in which the aromatic flat surface of the intercalator inserts between adjacent base pairs of DNA. The large surface area of 9-aminoacridine`s fused tricyclic ring system allows strong intercalative binding through van der Waals attractions. 9-aminoacridine and many of its derivatives have been tried as possible antitumor drugs. The cytotoxicity of an antitumor agent can be dramatically increased through the addition of one or two cationic side chains. This increase in cytotoxicity using the 9-aminoacridine compound as a parent molecule has been investigated through various derivatives with cationic side chains consisting of different number of carbon atoms between the proximal and distal N atoms. Similar derivatives varied the position of the carboxamide side chain on the aromatic ring system. The objective of this work is to first create a baseline study of the excited state kinetics of the 9-aminoacridine carboxamides in the absence of DNA. The baseline study will allow the excited state kinetics of these antitumor drugs when placed in DNA to be more fully understood.

  13. Kinetically driven switching and memory phenomena at the interface between a proton-conductive electrolyte and a titanium electrode (United States)

    Hibino, Takashi; Kobayashi, Kazuyo; Nagao, Masahiro


    Numerous studies have examined the switching properties of semi- or ion-conductors and isolators; however, most of these have focused on the ohmic resistance characteristics. Here, we report a new type of polarity-dependent switching phenomenon obtained for electrical devices with the configuration: metal working electrode│Si0.97Al0.03H0.03P2O7-polytetrafluoroethylene composite electrolyte│Pt/C counter electrode. The counter electrode is reversibly active for the water vapor oxidation and evolution reactions. The composite electrolyte exhibits high withstanding voltage capability in the bias voltage range of ±7 V. When titanium was employed as the working electrode, the anodic polarization resistance was approximately two orders of magnitude greater than the cathodic polarization resistance. The ohmic resistance of the device was almost unchanged, regardless of the bias voltage polarity. Moreover, kinetically induced high-resistance/low-resistance states could be cyclically switched through positive/negative bias voltage pulses, and these states were also confirmed to be memorized at open circuit.


    Directory of Open Access Journals (Sweden)

    Mounir Bennajah


    Full Text Available A variable order kinetic (VOK model derived from the langmuir-freundlish equation was applied to determine the kinetics of fluoride removal reaction by electrocoagulation (EC. Synthetic solutions were employed to elucidate the effects of the initial fluoride concentration, the applied current and the initial acidity on the simulation results of the model. The proposed model successfully describes the fluoride removal in Airlift reactor in comparison with the experimental results. In this study two EC cells with the same capacity (V = 20 L were used to carry out fluoride removal with aluminum electrodes, the first is a stirred tank reactor (STR the second is an airlift reactor (ALR. The comparison of energy consumption demonstrates that the (ALR is advantageous for carrying out the defluoridation removal process.


    Directory of Open Access Journals (Sweden)

    Bennajah Mounir


    Full Text Available A variable order kinetic (VOK model derived from the langmuir-freundlish equation was applied to determine the kinetics of fluoride removal reaction by electrocoagulation (EC. Synthetic solutions were employed to elucidate the effects of the initial fluoride concentration, the applied current and the initial acidity on the simulation results of the model. The proposed model successfully describes the fluoride removal in Airlift reactor in comparison with the experimental results. In this study two EC cells with the same capacity (V = 20 L were used to carry out fluoride removal with aluminum electrodes, the first is a stirred tank reactor (STR the second is an airlift reactor (ALR. The comparison of energy consumption demonstrates that the (ALR is advantageous for carrying out the defluoridation removal process.

  16. Kinematic reconstruction of atmospheric neutrino events in a large water Cherenkov detector with proton identification

    CERN Document Server

    Fechner, M


    We report the development of a proton identification method for the Super-Kamiokande detector. This new tool is applied to the search for events with a single proton track, a high purity neutral current sample of interest for sterile neutrino searches. After selection using a neural network, we observe 38 events in the combined SK-I and SK-II data corresponding to 2285.1 days of exposure, with an estimated signal to background ratio of 1.6 to 1. Proton identification was also applied to a direct search for charged-current quasi-elastic (CCQE) events, obtaining a high precision sample of fully kinematically reconstructed atmospheric neutrinos, which has not been previously reported in water Cherenkov detectors. The CCQE fraction of this sample is 55%, and its neutrino (as opposed to anti-neutrino) fraction is 91.7+/-3%. We selected 78 mu-like and 47 e-like events in the SK-I and SK-II data set. With this data, a clear zenith angle distortion of the neutrino direction itself is reported in a sub-GeV sample of m...

  17. Water equivalent thickness values of materials used in beams of protons, helium, carbon and iron ions (United States)

    Zhang, Rui; Taddei, Phillip J; Fitzek, Markus M; Newhauser, Wayne D


    Heavy charged particle beam radiotherapy for cancer is of increasing interest because it delivers a highly conformal radiation dose to the target volume. Accurate knowledge of the range of a heavy charged particle beam after it penetrates a patient’s body or other materials in the beam line is very important and is usually stated in terms of the water equivalent thickness (WET). However, methods of calculating WET for heavy charged particle beams are lacking. Our objective was to test several simple analytical formulas previously developed for proton beams for their ability to calculate WET values for materials exposed to beams of protons, helium, carbon and iron ions. Experimentally measured heavy charged particle beam ranges and WET values from an iterative numerical method were compared with the WET values calculated by the analytical formulas. Inmost cases, the deviations were within 1 mm. We conclude that the analytical formulas originally developed for proton beams can also be used to calculate WET values for helium, carbon and iron ion beams with good accuracy. PMID:20371908

  18. Lateral spread of dose distribution by therapeutic proton beams in liquid water

    Energy Technology Data Exchange (ETDEWEB)

    Abril, Isabel, E-mail: [Departament de Física Aplicada, Universitat d’Alacant, E-03080 Alacant (Spain); Vera, Pablo de [Departament de Física Aplicada, Universitat d’Alacant, E-03080 Alacant (Spain); Garcia-Molina, Rafael [Departamento de Física – Centro de Investigación en Óptica y Nanofísica, Regional Campus of International Excellence “Campus Mare Nostrum”, Universidad de Murcia, E-30100 Murcia (Spain); Kyriakou, Ioanna; Emfietzoglou, Dimitris [Medical Physics Laboratory, University of Ioannina Medical School, GR-45110 Ioannina (Greece)


    We have calculated the lateral spread of the dose distribution of protons in liquid water by means of the SEICS (Simulation of Energetic Ions and Clusters through Solids) code, which properly accounts for the electronic stopping force (including energy-loss straggling), multiple elastic scattering with the target nuclei, dynamical electron charge-exchange processes and nuclear fragmentation reactions between the projectile and the nuclei of the target. Due to the multiple elastic scattering processes part of the proton energy may be deposited at a given lateral distance from the initial beam direction, which is quantified by the root mean square radius (r{sub rms}). We find in our simulations that the r{sub rms} follows a parabolic dependence as a function of the depth in the target and the quotient between the r{sub rms} at the Bragg peak and the depth of the Bragg peak is around 3% independently of the proton energy. A rather good agreement is obtained when comparing our results of r{sub rms} with experimental data and with other models.

  19. Water equivalent thickness values of materials used in beams of protons, helium, carbon and iron ions. (United States)

    Zhang, Rui; Taddei, Phillip J; Fitzek, Markus M; Newhauser, Wayne D


    Heavy charged particle beam radiotherapy for cancer is of increasing interest because it delivers a highly conformal radiation dose to the target volume. Accurate knowledge of the range of a heavy charged particle beam after it penetrates a patient's body or other materials in the beam line is very important and is usually stated in terms of the water equivalent thickness (WET). However, methods of calculating WET for heavy charged particle beams are lacking. Our objective was to test several simple analytical formulas previously developed for proton beams for their ability to calculate WET values for materials exposed to beams of protons, helium, carbon and iron ions. Experimentally measured heavy charged particle beam ranges and WET values from an iterative numerical method were compared with the WET values calculated by the analytical formulas. In most cases, the deviations were within 1 mm. We conclude that the analytical formulas originally developed for proton beams can also be used to calculate WET values for helium, carbon and iron ion beams with good accuracy.

  20. Protonation of a hydroxide anion bridging two divalent magnesium cations in water probed by first-principles metadynamics simulation. (United States)

    Park, Jung Mee; Boero, Mauro


    The protonation of a hydroxide anion (OH(-)) located between two magnesium cations (Mg(2+)) in aqueous solution has been investigated by first-principles metadynamics simulation. We observe that the complex Mg(2+)-OH(-)-Mg(2+) is stabilized by the coparticipation of the hydroxide anion to the first hydration shells of both the Mg(2+) cations. Contrary to the cases of OH(-) in pure water, the transfer of protons in the presence of the divalent metal ions turns out to be a slow chemical event. This can be ascribed to the decreased proton affinity of the bridging OH(-). Metadynamics simulation, used to overcome the difficulty of the long time scale required by the protonation of the bridging OH(-), has shown that the system possesses a great stability on the reactant state, characterized by a bioctahedral (6,6) solvation structure around the two Mg(2+) cations. The exploration of the free energy landscape shows that this stable bioctahedral configuration converts into a lower coordinated (5,6) structure, leading to a proton transfer from a water molecule belonging to the first solvation shell of the Mg(2+) ion having the lower coordination to the bridging OH(-); the free energy barrier for the protonation reaction is 11 kcal/mol, meaning that the bridging hydroxide is a weak base. During the proton transfer, the bridging OH(-) reverts to an H(2)O molecule, and this breaks the electrostatic coupling of the two Mg(2+) ions, which depart independently with their own hydration shells, one of which is entirely formed by water molecules. The second one carries the newly created OH(-). Our results show that the flexibility in the metal coordination plays a crucial role in both the protonation process of the bridging OH(-) and the separation of the metal cations, providing useful insight into the nature of proton transfer in binuclear divalent metal ions, with several biological implications, such as, for instance, transesterification of catalytic RNA.

  1. Proton-Transfer Mechanisms at the Water-ZnO Interface: The Role of Presolvation. (United States)

    Quaranta, Vanessa; Hellström, Matti; Behler, Jörg


    The dissociation of water is an important step in many chemical processes at solid surfaces. In particular, water often spontaneously dissociates near metal oxide surfaces, resulting in a mixture of H2O, H+, and OH- at the interface. Ubiquitous proton-transfer (PT) reactions cause these species to dynamically interconvert, but the underlying mechanisms are poorly understood. Here, we develop and use a reactive high-dimensional neural-network potential based on density functional theory data to elucidate the structural and dynamical properties of the interfacial species at the liquid-water-metal-oxide interface, using the nonpolar ZnO(101̅0) surface as a prototypical case. Molecular dynamics simulations reveal that water dissociation and recombination proceed via two types of PT reactions: (i) to and from surface oxide and hydroxide anions ("surface-PT") and (ii) to and from neighboring adsorbed hydroxide ions and water molecules ("adlayer-PT"). We find that the adlayer-PT rate is significantly higher than the surface-PT rate. Water dissociation is, for both types of PT, governed by a predominant presolvation mechanism, i.e., thermal fluctuations that cause the adsorbed water molecules to occasionally accept a hydrogen bond, resulting in a decreased PT barrier and an increased dissociation rate as compared to when no hydrogen bond is present. Consequently, we are able to show that hydrogen bond fluctuations govern PT events at the water-metal-oxide interface in a way similar to that in acidic and basic aqueous bulk solutions.

  2. Proton conducting membranes for high temperature fuel cells with solid state water free membranes (United States)

    Narayanan, Sekharipuram R. (Inventor); Yen, Shiao-Pin S. (Inventor)


    A water free, proton conducting membrane for use in a fuel cell is fabricated as a highly conducting sheet of converted solid state organic amine salt, such as converted acid salt of triethylenediamine with two quaternized tertiary nitrogen atoms, combined with a nanoparticulate oxide and a stable binder combined with the converted solid state organic amine salt to form a polymeric electrolyte membrane. In one embodiment the membrane is derived from triethylenediamine sulfate, hydrogen phosphate or trifiate, an oxoanion with at least one ionizable hydrogen, organic tertiary amine bisulfate, polymeric quaternized amine bisulfate or phosphate, or polymeric organic compounds with quaternizable nitrogen combined with Nafion to form an intimate network with ionic interactions.

  3. Dissolution kinetics of volatile organic compound vapors in water : An integrated experimental and computational study

    NARCIS (Netherlands)

    G. Mahmoodlu, Mojtaba; Pontedeiro, Elizabeth M.; Pérez Guerrero, Jesús S.; Raoof, Amir; Hassanizadeh, S. Majid; van Genuchten, Martinus Th

    In this study we performed batch experiments to investigate the dissolution kinetics of trichloroethylene (TCE) and toluene vapors in water at room temperature and atmospheric pressure. The batch systems consisted of a water reservoir and a connected headspace, the latter containing a small glass


    Directory of Open Access Journals (Sweden)

    Gheorghe Duca


    Full Text Available The current paper contains a synthesis of the processes of chemical auto-purification that take place in natural waters; examples of mechanisms of such processes occurring with participation of dissolved organic matter, oxidants of the biogeochemical cycle of oxygen and of transition metals including copper and iron are presented. The kinetic indicators of natural water quality are presented as well.

  5. The kinetics of chromium(VI adsorption from water on some natural materials

    Directory of Open Access Journals (Sweden)

    Šćiban Marina B.


    Full Text Available This paper is concerned with the kinetics of chromium(VI adsorption by wood sawdust, pulp, and Kraft lignin. In our previous works we determined adsorption efficiency of these adsorbents. In this paper we focused our attention on the influence of contact time on chromium(VI adsorption from water by the same adsorbents. The analytical data were approached from the following kinetic models: First-order kinetic model, Parabolic diffusion model, Elovich model, and Modified Freundlich model. Elovich model was shown to be the best fit for the description of chromium(VI adsorption. It was found that adsorption was the fastest on pulp and slowest on Kraft lignin.

  6. Water oxidation by amorphous cobalt-based oxides: volume activity and proton transfer to electrolyte bases. (United States)

    Klingan, Katharina; Ringleb, Franziska; Zaharieva, Ivelina; Heidkamp, Jonathan; Chernev, Petko; Gonzalez-Flores, Diego; Risch, Marcel; Fischer, Anna; Dau, Holger


    Water oxidation in the neutral pH regime catalyzed by amorphous transition-metal oxides is of high interest in energy science. Crucial determinants of electrocatalytic activity were investigated for a cobalt-based oxide film electrodeposited at various thicknesses on inert electrodes. For water oxidation at low current densities, the turnover frequency (TOF) per cobalt ion of the bulk material stayed fully constant for variation of the thickness of the oxide film by a factor of 100 (from about 15 nm to 1.5 μm). Thickness variation changed neither the nanostructure of the outer film surface nor the atomic structure of the oxide catalyst significantly. These findings imply catalytic activity of the bulk hydrated oxide material. Nonclassical dependence on pH was observed. For buffered electrolytes with pKa values of the buffer base ranging from 4.7 (acetate) to 10.3 (hydrogen carbonate), the catalytic activity reflected the protonation state of the buffer base in the electrolyte solution directly and not the intrinsic catalytic properties of the oxide itself. It is proposed that catalysis of water oxidation occurs within the bulk hydrated oxide film at the margins of cobalt oxide fragments of molecular dimensions. At high current densities, the availability of a proton-accepting base at the catalyst-electrolyte interface controls the rate of water oxidation. The reported findings may be of general relevance for water oxidation catalyzed at moderate pH by amorphous transition-metal oxides. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Fundamental kinetics and mechanistic pathways for oxidation reactions in supercritical water (United States)

    Webley, Paul A.; Tester, Jefferson W.


    Oxidation of the products of human metabolism in supercritical water has been shown to be an efficient way to accomplish the on-board water/waste recycling in future long-term space flights. Studies of the oxidation kinetics of methane to carbon dioxide in supercritical water are presented in this paper in order to enhance the fundamental understanding of the oxidation of human waste compounds in supercritical water. It is concluded that, although the elementary reaction models remain the best hope for simulating oxidation in supercritical water, several modifications to existing mechanisms need to be made to account for the role of water in the reaction mechanism.

  8. On the Experimental Investigation of the Clamping Pressure Effects on the Proton Exchange Membrane Water Electrolyser Cell Performance

    DEFF Research Database (Denmark)

    Al Shakhshir, Saher; Frensch, Steffen Henrik; Kær, Søren Knudsen


    energy sources. The proton exchange membrane water electrolyser(PEMWE) is the most candidate technology to produce hydrogen from renewable energysources. PEMWE cell splits water into hydrogen and oxygen when an electric current is passedthrough it. Electrical current forces the positively charged ions...

  9. A study on the kinetics of ozone decomposition in waters of different quality

    Directory of Open Access Journals (Sweden)

    Takić Ljiljana M.


    Full Text Available The kinetics of ozone decomposition in waters of different quality, namely distilled water, tap water previously treated with ozone, tap water not treated with ozone and raw water from an accumulation lake, were studied in a batch stirred reactor at different temperatures (18-28°C. The dissolved ozone concentration was measured by the iodometric titration method. It was determined that an empirical kinetic equation of the form: dc(O3/dt= k0 + k1c(O3 fitted the experimental data better than a first-order reaction rate equation. The apparent reaction rate constants in the case of ozone decomposition in distilled water were shown to be a function of temperature in accordance with the Arrhenius equation.

  10. Kinetic model for predicting the concentrations of active halogen species in chlorinated saline cooling waters

    Energy Technology Data Exchange (ETDEWEB)

    Lietzke, M. H.; Haag, W. R.


    A kinetic model for predicting the composition of chlorinated water discharged from power plants using fresh water for cooling was previously reported. The model has now been extended to be applicable to power plants located on estuaries or on the seacoast where saline water is used for cooling purposes. When chloride is added to seawater to prevent biofouling in cooling systems, bromine is liberated. Since this reaction proceeds at a finite rate there is a competition between the bromine (i.e., hypobromous acid) and the added chlorine (i.e., hypochlorous acid) for halogenation of any amine species present in the water. Hence not only chloramines but also bromamines and bromochloramines will be formed, with the relative concentrations a function of the pH, temperature, and salinity of the water. The kinetic model takes into account the chemical reactions leading to the formation and disappearance of the more important halamines and hypohalous acids likely to be encountered in chlorinated saline water.

  11. Nuclear halo of a 177\\,MeV proton beam in water

    CERN Document Server

    Gottschalk, Bernard; Daartz, Juliane; Wagner, Miles S


    The dose distribution of a pencil beam in a water tank consists of a core, a halo and an aura. The core consists of primary protons which suffer multiple Coulomb scattering (MCS) and slow down by multiple collisions with atomic electrons (Bethe-Bloch theory). The halo consists of charged secondaries, many of them protons, from elastic interactions with H, elastic and inelastic interactions with O, and nonelastic interactions with O. We show that the halo radius is roughly one third of the beam range. The aura consists of neutral secondaries (neutrons and gamma rays) and the charged particles they set in motion. We have measured the core/halo at 177 MeV using a test beam offset in a water tank. The beam monitor was a plane parallel ionization chamber (IC) and the field IC a dose calibrated Exradin T1. Our dose measurements are absolute. We took depth-dose scans at ten displacements from the beam axis ranging from 0 to 10 cm. The dose spans five orders of magnitude, and the transition from halo to aura is obvio...

  12. Water-in-Water Emulsion Based Synthesis of Hydrogel Nanospheres with Tunable Release Kinetics (United States)

    Aydın, Derya; Kızılel, Seda


    Poly(ethylene glycol) (PEG) micro/nanospheres have several unique advantages as polymer based drug delivery systems (DDS) such as tunable size, large surface area to volume ratio, and colloidal stability. Emulsification is one of the widely used methods for facile synthesis of micro/nanospheres. Two-phase aqueous system based on polymer-polymer immiscibility is a novel approach for preparation of water-in-water (w/w) emulsions. This method is promising for the synthesis of PEG micro/nanospheres for biological systems, since the emulsion is aqueous and do not require organic solvents or surfactants. Here, we report the synthesis of nano-scale PEG hydrogel particles using w/w emulsions using phase separation of dextran and PEG prepolymer. Dynamic light scattering (DLS) and scaning electron microscopy (SEM) results demonstrated that nano-scale hydrogel spheres could be obtained with this approach. We investigated the release kinetics of a model drug, pregabalin (PGB) from PEG nanospheres and demonstrated the influence of polymerization conditions on loading and release of the drug as well as the morphology and size distribution of PEG nanospheres. The experimental drug release data was fitted to a stretched exponential function which suggested high correlation with experimental results to predict half-time and drug release rates from the model equation. The biocompatibility of nanospheres on human dermal fibroblasts using cell-survival assay suggested that PEG nanospheres with altered concentrations are non-toxic, and can be considered for controlled drug/molecule delivery.

  13. The “Autothixotropic” Phenomenon of Water and its Role in Proton Transfer

    Directory of Open Access Journals (Sweden)

    Peter Bukovec


    Full Text Available In an experimental study, significantly higher conductivity values than those of freshly prepared chemically analogous solutions were found in aged (~one year old aqueous solutions, except for those stored frozen. The results surprisingly resemble a previously noticed phenomenon in liquid water, which develops when water is stored in closed vessels. This was observed as a disturbing phenomenon in gravimetric measurements and in luminescence spectroscopy measurements. The phenomenon was termed “autothixotropy of water” due to the weak gel-like behavior which develops spontaneously over time, in which ions seem to play an important role. Here, according to experimental results we propose that contact with hydrophilic surfaces also plays an important role. The role of the “autothixotropy of water” in proton transfer is also discussed.

  14. Covalency of hydrogen bonds in liquid water can be probed by proton nuclear magnetic resonance experiments. (United States)

    Elgabarty, Hossam; Khaliullin, Rustam Z; Kühne, Thomas D


    The concept of covalency is widely used to describe the nature of intermolecular bonds, to explain their spectroscopic features and to rationalize their chemical behaviour. Unfortunately, the degree of covalency of an intermolecular bond cannot be directly measured in an experiment. Here we established a simple quantitative relationship between the calculated covalency of hydrogen bonds in liquid water and the anisotropy of the proton magnetic shielding tensor that can be measured experimentally. This relationship enabled us to quantify the degree of covalency of hydrogen bonds in liquid water using the experimentally measured anisotropy. We estimated that the amount of electron density transferred between molecules is on the order of 10  m while the stabilization energy due to this charge transfer is ∼15 kJ mol(-1). The physical insight into the fundamental nature of hydrogen bonding provided in this work will facilitate new studies of intermolecular bonding in a variety of molecular systems.

  15. A review of proton exchange membrane water electrolysis on degradation mechanisms and mitigation strategies (United States)

    Feng, Qi; Yuan, Xiao-Zi; Liu, Gaoyang; Wei, Bing; Zhang, Zhen; Li, Hui; Wang, Haijiang


    Proton exchange membrane water electrolysis (PEMWE) is an advanced and effective solution to the primary energy storage technologies. A better understanding of performance and durability of PEMWE is critical for the engineers and researchers to further advance this technology for its market penetration, and for the manufacturers of PEM water electrolyzers to implement quality control procedures for the production line or on-site process monitoring/diagnosis. This paper reviews the published works on performance degradations and mitigation strategies for PEMWE. Sources of degradation for individual components are introduced. With degradation causes discussed and degradation mechanisms examined, the review emphasizes on feasible strategies to mitigate the components degradation. To avoid lengthy real lifetime degradation tests and their high costs, the importance of accelerated stress tests and protocols is highlighted for various components. In the end, R&D directions are proposed to move the PEMWE technology forward to become a key element in future energy scenarios.

  16. Kinetic isotope effect of proton-coupled electron transfer in a hydrogen bonded phenol-pyrrolidino[60]fullerene

    NARCIS (Netherlands)

    Ravensbergen, J.; Brown, C.L.; Moore, G.F.; Frese, R.N.; van Grondelle, R.; Gust, D.; Moore, T.A.; Moore, A.L.; Kennis, J.T.M.


    Proton-coupled electron transfer (PCET) plays a central role in photosynthesis and potentially in solar-to-fuel systems. We report a spectroscopy study on a phenol-pyrrolidino[60]fullerene. Quenching of the singlet excited state from 1 ns to 250 ps is assigned to PCET. A H/D exchange study reveals a

  17. Encapsulation and Characterization of Proton-Bound Amine Homodimers in a Water Soluble, Self-Assembled Supramolecular Host

    Energy Technology Data Exchange (ETDEWEB)

    Pluth, Michael; Fiedler, Dorothea; Mugridge, Jeffrey; Bergman, Robert; Raymond, Kenneth


    Cyclic amines can be encapsulated in a water-soluble self-assembled supramolecular host upon protonation. The hydrogen bonding ability of the cyclic amines, as well as the reduced degrees of rotational freedom, allows for the formation of proton-bound homodimers inside of the assembly which are otherwise not observable in aqueous solution. The generality of homodimer formation was explored with small N-alkyl aziridines, azetidines, pyrrolidines and piperidines. Proton-bound homodimer formation is observed for N-alkylaziridines (R = methyl, isopropyl, tert-butyl), N-alkylazetidines (R = isopropyl, tertbutyl), and N-methylpyrrolidine. At high concentration, formation of a proton-bound homotrimer is observed in the case of N-methylaziridine. The homodimers stay intact inside the assembly over a large concentration range, thereby suggesting cooperative encapsulation. Both G3(MP2)B3 and G3B3 calculations of the proton-bound homodimers were used to investigate the enthalpy of the hydrogen bond in the proton-bound homodimers and suggest that the enthalpic gain upon formation of the proton-bound homodimers may drive guest encapsulation.

  18. Theoretical analysis of co-solvent effect on the proton transfer reaction of glycine in a water-acetonitrile mixture. (United States)

    Kasai, Yukako; Yoshida, Norio; Nakano, Haruyuki


    The co-solvent effect on the proton transfer reaction of glycine in a water-acetonitrile mixture was examined using the reference interaction-site model self-consistent field theory. The free energy profiles of the proton transfer reaction of glycine between the carboxyl oxygen and amino nitrogen were computed in a water-acetonitrile mixture solvent at various molar fractions. Two types of reactions, the intramolecular proton transfer and water-mediated proton transfer, were considered. In both types of the reactions, a similar tendency was observed. In the pure water solvent, the zwitterionic form, where the carboxyl oxygen is deprotonated while the amino nitrogen is protonated, is more stable than the neutral form. The reaction free energy is -10.6 kcal mol(-1). On the other hand, in the pure acetonitrile solvent, glycine takes only the neutral form. The reaction free energy from the neutral to zwitterionic form gradually increases with increasing acetonitrile concentration, and in an equally mixed solvent, the zwitterionic and neutral forms are almost isoenergetic, with a difference of only 0.3 kcal mol(-1). The free energy component analysis based on the thermodynamic cycle of the reaction also revealed that the free energy change of the neutral form is insensitive to the change of solvent environment but the zwitterionic form shows drastic changes. In particular, the excess chemical potential, one of the components of the solvation free energy, is dominant and contributes to the stabilization of the zwitterionic form.

  19. Double quantum 1H MAS NMR studies of hydrogen-bonded protons and water dynamics in materials. (United States)

    Alam, Todd M; Nyman, May; McIntyre, Sarah K


    Two-dimensional double quantum (DQ) 1H MAS NMR was used to investigate different proton environments in a series of alkali (Na, K, Rb, Cs) [Nb6O19]8- Lindqvist salts, with the water and hydrogen-bound intercluster protons being clearly resolved. Through the analysis of the DQ 1H NMR spinning sideband pattern, it is possible to extract both the mean and distribution of the motionally averaged intramolecular homonuclear 1H-1H dipolar coupling for the different water environments and the intercluster protons. Motional order parameters for the water environments were then calculated from the averaged dipolar couplings. The influence of additional intermolecular dipolar couplings due to multispin interactions were simulated and discussed.

  20. Experimental study of the atmospheric neutrino backgrounds for proton decay to positron and neutral pion searches in water Cherenkov detectors

    CERN Document Server

    Mine, S; Andringa, S; Aoki, S; Argyriades, J; Asakura, K; Ashie, R; Berghaus, F; Berns, H; Bhang, H; Blondel, A; Borghi, S; Bouchez, J; Burguet-Castell, J; Casper, D; Catala, J; Cavata, C; Cervera-Villanueva, Anselmo; Chen, S M; Cho, K O; Choi, J H; Dore, U; Espinal, X; Fechner, M; Fernández, E; Fujii, Y; Fukuda, Y; Gomez-Cadenas, J; Gran, R; Hara, T; Hasegawa, M; Hasegawa, T; Hayato, Y; Helmer, R L; Hiraide, K; Hosaka, J; Ichikawa, A K; Iinuma, M; Ikeda, A; Ishida, T; Ishihara, K; Ishii, T; Ishitsuka, M; Itow, Y; Iwashita, T; Jang, H I; Jeon, E J; Jeong, I S; Joo, K K; Jover, G; Jung, C K; Kajita, T; Kameda, J; Kaneyuki, K; Kato, I; Kearns, E; Kim, C O; Khabibullin, M; Khotjantsev, A; Kielczewska, D; Kim, J Y; Kim, S B; Kitching, P; Kobayashi, K; Kobayashi, T; Konaka, A; Koshio, Y; Kropp, W; Kudenko, Yu; Kuno, Y; Kurimoto, Y; Kutter, T; Learned, J; Likhoded, S; Lim, I T; Loverre, P F; Ludovici, L; Maesaka, H; Mallet, J; Mariani, C; Matsuno, S; Matveev, V; McConnel, K; McGrew, C; Mikheyev, S; Minamino, A; Mineev, O; Mitsuda, C; Miura, M; Moriguchi, Y; Moriyama, S; Nakadaira, T; Nakahata, M; Nakamura, K; Nakano, I; Nakaya, T; Nakayama, S; Namba, T; Nambu, R; Nawang, S; Nishikawa, K; Nitta, K; Nova, F; Novella, P; Obayashi, Y; Okada, A; Okumura, K; Oser, S M; Oyama, Y; Pac, M Y; Pierre, F; Rodríguez, A; Saji, C; Sakuda, M; Sánchez, F; Scholberg, K; Schroeter, R; Sekiguchi, M; Shiozawa, M; Shiraishi, K; Sitjes, G; Smy, M; Sobel, H; Sorel, M; Stone, J; Sulak, L; Suzuki, A; Suzuki, Y; Tada, M; Takahashi, T; Takenaga, Y; Takeuchi, Y; Taki, K; Takubo, Y; Tamura, N; Tanaka, M; Terri, R; T'Jampens, S; Tornero-Lopez, A; Totsuka, Y; Vagins, M; Whitehead, L; Walter, C W; Wang, W; Wilkes, R J; Yamada, S; Yamada, Y; Yamamoto, S; Yanagisawa, C; Yershov, N; Yokoyama, H; Yokoyama, M; Yoo, J; Yoshida, M; Zalipska, J


    The atmospheric neutrino background for proton decay to positron and neutral pion in ring imaging water Cherenkov detectors is studied with an artificial accelerator neutrino beam for the first time. In total, about 314,000 neutrino events corresponding to about 10 megaton-years of atmospheric neutrino interactions were collected by a 1,000 ton water Cherenkov detector (KT). The KT charged-current single neutral pion production data are well reproduced by simulation programs of neutrino and secondary hadronic interactions used in the Super-Kamiokande (SK) proton decay search. The obtained proton to positron and neutral pion background rate by the KT data for SK from the atmospheric neutrinos whose energies are below 3 GeV is about two per megaton-year. This result is also relevant to possible future, megaton-scale water Cherenkov detectors.

  1. Kinetic model of water vapour adsorption by gluten-free starch (United States)

    Ocieczek, Aneta; Kostek, Robert; Ruszkowska, Millena


    This study evaluated the kinetics of water vapour adsorption on the surface of starch molecules derived from wheat. The aim of the study was to determine an equation that would allow estimation of water content in tested material in any timepoint of the adsorption process aimed at settling a balance with the environment. An adsorption isotherm of water vapour on starch granules was drawn. The parameters of the Guggenheim, Anderson, and De Boer equation were determined by characterizing the tested product and adsorption process. The equation of kinetics of water vapour adsorption on the surface of starch was determined based on the Guggenheim, Anderson, and De Boer model describing the state of equilibrium and on the model of a first-order linear inert element describing the changes in water content over time.

  2. The proton momentum distribution in strongly H-bonded phases of water; a critical test of electrostatic models

    CERN Document Server

    Burnham, C J; Hayashi, T; Mukamel, S; Napoleon, R L; Keyes, T


    Water is often viewed as a collection of monomers interacting electrostatically with each other. We compare the water proton momentum distributions from recent neutron scattering data with those calculated from two electronic structure based models. We find that below 500 K the electrostatic models are not able to even qualitatively account for the sizable vibrational zero-point contribution to the enthalpy of vaporization. This discrepancy is evidence that the change in the proton well upon solvation cannot be entirely explained by electrostatic effects alone.

  3. Ocean swell within the kinetic equation for water waves

    Directory of Open Access Journals (Sweden)

    S. I. Badulin


    Full Text Available Results of extensive simulations of swell evolution within the duration-limited setup for the kinetic Hasselmann equation for long durations of up to 2  ×  106 s are presented. Basic solutions of the theory of weak turbulence, the so-called Kolmogorov–Zakharov solutions, are shown to be relevant to the results of the simulations. Features of self-similarity of wave spectra are detailed and their impact on methods of ocean swell monitoring is discussed. Essential drop in wave energy (wave height due to wave–wave interactions is found at the initial stages of swell evolution (on the order of 1000 km for typical parameters of the ocean swell. At longer times, wave–wave interactions are responsible for a universal angular distribution of wave spectra in a wide range of initial conditions. Weak power-law attenuation of swell within the Hasselmann equation is not consistent with results of ocean swell tracking from satellite altimetry and SAR (synthetic aperture radar data. At the same time, the relatively fast weakening of wave–wave interactions makes the swell evolution sensitive to other effects. In particular, as shown, coupling with locally generated wind waves can force the swell to grow in relatively light winds.

  4. Electron Emission from Amorphous Solid Water Induced by Passage of Energetic Protons and Fluorine Ions (United States)

    Toburen, L. H.; McLawhorn, S. L.; McLawhorn, R. A.; Carnes, K. D.; Dingfelder, M.; Shinpaugh, J. L.


    Absolute doubly differential electron emission yields were measured from thin films of amorphous solid water (ASW) after the transmission of 6 MeV protons and 19 MeV (1 MeV/nucleon) fluorine ions. The ASW films were frozen on thin (1-μm) copper foils cooled to approximately 50 K. Electrons emitted from the films were detected as a function of angle in both the forward and backward direction and as a function of the film thickness. Electron energies were determined by measuring the ejected electron time of flight, a technique that optimizes the accuracy of measuring low-energy electron yields, where the effects of molecular environment on electron transport are expected to be most evident. Relative electron emission yields were normalized to an absolute scale by comparison of the integrated total yields for proton-induced electron emission from the copper substrate to values published previously. The absolute doubly differential yields from ASW are presented along with integrated values, providing single differential and total electron emission yields. These data may provide benchmark tests of Monte Carlo track structure codes commonly used for assessing the effects of radiation quality on biological effectiveness. PMID:20681805

  5. Decoupling hydrogen and oxygen evolution during electrolytic water splitting using an electron-coupled-proton buffer. (United States)

    Symes, Mark D; Cronin, Leroy


    Hydrogen is essential to several key industrial processes and could play a major role as an energy carrier in a future 'hydrogen economy'. Although the majority of the world's hydrogen supply currently comes from the reformation of fossil fuels, its generation from water using renewables-generated power could provide a hydrogen source without increasing atmospheric CO₂ levels. Conventional water electrolysis produces H₂ and O₂ simultaneously, such that these gases must be generated in separate spaces to prevent their mixing. Herein, using the polyoxometalate H₃PMo₁₂O₄₀, we introduce the concept of the electron-coupled-proton buffer (ECPB), whereby O₂ and H₂ can be produced at separate times during water electrolysis. This could have advantages in preventing gas mixing in the headspaces of high-pressure electrolysis cells, with implications for safety and electrolyser degradation. Furthermore, we demonstrate that temporally separated O₂ and H₂ production allows greater flexibility regarding the membranes and electrodes that can be used in water-splitting cells.

  6. Equilibrium and kinetics of water adsorption in carbon molecular sieve: theory and experiment. (United States)

    Rutherford, S W; Coons, J E


    Measurements of water adsorption equilibrium and kinetics in Takeda carbon molecular sieve (CMS) were undertaken in an effort to characterize fundamental mechanisms of adsorption and transport. Adsorption equilibrium revealed a type III isotherm that was characterized by cooperative multimolecular sorption theory. Water adsorption was found to be reversible and did not display hysteresis upon desorption over the conditions studied. Adsorption kinetics measurements revealed that a Fickian diffusion mechanism governed the uptake of water and that the rate of adsorption decreased with increasing relative pressure. Previous investigations have attributed the observed decreasing trend in the rate of adsorption to blocking of micropores. Here, it is proposed that the decrease is attributed to the thermodynamic correction to Fick's law which is formulated on the basis of the chemical potential as the driving force for transport. The thermodynamically corrected formulation accounted for observations of transport of water and other molecules in CMS.

  7. Collecting meaningful early-time kinetic data in homogeneous catalytic water oxidation with a sacrificial oxidant. (United States)

    Vickers, James W; Sumliner, Jordan M; Lv, Hongjin; Morris, Mike; Geletii, Yurii V; Hill, Craig L


    As the field of water oxidation catalysis grows, so does the sophistication of the associated experimental apparatuses. However, problems persist in studying some of the most basic aspects of catalytic water oxidation including acquisition of satisfactory early-reaction-time kinetics and rapid quantification of O2 concentration. We seek to remedy these problems and through better experimental design, elucidate mechanistic aspects of catalytic water oxidation with theory backed by experimental data. Two new methods for evaluating homogeneous water oxidation catalysts by reaction with a stoichiometric oxidant are presented which eliminate problems of incomplete fast mixing and O2 measurement response time. These methods generate early-reaction-time kinetics that have previously been unavailable.

  8. MP4 Study of the Anharmonic Coupling of the Shared Proton Stretching Vibration of the Protonated Water Dimer in Equilibrium and Transition States. (United States)

    Pitsevich, G; Malevich, A; Kozlovskaya, E; Mahnach, E; Doroshenko, I; Pogorelov, V; Pettersson, Lars G M; Sablinskas, V; Balevicius, V


    The structure and harmonic and anharmonic IR spectra of the protonated water dimer (PWD) were calculated in C1, C2, and Cs symmetry at the MP4/acc-pVTZ level of theory. We found that structure and IR spectra are practically identical in C2 and C1 symmetry, demonstrating that an equilibrium C1 configuration of the PWD is not realized. Anharmonic coupling of the shared proton stretching vibration with all other modes in the PWD in C2 and Cs symmetry was the focus of this investigation. For this purpose, 28 two-dimensional potential energy surfaces (2D PES) were built at the MP4/acc-pVTZ level of theory and the corresponding vibrational Schrödinger equations were solved using the DVR method. Differences in the coupling of the investigated mode with other modes in the C2 and Cs configurations, along with some factors that determine the red- or blue-shift of the stretching vibration frequency, were analyzed. We obtained a rather reasonable value of the stretching frequency of the bridging proton (1058.4 cm(-1)) unperturbed by Fermi resonance. The Fermi resonance between the fundamental vibration ν7 and the combined vibration ν2 + ν6 of the same symmetry was analyzed through anharmonic second-order perturbation theory calculations, as well as by 3D PES constructed using Q2, Q6, and Q7 as normal coordinates. A significant (up to 50%) transfer of intensity from the fundamental vibration to the combined one was found. We have estimated the frequency of the bridging proton stretching vibration in the Cs configuration of the PWD based on calculations of the intrinsic anharmonicity and anharmonic double modes interactions at the MP4/acc-pVTZ level of theory (1261 cm(-1)).

  9. Organic materials retain high proportion of protons, iron and aluminium from acid sulphate soil drainage water with little subsequent release. (United States)

    Dang, Tan; Mosley, Luke M; Fitzpatrick, Rob; Marschner, Petra


    When previously oxidised acid sulphate soils are leached, they can release large amounts of protons and metals, which threaten the surrounding environment. To minimise the impact of the acidic leachate, protons and metals have to be retained before the drainage water reaches surrounding waterways. One possible amelioration strategy is to pass drainage water through permeable reactive barriers. The suitability of organic materials for such barriers was tested. Eight organic materials including two plant residues, compost and five biochars differing in feedstock and production temperature were finely ground and filled into PVC cores at 3.5 g dry wt/core. Field-collected acidic drainage water (pH 3, Al 22 mg L(-1) and Fe 48 mg L(-1)) was applied in six leaching events followed by six leaching events with reverse osmosis (RO) water (45 mL/event). Compost and biochars increased the leachate pH by up to 4.5 units and had a high retention capacity for metals. The metal and proton release during subsequent leaching with RO water was very small, cumulatively only 0.05-0.8 % of retained metals and protons. Retention was lower in the two plant residues, particularly wheat straw, which raised leachate pH by 2 units only in the first leaching event with drainage water, but had little effect on leachate pH in the following leaching events. It can be concluded that organic materials and particularly biochars and compost have the potential to be used in acid drainage treatment to remove and retain protons and metals.

  10. Proton transport in water and DNA components: A Geant4 Monte Carlo simulation

    Energy Technology Data Exchange (ETDEWEB)

    Champion, C., E-mail: [Université Bordeaux 1, CNRS/IN2P3, Centre d’Etudes Nucléaires de Bordeaux Gradignan, CENBG, 33175 Gradignan (France); Incerti, S.; Tran, H.N.; Karamitros, M. [Université Bordeaux 1, CNRS/IN2P3, Centre d’Etudes Nucléaires de Bordeaux Gradignan, CENBG, 33175 Gradignan (France); Shin, J.I.; Lee, S.B. [Proton Therapy Center, National Cancer Center, 323 Ilsan-ro, Ilsandong-gu, Goyan (Korea, Republic of); Lekadir, H. [Laboratoire de Physique Moléculaire et des Collisions, Université de Lorraine (France); Bernal, M. [Instituto de Física Gleb Wataghin, Universidade Estadual de Campinas, SP (Brazil); Francis, Z. [Université Saint Joseph, Science Faculty, Department of Physics, Beirut (Lebanon); Ivanchenko, V. [Ecoanalytica, 119899 Moscow (Russian Federation); Fojón, O.A. [Instituto de Física Rosario, CONICET and Universidad Nacional de Rosario (Argentina); Hanssen, J. [Laboratoire de Physique Moléculaire et des Collisions, Université de Lorraine (France); Rivarola, R.D. [Instituto de Física Rosario, CONICET and Universidad Nacional de Rosario (Argentina)


    Accurate modeling of DNA damages resulting from ionizing radiation remains a challenge of today’s radiobiology research. An original set of physics processes has been recently developed for modeling the detailed transport of protons and neutral hydrogen atoms in liquid water and in DNA nucleobases using the Geant4-DNA extension of the open source Geant4 Monte Carlo simulation toolkit. The theoretical cross sections as well as the mean energy transfers during the different ionizing processes were taken from recent works based on classical as well as quantum mechanical predictions. Furthermore, in order to compare energy deposition patterns in liquid water and DNA material, we here propose a simplified cellular nucleus model made of spherical voxels, each containing randomly oriented nanometer-size cylindrical targets filled with either liquid water or DNA material (DNA nucleobases) both with a density of 1 g/cm{sup 3}. These cylindrical volumes have dimensions comparable to genetic material units of mammalian cells, namely, 25 nm (diameter) × 25 nm (height) for chromatin fiber segments, 10 nm (d) × 5 nm (h) for nucleosomes and 2 nm (d) × 2 nm (h) for DNA segments. Frequencies of energy deposition in the cylindrical targets are presented and discussed.

  11. Oxidation of phenyl alanine by pyridinium chlorochromate in acidic DMF–water medium: A kinetic study

    Directory of Open Access Journals (Sweden)

    B.L. Hiran


    Full Text Available The kinetics of oxidation of phenyl alanine by pyridinium chlorochromate in DMF–water (70:30% mixture in presence of perchloric acid leads to the formation of corresponding aldehyde. The reaction is of first order each in [PCC], [HClO4] and [AA]. Michaelis–Menten type kinetics was observed with phenyl alanine. The reaction rates were determined at different temperatures [25, 30, 35, 40, 45, 50 °C] and the activation parameters were calculated. The reaction does not induce polymerization of acrylonitrile. With an increase in the amount of DMF in its aqueous mixture, the rate increases. A suitable mechanism for the reaction was postulated.

  12. Full dimensional (15-dimensional) quantum-dynamical simulation of the protonated water dimer. II. Infrared spectrum and vibrational dynamics

    DEFF Research Database (Denmark)

    Vendrell, Oriol; Gatti, Fabien; Meyer, Hans-Dieter


    The infrared absorption spectrum of the protonated water dimer (H5O2+) is simulated in full dimensionality (15 dimensional) in the spectral range of 0-4000 cm(-1). The calculations are performed using the multiconfiguration time-dependent Hartree (MCTDH) method for propagation of wavepackets. All...

  13. Thermal and water management of low temperature Proton Exchange Membrane Fuel Cell in fork-lift truck power system

    DEFF Research Database (Denmark)

    Hosseinzadeh, Elham; Rokni, Masoud; Rabbani, Raja Abid


    A general zero-dimensional Proton Exchange Membrane Fuel Cell (PEMFC) model has been developed for forklift truck application. The balance of plant (BOP) comprises of a compressor, an air humidifier, a set of heat exchangers and a recirculation pump. Water and thermal management of the fuel cell...

  14. Kinetics and mechanisms of formation of earthy and musty odor compounds: Chloroanisoles during water chlorination. (United States)

    Zhang, Kejia; Zhou, Xinyan; Zhang, Tuqiao; Mao, Minmin; Li, Lei; Liao, Wenchao


    Chloroanisoles are often reported as off-flavor compounds which produce an earthy and musty flavors and odors in drinking water. To improve understanding and ultimately minimize the formation of 2,4-dichloroanisole (2,4-DCA), 2,6-dichloroanisole (2,6-DCA) and 2,4,6-trichloroanisole (2,4,6-TCA), which have low odor threshold concentrations (OTC: 0.03-4 ng L(-1)), a kinetic database for the chlorination of anisole was established by kinetic measurements. The results showed that HOCl reacted with anisole in acidic solution, with the hydrogen ion as an important catalyst. Quantification of product distribution of the produced chloroanisoles demonstrated that a chlorine attack in the para-position was favored over the ortho-position. A kinetic model was formulated, which permitted investigation of the relative importance of the chlorine dose and other water quality parameters including the concentrations of anisole and several metal ions, as well as temperature, on the product distribution of chloroanisoles. In general, high chlorine doses led to low concentrations of intermediates. The presence of ions such as Fe(3+) and Al(3+) facilitated the formation of chloroanisoles, but Zn(2+) and Mn(2+) did not. The kinetic model can be applied to optimize water chlorination and minimize earthy and musty odors. Copyright © 2016 Elsevier Ltd. All rights reserved.

  15. Calculations and measurements of the scintillator-to-water stopping power ratio of liquid scintillators for use in proton radiotherapy. (United States)

    Ingram, W Scott; Robertson, Daniel; Beddar, Sam


    Liquid scintillators are a promising detector for high-resolution three-dimensional proton therapy dosimetry. Because the scintillator comprises both the active volume of the detector and the phantom material, an ideal scintillator will exhibit water equivalence in its radiological properties. One of the most fundamental of these is the scintillator's stopping power. The objective of this study was to compare calculations and measurements of scintillator-to-water stopping power ratios to evaluate the suitability of the liquid scintillators BC-531 and OptiPhase HiSafe 3 for proton dosimetry. We also measured the relative scintillation output of the two scintillators. Both calculations and measurements show that the linear stopping power of OptiPhase is significantly closer to water than that of BC-531. BC-531 has a somewhat higher scintillation output. OptiPhase can be mixed with water at high concentrations, which further improves its scintillator-to-water stopping power ratio. However, this causes the solution to become cloudy, which has a negative impact on the scintillation output and spatial resolution of the detector. OptiPhase is preferred over BC-531 for proton dosimetry because its density and scintillator-to-water stopping power ratio are more water equivalent.

  16. Transport-Relevant Protein Conformational Dynamics and Water Dynamics on Multiple Timescales in an Archetypal Proton Channel - Insights from Solid-State NMR. (United States)

    Mandala, Venkata; Gelenter, Martin D; Hong, Mei


    The influenza M2 protein forms a tetrameric proton channel that conducts protons from the acidic endosome into the virion by shuttling protons between water and a transmembrane histidine. Previous NMR studies have shown that this histidine protonates and deprotonates on the microsecond timescale. However, M2's proton conduction rate is 10 - 1000 s-1, more than two orders of magnitude slower than the histidine-water proton-exchange rate. M2 is also known to be conformationally plastic. To address the disparity between the functional timescale and the timescales of protein conformational dynamics and water dynamics, we have now investigated a W41F mutant of the M2 transmembrane domain using solid-state NMR. 13C chemical shifts of the membrane-bound peptide indicate the presence of two distinct tetramer conformations, whose concentrations depend exclusively on pH and hence the charge-state distribution of the tetramers. High-temperature 2D correlation spectra indicate that these two conformations interconvert at a rate of ~400 s-1 when the +2 and +3 charge states dominate, which gives the first experimental evidence of protein conformational motion on the transport timescale. Protein 13C-detected water 1H T2 relaxation measurements show that channel water relaxes an order of magnitude faster than bulk water and membrane-associated water, indicating that channel water undergoes nanosecond motion in a pH-independent fashion. These results connect motions on three timescales to explain M2's proton-conduction mechanism: picosecond-to-nanosecond motions of water molecules facilitate proton Grotthuss hopping, microsecond motions of the histidine sidechain allow water-histidine proton transfer, while millisecond motions of the entire four-helix bundle constitute the rate-limiting step, dictating the number of protons released into the virion.

  17. Effects of soil water saturation on sampling equilibrium and kinetics of selected polycyclic aromatic hydrocarbons. (United States)

    Kim, Pil-Gon; Roh, Ji-Yeon; Hong, Yongseok; Kwon, Jung-Hwan


    Passive sampling can be applied for measuring the freely dissolved concentration of hydrophobic organic chemicals (HOCs) in soil pore water. When using passive samplers under field conditions, however, there are factors that might affect passive sampling equilibrium and kinetics, such as soil water saturation. To determine the effects of soil water saturation on passive sampling, the equilibrium and kinetics of passive sampling were evaluated by observing changes in the distribution coefficient between sampler and soil (Ksampler/soil) and the uptake rate constant (ku) at various soil water saturations. Polydimethylsiloxane (PDMS) passive samplers were deployed into artificial soils spiked with seven selected polycyclic aromatic hydrocarbons (PAHs). In dry soil (0% water saturation), both Ksampler/soil and ku values were much lower than those in wet soils likely due to the contribution of adsorption of PAHs onto soil mineral surfaces and the conformational changes in soil organic matter. For high molecular weight PAHs (chrysene, benzo[a]pyrene, and dibenzo[a,h]anthracene), both Ksampler/soil and ku values increased with increasing soil water saturation, whereas they decreased with increasing soil water saturation for low molecular weight PAHs (phenanthrene, anthracene, fluoranthene, and pyrene). Changes in the sorption capacity of soil organic matter with soil water content would be the main cause of the changes in passive sampling equilibrium. Henry's law constant could explain the different behaviors in uptake kinetics of the selected PAHs. The results of this study would be helpful when passive samplers are deployed under various soil water saturations. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Comparison of the swelling kinetics of a partially neutralized poly(acrylic acid) hydrogel in distilled water and physiological solution




    The isothermal kinetics curves of the swelling of a poly(acrylic acid) hydrogel in distilled water and physiological solution at temperatures ranging from 20 to 40 ºC were determined. The possibility of applying both the Fick’s kinetics model and kinetics model of the first order chemical reaction to the swelling kinetics of the PAA hydrogel in distilled water and physiological solution were examined. It was found that the possibilities of applying these models were limited. The new model of ...

  19. Kinetic analyses of plant water relocation using deuterium as tracer - reduced water flux of Arabidopsis pip2 aquaporin knockout mutants. (United States)

    Da Ines, O; Graf, W; Franck, K I; Albert, A; Winkler, J B; Scherb, H; Stichler, W; Schäffner, A R


    Due to reduced evaporation and diffusion of water molecules containing heavier isotopes, leaf water possesses an elevated (18)O or (2)H steady-state content. This enrichment has been exploited in plant physiology and ecology to assess transpiration and leaf water relations. In contrast to these studies, in this work the (2)H content of the medium of hydroponically grown Arabidopsis thaliana was artificially raised, and the kinetics of (2)H increase in the aerial parts recorded during a short phase of 6-8 h, until a new equilibrium at a higher level was reached. A basic version of the enrichment models was modified to establish an equation that could be fitted to measured leaf (2)H content during uptake kinetics. The fitting parameters allowed estimation of the relative water flux q(leaf) into the Arabidopsis rosette. This approach is quasi-non-invasive, since plants are not manipulated during the uptake process, and therefore, offers a new tool for integrated analysis of plant water relations. The deuterium tracer method was employed to assess water relocation in Arabidopsis pip2;1 and pip2;2 aquaporin knockout plants. In both cases, q(leaf) was significantly reduced by about 20%. The organ and cellular expression patterns of both genes imply that changes in root hydraulic conductivity, as previously demonstrated for pip2;2 mutants, and leaf water uptake and distribution contributed in an integrated fashion to this reduced flux in intact plants.

  20. Impact of heat and water management on proton exchange membrane fuel cells degradation in automotive application (United States)

    Nandjou, F.; Poirot-Crouvezier, J.-P.; Chandesris, M.; Blachot, J.-F.; Bonnaud, C.; Bultel, Y.


    In Proton Exchange Membrane Fuel Cells, local temperature is a driving force for many degradation mechanisms such as hygrothermal deformation and creep of the membrane, platinum dissolution and bipolar plates corrosion. In order to investigate and quantify those effects in automotive application, durability testing is conducted in this work. During the ageing tests, the local performance and temperature are investigated using in situ measurements of a printed circuit board. At the end of life, post-mortem analyses of the aged components are conducted. The experimental results are compared with the simulated temperature and humidity in the cell obtained from a pseudo-3D multiphysics model in order to correlate the observed degradations to the local conditions inside the stack. The primary cause of failure in automotive cycling is pinhole/crack formation in the membrane, induced by high variations of its water content over time. It is also observed that water condensation largely increases the probability of the bipolar plates corrosion while evaporation phenomena induce local deposits in the cell.

  1. In situ measurements of water transfer due to different mechanisms in a proton exchange membrane fuel cell (United States)

    Husar, Attila; Higier, Andrew; Liu, Hongtan

    Water management is of critical importance in a proton exchange membrane (PEM) fuel cell, in particular, those based on a sulfonic acid polymer, which requires water to conduct protons. Yet there are limited in situ studies of water transfer through the membrane and no data are available for water transfer due to individual mechanisms through the membrane in an operational fuel cell. Thus it is the objective of this study to measure water transfer through the membrane due to each individual mechanism in an operational PEM fuel cell. The three different mechanisms of water transfer, i.e., electro-osmotic drag, diffusion and hydraulic permeation are isolated by specially imposed boundary conditions. Therefore water transfer through the membrane due to each mechanism is measured separately. In this study, all the data is collected in an actual assembled operational fuel cell. The experimental results show that water transfer due to hydraulic permeation, i.e. the pressure difference between the anode and cathode is at least an order of magnitude lower than those due to the other two mechanisms. The data for water transfer due to diffusion through the membrane are in good agreement with some of the ex situ data in the literature. The data for electro-osmosis show that the number of water molecules dragged per proton increases not only with temperature but also with current density, which is different from existing data in the literature. The methodology used in this study is simple and can be easily adopted for in situ water transfer measurement due to different mechanisms in other PEM fuel cells without any cell modifications.

  2. Calculation of the protons stopping power in water using dielectric formalism in the MELF-GOS approach; Calculo do poder de freamento de protons em agua utilizando o formalismo dieletrico na aproximacao MELF-GOS

    Energy Technology Data Exchange (ETDEWEB)

    Ribeiro, Franciane; Mazer, Amanda Cristina; Hormaza, Joel Mesa [Universidade Estadual Paulista Julio de Mesquita Filho (UNESP), Botucatu, SP (Brazil)


    In order to calculate the stopping power of protons, there are many very successful models at high energies, which are extrapolated to low-energy regions. From the point of view of application of proton beam in cancer treatment is just this low energy region the most relevant due to the dose deposition profile in depth for protons. In this work, we present a calculation of the stopping power of protons in a water target using the dielectric formalism in MELF-GOS approach. The results when compared to other models show good agreement for energies above 100 keV and lower values below this energy. This result should impact the range of values of protons and the Bragg peak position. (author)

  3. Fourier transform infrared difference and time-resolved infrared detection of the electron and proton transfer dynamics in photosynthetic water oxidation. (United States)

    Noguchi, Takumi


    Photosynthetic water oxidation, which provides the electrons necessary for CO₂ reduction and releases O₂ and protons, is performed at the Mn₄CaO₅ cluster in photosystem II (PSII). In this review, studies that assessed the mechanism of water oxidation using infrared spectroscopy are summarized focusing on electron and proton transfer dynamics. Structural changes in proteins and water molecules between intermediates known as Si states (i=0-3) were detected using flash-induced Fourier transform infrared (FTIR) difference spectroscopy. Electron flow in PSII and proton release from substrate water were monitored using the infrared changes in ferricyanide as an exogenous electron acceptor and Mes buffer as a proton acceptor. Time-resolved infrared (TRIR) spectroscopy provided information on the dynamics of proton-coupled electron transfer during the S-state transitions. In particular, a drastic proton movement during the lag phase (~200μs) before electron transfer in the S3→S0 transition was detected directly by monitoring the infrared absorption of a polarizable proton in a hydrogen bond network. Furthermore, the proton release pathways in the PSII proteins were analyzed by FTIR difference measurements in combination with site-directed mutagenesis, isotopic substitutions, and quantum chemical calculations. Therefore, infrared spectroscopy is a powerful tool for understanding the molecular mechanism of photosynthetic water oxidation. This article is part of a Special Issue entitled: Vibrational spectroscopies and bioenergetic systems. Copyright © 2014 Elsevier B.V. All rights reserved.

  4. Absolute quantitative proton NMR spectroscopy based on the amplitude of the local water suppression pulse. Quantification of brain water and metabolites

    DEFF Research Database (Denmark)

    Danielsen, E R; Henriksen, O


    volunteers. Localized proton NMR spectra were obtained from a region of primarily white matter in the occipital lobe. The observable water content in the NMR spectra was 0.685 +/- 0.025. The absolute metabolite concentrations were: [total choline] = 1.25 +/- 0.21 nM, [total creatine] = 6.71 +/- 0.59 n...

  5. Localized proton spectroscopy without water suppression: removal of gradient induced frequency modulations by modulus signal selection. (United States)

    Serrai, Haçène; Clayton, David B; Senhadji, Lotfi; Zuo, Chun; Lenkinski, Robert E


    Most Magnetic Resonance Spectroscopy (MRS) localization methods can generate gradient vibrations at acoustic frequencies and/or magnetic field oscillation, which can cause a time-varying magnetic field superimposed onto the static one. This effect can produce frequency modulations of the spectral resonances. When localized MRS data are acquired without water suppression, the associated frequency modulations are manifested as a manifold of spurious peaks, called sidebands, which occur symmetrically around the water resonance. These sidebands can be larger than the small metabolite resonances and can present a problem for the quantitation of the spectra, especially at short echo times. Furthermore, the resonance lineshapes may be distorted if any low frequency modulations are present. A simple solution is presented which consists of selecting the modulus of the acquired Free Induction Decay (FID) signal. Since the frequency modulations affect only the phase of the FID signal, the obtained real spectrum of the modulus is free from the spurious peaks where quantitative results may be directly obtained. Using this method, the distortions caused by the sidebands are removed. This is demonstrated by processing proton MRS spectra acquired without water suppression collected from a phantom containing metabolites at concentrations comparable to those in human brain and from a human subject using two different localization methods (PRESS and Chemical Shift Imaging PRESS-(CSI)). The results obtained illustrate the ability of this approach to remove the spurious peaks. The corrected spectra can then be fit accurately. This is confirmed by the results obtained from both the relative and the absolute metabolites concentrations in phantoms and in vivo.

  6. Kinetic Study of the Hydrolisys of Phenyl Perfluorooctanoate in Water: Deaggregation Effect of b-Cyclodextrin

    Directory of Open Access Journals (Sweden)

    M. A. Fernández


    Full Text Available The kinetics of the hydrolysis of phenyl perfluorooctanoate was studied at pH 6.00 and 9.90 in water. The substrate is aggregated under all working reaction conditions, which is indicated from the decrease in the reaction rate when the substrate concentration is raised. The addition of β-cyclodextrin produces the deaggregation of the ester catalyzing the reaction.

  7. Theoretical study on water-mediated excited-state multiple proton transfer in 7-azaindole: significance of hydrogen bond rearrangement. (United States)

    Yu, Xue-fang; Yamazaki, Shohei; Taketsugu, Tetsuya


    Excited-state multiple proton transfer (ESMPT) in the cluster of 7-azaindole with three water molecules [7-azaindole(H(2)O)(3)] is theoretically investigated by the TDDFT, CASPT2, and CC2 methods. Examination of the potential energy surface in the first excited state indicates that ESMPT in 7-azaindole(H(2)O)(3) proceeds initially with the rearrangement of hydrogen bond structure of water molecules from a bridged-planar isomer to a cyclic-nonplanar isomer, followed by triple proton transfer in the latter. This reaction is found to be energetically more favorable than quadruple proton transfer in the bridged-planar isomer without hydrogen bond reorganization. It is also shown that all proton-transfer processes follow a concerted mechanism rather than a stepwise mechanism. The computational results show good consistency with the unexpected experimental observations as to the electronic spectra and excited-state lifetime. In particular, the barrier of the hydrogen bond rearrangement is found to be less than 1 kcal/mol, consistent with the missing vibronic bands for 7-azaindole(H(2)O)(3) with an excess energy of more than 200 cm(-1) in the S(1) state.

  8. Kinetics of Chronic Oxidation of NBG-17 Nuclear Graphite by Water Vapor

    Energy Technology Data Exchange (ETDEWEB)

    Contescu, Cristian I [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Burchell, Timothy D [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Mee, Robert [Univ. of Tennessee, Knoxville, TN (United States)


    This report presents the results of kinetic measurements during accelerated oxidation tests of NBG-17 nuclear graphite by low concentration of water vapor and hydrogen in ultra-high purity helium. The objective is to determine the parameters in the Langmuir-Hinshelwood (L-H) equation describing the oxidation kinetics of nuclear graphite in the helium coolant of high temperature gas-cooled reactors (HTGR). Although the helium coolant chemistry is strictly controlled during normal operating conditions, trace amounts of moisture (predictably < 0.2 ppm) cannot be avoided. Prolonged exposure of graphite components to water vapor at high temperature will cause very slow (chronic) oxidation over the lifetime of graphite components. This behavior must be understood and predicted for the design and safe operation of gas-cooled nuclear reactors. The results reported here show that, in general, oxidation by water of graphite NBG-17 obeys the L-H mechanism, previously documented for other graphite grades. However, the characteristic kinetic parameters that best describe oxidation rates measured for graphite NBG-17 are different than those reported previously for grades H-451 (General Atomics, 1978) and PCEA (ORNL, 2013). In some specific conditions, certain deviations from the generally accepted L-H model were observed for graphite NBG-17. This graphite is manufactured in Germany by SGL Carbon Group and is a possible candidate for the fuel elements and reflector blocks of HTGR.

  9. Photodegradation kinetics and transformation products of ketoprofen, diclofenac and atenolol in pure water and treated wastewater

    Energy Technology Data Exchange (ETDEWEB)

    Salgado, R. [REQUIMTE/CQFB, Chemistry Department, FCT, Universidade Nova de Lisboa, 2829-516 Caparica (Portugal); ESTS-IPS, Escola Superior de Tecnologia de Setúbal do Instituto Politécnico de Setúbal, Rua Vale de Chaves, Campus do IPS, Estefanilha, 2910-761 Setúbal (Portugal); Pereira, V.J. [Instituto de Biologia Experimental e Tecnológica (IBET), Av. da República (EAN), 2784-505 Oeiras (Portugal); Instituto de Tecnologia Química e Biológica (ITQB) – Universidade Nova de Lisboa (UNL), Av. da República, Estação Agronómica Nacional, 2780-157 Oeiras, 5 Portugal (Portugal); Carvalho, G., E-mail: [REQUIMTE/CQFB, Chemistry Department, FCT, Universidade Nova de Lisboa, 2829-516 Caparica (Portugal); Instituto de Biologia Experimental e Tecnológica (IBET), Av. da República (EAN), 2784-505 Oeiras (Portugal); Soeiro, R. [REQUIMTE/CQFB, Chemistry Department, FCT, Universidade Nova de Lisboa, 2829-516 Caparica (Portugal); Gaffney, V.; Almeida, C. [Institute for Medicines and Pharmaceutical Sciences (iMed.UL), Faculdade de Farmácia da Universidade de Lisboa (FFUL), Av. Prof. Gama Pinto, 1600-049 Lisboa (Portugal); Cardoso, V. Vale; Ferreira, E.; Benoliel, M.J. [Empresa Portuguesa das Águas Livres, S.A., Direcção de Controlo de Qualidade da Água, Laboratório Central, Avenida de Berlim, 15, 1800-031 Lisboa (Portugal); and others


    Highlights: ► Direct UV photolysis of 3 pharmaceuticals in pure and waste water was investigated. ► Ketoprofen has higher photodegradion kinetics, followed by diclofenac and atenolol. ► MP/UV photodegradation products were identified for the 3 compounds. ► Photodegradation pathways were proposed to explain the obtained products. ► The persistent photoproducts were identified for each compound. -- Abstract: Pharmaceutical compounds such as ketoprofen, diclofenac and atenolol are frequently detected at relatively high concentrations in secondary effluents from wastewater treatment plants. Therefore, it is important to assess their transformation kinetics and intermediates in subsequent disinfection processes, such as direct ultraviolet (UV) irradiation. The photodegradation kinetics of these compounds using a medium pressure (MP) lamp was assessed in pure water, as well as in filtered and unfiltered treated wastewater. Ketoprofen had the highest time- and fluence-based rate constants in all experiments, whereas atenolol had the lowest values, which is consistent with the corresponding decadic molar absorption coefficient and quantum yield. The fluence-based rate constants of all compounds were evaluated in filtered and unfiltered wastewater matrices as well as in pure water. Furthermore, transformation products of ketoprofen, diclofenac and atenolol were identified and monitored throughout the irradiation experiments, and photodegradation pathways were proposed for each compound. This enabled the identification of persistent transformation products, which are potentially discharged from WWTP disinfection works employing UV photolysis.

  10. Visible light photocatalytic water disinfection and its kinetics using Ag-doped titania nanoparticles. (United States)

    Younas, Hassan; Qazi, Ishtiaq A; Hashmi, Imran; Awan, M Ali; Mahmood, Asif; Qayyum, Hafiz Adil


    The UN estimated about five million deaths every year due to water-borne diseases, accounting from four billion patients. Keeping in view, the ever increasing health issues and to undermine this statistics, a reliable and sustainable water-treatment method has been developed using visible light for water treatment. titania nanoparticles (NPs) have been synthesized successfully by a more applicable method Viz: liquid impregnation (LI) method. The bacterial death rate by photocatalysis under visible light was studied by employing a typical fluorescent source and was found to follow pseudo first-order reaction kinetics. The nanoparticles were characterized using X-ray diffraction (XRD), scanning electron microscopy, and energy-dispersive X-ray spectroscopy to deduce their size range, surface morphology, and elemental compositions, respectively. Among all the prepared grades, 1% Ag-TiO2 was found to be a very effective photocatalytic agent against Escherichia coli. The resulted photoinactivated data were also evaluated by different empirical kinetic models for bacterial inactivation. Hom, Hom-power, Rational, and Selleck models were not able to explain the disinfection kinetics but modified-Hom model fitted best with the experimentally obtained data by producing a shoulder, log-linear, and a tail region.

  11. Kinetics of natural organic matter (NOM) removal during drinking water biofiltration using different NOM characterization approaches. (United States)

    Chen, Fei; Peldszus, Sigrid; Elhadidy, Ahmed M; Legge, Raymond L; Van Dyke, Michele I; Huck, Peter M


    To better understand biofiltration, concentration profiles of various natural organic matter (NOM) components throughout a pilot-scale drinking water biofilter were investigated using liquid chromatography - organic carbon detection (LC-OCD) and fluorescence excitation and emission matrices (FEEM). Over a 2 month period, water samples were collected from six ports at different biofilter media depths. Results showed substantial removal of biopolymers (i.e. high molecular weight (MW) NOM components as characterized by LC-OCD) and FEEM protein-like materials, but low removal of humic substances, building blocks and low MW neutrals and low MW acids. For the first time, relative biodegradability of different NOM components characterized by LC-OCD and FEEM approaches were investigated across the entire MW range and for different fluorophore compositions, in addition to establishing the biodegradation kinetics. The removal kinetics for FEEM protein-like materials were different than for the LC-OCD-based biopolymers, illustrating the complementary nature of the LC-OCD and FEEM approaches. LC-OCD biopolymers (both organic carbon and organic nitrogen) and FEEM protein-like materials were shown to follow either first or second order biodegradation kinetics. Due to the low percent removal and small number of data points, the performance of three kinetic models was not distinguishable for humic substances. Pre-filtration of samples for FEEM analyses affected the removal behaviours and/or kinetics especially of protein-like materials which was attributed to the removal of the colloidal/particulate materials. Copyright © 2016 Elsevier Ltd. All rights reserved.

  12. Concerted proton-coupled electron transfers in aquo/hydroxo/oxo metal complexes: electrochemistry of [OsII(bpy)2py(OH2)]2+ in water. (United States)

    Costentin, Cyrille; Robert, Marc; Savéant, Jean-Michel; Teillout, Anne-Lucie


    Kinetic analysis of the successive oxidative cyclic voltammetric responses of [Os(II)(bpy)(2)py(OH(2))](2+) in buffered water, together with determination of H/D isotope effects, has allowed the determination of the mechanisms of the successive proton-coupled electron transfers that convert the Os(II)-aquo complex into the Os(III)-hydroxo complex and the later into the Os(IV)-oxo complex. The stepwise pathways prevail over the concerted pathway in the first case. However, very large concentrations of a base, such as acetate, trigger the beginning of a concerted reaction. The same trend appears, but to a much larger extent, when high local concentration of carboxylates are attached close to the Os complex. The Os(III)-hydroxo/Os(IV)-oxo couple is globally much slower and concerted pathways predominate over the stepwise pathways. Water is, however, not an appropriate proton acceptor in this respect. Other bases, such as citrate or phosphate, are instead quite effective for triggering concerted pathways. Here, we suggest factors causing these contrasting behaviors, providing a practical illustration of the prediction that concerted processes are an efficient way of avoiding high-energy intermediates. Observation of a strong decelerating effect of inactive ions together with the positive role of high local concentrations of carboxylates to initiate a concerted route underscores the variety of structural and medium factors that may operate to modulate and control the occurrence of concerted pathways. These demonstrations and analyses of the occurrence of concerted pathways in an aquo-hydroxo-oxo series are expected to serve as guidelines for studies in term of methodology and factor analysis.

  13. Employing Hot Wire Anemometry to Directly Measure the Water Balance in a Proton Exchange membrane Fuel Cell

    DEFF Research Database (Denmark)

    Shakhshir, Saher Al; Hussain, Nabeel; Berning, Torsten


    Water management in proton exchange membrane fuel cells (PEMFC’s) remains a critical problem for their durability, cost, and performance. Because the anode side of this fuel cell has the tendency to become dehydrated, measuring the water balance can be an important diagnosis tool during fuel cell...... operation. The water balance indicates how much of the product water leaves at the anode side versus the cathode side. Previous methods of determining the fuel cell water balance often relied on condensing the water in the exhaust gas streams and weighing the accumulated mass which is a time consuming...... process that has limited accuracy. Currently, our group is developing a novel method to accurately determine the water balance in a PEMFC in real time by employing hot-wire anemometry. The amount of heat transferred from the wire to the anode exhaust stream can be translated into a voltage signal which...

  14. Water absorption and biodegradation kinetics of highly filled EOC-FS biocomposites (United States)

    Zykova, A. K.; Pantyukhov, P. V.; Platov, Yu. T.; Bobojonova, G. A.; Ramos, C. Chaverri; Popov, A. A.


    The paper analyzes the water absorption and biodegradation kinetics in highly filled biocomposites based on ethylene-octene copolymer (EOC) and oil flax straw (FS). It is shown that adding the filler to EOC increases the water absorption from 0 to 22%. The tendency can be explained both by the low interfacial adhesion of EOC to FS and by the hydrophilic nature of the filler. According to biodegradation tests (10 months), the mass of pure EOC remains unchanged, suggesting that it fails to biodegrade in the environment. Increasing the filler content increases the weight loss of the composites and the degree of microbiological contamination (fungi filaments, bacteria) as evidenced by optical microscopy.

  15. Quantification of Water-Soluble Metabolites in Medicinal Mushrooms Using Proton NMR Spectroscopy. (United States)

    Lo, Yu-Chang; Chien, Shih-Chang; Mishchuk, Darya O; Slupsky, Carolyn M; Mau, Jeng-Leun


    The water-soluble metabolites in 5 mushrooms were identified and quantified using proton nuclear magnetic resonance (NMR) spectroscopy and software for targeted metabolite detection and quantification. In total, 35 compounds were found in Agaricus brasiliensis, 25 in Taiwanofungus camphoratus, 23 in Ganoderma lucidum (Taiwan) and Lentinus edodes, and 16 in G. lucidum (China). Total amounts of all identified metabolites in A. brasiliensis, T. camphoratus, G. lucidum, G. lucidum (China), and L. edodes were 149,950.51, 12,834.18, 9,549.09, 2,788.41, and 111,726.51 mg/kg dry weight, respectively. These metabolites were categorized into 4 groups: free amino acids and derivatives, carbohydrates, carboxylic acids, and nucleosides. Carbohydrates were the most abundant metabolites among all 4 groups, with mannitol having the highest concentration among all analyzed metabolites (848-94,104 mg/kg dry weight). Principal components analysis (PCA) showed obvious distinction among the metabolites of the 5 different kinds of mushrooms analyzed in this study. Thus PCA could provide an optional analytical way of identifying and recognizing the compositions of flavor products. Furthermore, the results of this study demonstrate that NMRbased metabolomics is a powerful tool for differentiating between various medicinal mushrooms.

  16. High-dimensional neural network potentials for solvation: The case of protonated water clusters in helium (United States)

    Schran, Christoph; Uhl, Felix; Behler, Jörg; Marx, Dominik


    The design of accurate helium-solute interaction potentials for the simulation of chemically complex molecules solvated in superfluid helium has long been a cumbersome task due to the rather weak but strongly anisotropic nature of the interactions. We show that this challenge can be met by using a combination of an effective pair potential for the He-He interactions and a flexible high-dimensional neural network potential (NNP) for describing the complex interaction between helium and the solute in a pairwise additive manner. This approach yields an excellent agreement with a mean absolute deviation as small as 0.04 kJ mol-1 for the interaction energy between helium and both hydronium and Zundel cations compared with coupled cluster reference calculations with an energetically converged basis set. The construction and improvement of the potential can be performed in a highly automated way, which opens the door for applications to a variety of reactive molecules to study the effect of solvation on the solute as well as the solute-induced structuring of the solvent. Furthermore, we show that this NNP approach yields very convincing agreement with the coupled cluster reference for properties like many-body spatial and radial distribution functions. This holds for the microsolvation of the protonated water monomer and dimer by a few helium atoms up to their solvation in bulk helium as obtained from path integral simulations at about 1 K.

  17. Microbial species diversity, community dynamics, and metabolite kinetics of water kefir fermentation. (United States)

    Laureys, David; De Vuyst, Luc


    Water kefir is a sour, alcoholic, and fruity fermented beverage of which the fermentation is started with water kefir grains. These water kefir grains consist of polysaccharide and contain the microorganisms responsible for the water kefir fermentation. In this work, a water kefir fermentation process was followed as a function of time during 192 h to unravel the community dynamics, the species diversity, and the kinetics of substrate consumption and metabolite production. The majority of the water kefir ecosystem was found to be present on the water kefir grains. The most important microbial species present were Lactobacillus casei/paracasei, Lactobacillus harbinensis, Lactobacillus hilgardii, Bifidobacterium psychraerophilum/crudilactis, Saccharomyces cerevisiae, and Dekkera bruxellensis. The microbial species diversities in the water kefir liquor and on the water kefir grains were similar and remained stable during the whole fermentation process. The major substrate, sucrose, was completely converted after 24 h of fermentation, which coincided with the production of the major part of the water kefir grain polysaccharide. The main metabolites of the fermentation were ethanol and lactic acid. Glycerol, acetic acid, and mannitol were produced in low concentrations. The major part of these metabolites was produced during the first 72 h of fermentation, during which the pH decreased from 4.26 to 3.45. The most prevalent volatile aroma compounds were ethyl acetate, isoamyl acetate, ethyl hexanoate, ethyl octanoate, and ethyl decanoate, which might be of significance with respect to the aroma of the end product.

  18. Evaluation of the water-equivalence of plastic materials in low- and high-energy clinical proton beams (United States)

    Lourenço, A.; Shipley, D.; Wellock, N.; Thomas, R.; Bouchard, H.; Kacperek, A.; Fracchiolla, F.; Lorentini, S.; Schwarz, M.; MacDougall, N.; Royle, G.; Palmans, H.


    The aim of this work was to evaluate the water-equivalence of new trial plastics designed specifically for light-ion beam dosimetry as well as commercially available plastics in clinical proton beams. The water-equivalence of materials was tested by computing a plastic-to-water conversion factor, {{H}\\text{pl,\\text{w}}} . Trial materials were characterized experimentally in 60 MeV and 226 MeV un-modulated proton beams and the results were compared with Monte Carlo simulations using the FLUKA code. For the high-energy beam, a comparison between the trial plastics and various commercial plastics was also performed using FLUKA and Geant4 Monte Carlo codes. Experimental information was obtained from laterally integrated depth-dose ionization chamber measurements in water, with and without plastic slabs with variable thicknesses in front of the water phantom. Fluence correction factors, {{k}\\text{fl}} , between water and various materials were also derived using the Monte Carlo method. For the 60 MeV proton beam, {{H}\\text{pl,\\text{w}}} and {{k}\\text{fl}} factors were within 1% from unity for all trial plastics. For the 226 MeV proton beam, experimental {{H}\\text{pl,\\text{w}}} values deviated from unity by a maximum of about 1% for the three trial plastics and experimental results showed no advantage regarding which of the plastics was the most equivalent to water. Different magnitudes of corrections were found between Geant4 and FLUKA for the various materials due mainly to the use of different nonelastic nuclear data. Nevertheless, for the 226 MeV proton beam, {{H}\\text{pl,\\text{w}}} correction factors were within 2% from unity for all the materials. Considering the results from the two Monte Carlo codes, PMMA and trial plastic #3 had the smallest {{H}\\text{pl,\\text{w}}} values, where maximum deviations from unity were 1%, however, PMMA range differed by 16% from that of water. Overall, {{k}\\text{fl}} factors were deviating more from unity than {{H

  19. Evaluation of the water-equivalence of plastic materials in low- and high-energy clinical proton beams. (United States)

    Lourenço, A; Shipley, D; Wellock, N; Thomas, R; Bouchard, H; Kacperek, A; Fracchiolla, F; Lorentini, S; Schwarz, M; MacDougall, N; Royle, G; Palmans, H


    The aim of this work was to evaluate the water-equivalence of new trial plastics designed specifically for light-ion beam dosimetry as well as commercially available plastics in clinical proton beams. The water-equivalence of materials was tested by computing a plastic-to-water conversion factor, [Formula: see text]. Trial materials were characterized experimentally in 60 MeV and 226 MeV un-modulated proton beams and the results were compared with Monte Carlo simulations using the FLUKA code. For the high-energy beam, a comparison between the trial plastics and various commercial plastics was also performed using FLUKA and Geant4 Monte Carlo codes. Experimental information was obtained from laterally integrated depth-dose ionization chamber measurements in water, with and without plastic slabs with variable thicknesses in front of the water phantom. Fluence correction factors, [Formula: see text], between water and various materials were also derived using the Monte Carlo method. For the 60 MeV proton beam, [Formula: see text] and [Formula: see text] factors were within 1% from unity for all trial plastics. For the 226 MeV proton beam, experimental [Formula: see text] values deviated from unity by a maximum of about 1% for the three trial plastics and experimental results showed no advantage regarding which of the plastics was the most equivalent to water. Different magnitudes of corrections were found between Geant4 and FLUKA for the various materials due mainly to the use of different nonelastic nuclear data. Nevertheless, for the 226 MeV proton beam, [Formula: see text] correction factors were within 2% from unity for all the materials. Considering the results from the two Monte Carlo codes, PMMA and trial plastic #3 had the smallest [Formula: see text] values, where maximum deviations from unity were 1%, however, PMMA range differed by 16% from that of water. Overall, [Formula: see text] factors were deviating more from unity than [Formula: see text] factors

  20. Modeling the Release Kinetics of Poorly Water-Soluble Drug Molecules from Liposomal Nanocarriers

    Directory of Open Access Journals (Sweden)

    Stephan Loew


    Full Text Available Liposomes are frequently used as pharmaceutical nanocarriers to deliver poorly water-soluble drugs such as temoporfin, cyclosporine A, amphotericin B, and paclitaxel to their target site. Optimal drug delivery depends on understanding the release kinetics of the drug molecules from the host liposomes during the journey to the target site and at the target site. Transfer of drugs in model systems consisting of donor liposomes and acceptor liposomes is known from experimental work to typically exhibit a first-order kinetics with a simple exponential behavior. In some cases, a fast component in the initial transfer is present, in other cases the transfer is sigmoidal. We present and analyze a theoretical model for the transfer that accounts for two physical mechanisms, collisions between liposomes and diffusion of the drug molecules through the aqueous phase. Starting with the detailed distribution of drug molecules among the individual liposomes, we specify the conditions that lead to an apparent first-order kinetic behavior. We also discuss possible implications on the transfer kinetics of (1 high drug loading of donor liposomes, (2 attractive interactions between drug molecules within the liposomes, and (3 slow transfer of drugs between the inner and outer leaflets of the liposomes.

  1. Intramolecular Proton Transfer Boosts Water Oxidation Catalyzed by a Ru Complex

    Energy Technology Data Exchange (ETDEWEB)

    Matheu, Roc; Ertem, Mehmed Z.; Benet-Buchholz, Jordi; Coronado, Eugenio; Batista, Victor S.; Sala, Xavier; Llobet, Antoni


    We introduce a new family of complexes with the general formula [Run(tda)(py)2]m+ (n = 2, m = 0, 1; n = 3, m = 1, 2+; n = 4, m = 2, 32+), with tda2– being [2,2':6',2''-terpyridine]-6,6''-dicarboxylate, including complex [RuIV(OH)(tda-κ-N3O)(py)2]+, 4H+, which we find to be an impressive water oxidation catalyst, formed by hydroxo coordination to 32+ under basic conditions. The complexes are synthesized, isolated, and thoroughly characterized by analytical, spectroscopic (UV–vis, nuclear magnetic resonance, electron paramagnetic resonance), computational, and electrochemical techniques (cyclic voltammetry, differential pulse voltammetry, coulometry), including solid-state monocrystal X-ray diffraction analysis. In oxidation state IV, the Ru center is seven-coordinated and diamagnetic, whereas in oxidation state II, the complex has an unbonded dangling carboxylate and is six-coordinated while still diamagnetic. With oxidation state III, the coordination number is halfway between the coordination of oxidation states II and IV. Species generated in situ have also been characterized by spectroscopic, computational, and electrochemical techniques, together with the related species derived from a different degree of protonation and oxidation states. 4H+ can be generated potentiometrically, or voltammetrically, from 32+, and both coexist in solution. While complex 32+ is not catalytically active, the catalytic performance of complex 4H+ is characterized by the foot of the wave analysis, giving an impressive turnover frequency record of 8000 s–1 at pH 7.0 and 50 000 s–1 at pH 10.0. Density functional theory calculations provide a complete description of the water oxidation catalytic cycle of 4H+, manifesting the key functional role of the dangling carboxylate in lowering the activation free energies that lead to O–O bond formation.

  2. Superacidity in Nafion/MOF Hybrid Membranes Retains Water at Low Humidity to Enhance Proton Conduction for Fuel Cells. (United States)

    Patel, Hasmukh A; Mansor, Noramalina; Gadipelli, Srinivas; Brett, Dan J L; Guo, Zhengxiao


    A hybrid membrane of superacid sulfated Zr-MOF (SZM) and Nafion shows much superior performance to Nafion, particularly for fuel cell operating under low humidity. The Brønsted acidic sites in SZM networks retain an ample amount of water which facilitated proton conduction under low humidity. The water retention properties of Nafion-SZM hybrid membranes with 1 wt % loading of SZM increased at 35% relative humidity and outperformed commercial unfilled Nafion membrane. The proton conductivity increases by 23% for Nafion-SZM hybrid compared to unfilled Nafion membrane. The Nafion-SZM membrane also shows higher performance stability at 35% relative humidity than Nafion, as confirmed by close monitoring of the change of open circuit voltage for 24 h.

  3. Proton therapy (United States)

    Proton beam therapy; Cancer - proton therapy; Radiation therapy - proton therapy; Prostate cancer - proton therapy ... that use x-rays to destroy cancer cells, proton therapy uses a beam of special particles called ...

  4. Aqueous photochemical degradation of hydroxylated PAHs: Kinetics, pathways, and multivariate effects of main water constituents

    Energy Technology Data Exchange (ETDEWEB)

    Ge, Linke; Na, Guangshui [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China); Chen, Chang-Er [Lancaster Environment Centre, Lancaster University, Lancaster LA1 4YQ (United Kingdom); Li, Jun [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China); College of Marine Science, Shanghai Ocean University, Shanghai 201306 (China); Ju, Maowei; Wang, Ying; Li, Kai [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China); Zhang, Peng, E-mail: [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China); Yao, Ziwei [Key Laboratory for Ecological Environment in Coastal Areas (SOA), National Marine Environmental Monitoring Center, Dalian 116023 (China)


    Hydroxylated polycyclic aromatic hydrocarbons (OH-PAHs) are contaminants of emerging concern in the aquatic environment, so it is of great significance to understand their environmental transformation and toxicity. This study investigated the aqueous photochemical behavior of four OH-PAHs, 9-Hydroxyfluorene (9-OHFL), 2-Hydroxyfluorene, 9-Hydroxyphenanthrene and 1-Hydroxypyrene, under simulated sunlight irradiation (λ > 290 nm). It was observed that their photodegradation followed the pseudo-first-order kinetics. Based on the determined quantum yields, their calculated solar apparent photodegradation half-lives in surface waters at 45° N latitude ranged from 0.4 min for 9-Hydroxyphenanthrene to 7.5 × 10{sup 3} min for 9-OHFL, indicating that the OH-PAHs would intrinsically photodegrade fast in sunlit surface waters. Furthermore, 9-OHFL as an example was found to undergo direct photolysis, and self-sensitized photooxidation via ·OH rather than {sup 1}O{sub 2} in pure water. The potential photoreactions involved photoinduced hydroxylation, dehydrogenation and isomerization based on product identification by GC–MS/MS. 9-OHFL photodegraded slower in natural waters than in pure water, which was attributed to the integrative effects of the most photoreactive species, such as Fe(III), NO{sub 3}{sup −}, Cl{sup −} and humic acid. The photomodified toxicity was further examined using Vibrio fischeri, and it was found that the toxicity of photolyzed 9-OHFL did not decrease significantly (p > 0.05) either in pure water or in seawater, implying the comparable or higher toxicity of some intermediates. These results are important for assessing the fate and risks of OH-PAHs in surface waters. - Graphical abstract: Aqueous photochemical behavior of 4 hydroxylated PAHs is first reported on revealing the kinetics, mechanisms, toxicity, and multivariate effects of water constituents. - Highlights: • It is first reported on aqueous photochemical behavior of 4 hydroxylated

  5. PREFACE: Transport phenomena in proton conducting media Transport phenomena in proton conducting media (United States)

    Eikerling, Michael


    , charge-bearing species at interfaces and porous host materials on proton transport properties. As a common thread, articles in this special issue contribute to understanding the functionality provided by complex materials, beyond hydrogen bond fluctuations in water. The first group of articles (Smirnov et al, Henry et al, Medvedev and Stuchebrukhov) elucidates various aspects of the impact of local structural fluctuations, hydrogen bonding and long-range electrostatic forces on proton transfer across and at the surface of mitochondrial membranes. The second group of articles (Ilhan and Spohr, Allahyarov et al and Idupulapati et al) employ molecular dynamics simulations to rationalize vital dependencies of proton transport mechanisms in aqueous-based polymer electrolyte membranes on the nanoporous, phase-separated ionomer morphology, and on the level of hydration. The articles by Gebel et al, Boillat et al, and Aleksandrova et al employ small angle neutron scattering, neutron radiography, and electrochemical atomic force microscopy, respectively, to obtain detailed insights into the kinetics of water sorption, water distribution, water transport properties, as well as spatial maps of proton conductivity in fuel cell membranes. The contribution of Paschos et al provides a comprehensive review of phosphate-based solid state protonic conductors for intermediate temperature fuel cells. The topic of proton conductive materials for high-temperature, water-free operation of fuel cells is continued in the article of Verbraeken et al which addresses synthesis and characterization of a proton conducting perovskite. The guest editor wishes to acknowledge and thank all contributing authors for their commitment to this special issue. Moreover, I would like to thank the staff at IOP Publishing for coordinating submission and refereeing processes. Finally, for the readers, I hope that this special issue will be a valuable and stimulating source of insights into the versatile and

  6. Kinetics of acrylamide formation/elimination reactions as affected by water activity. (United States)

    De Vleeschouwer, Kristel; Van der Plancken, Iesel; Van Loey, Ann; Hendrickx, Marc E


    The influence of water activity on the kinetics of acrylamide formation and elimination reaction was investigated using low-moisture equimolar asparagine-glucose model systems, which were heated at temperatures between 120 and 200 degrees C for variable heating times. To determine the water content corresponding to the water activities tested, a sorption moisture isotherm was constructed experimentally. The acrylamide concentrations measured at different water activities could be modeled on the basis of a reaction scheme including not only acrylamide formation and elimination reactions but also an alternative Maillard reaction between both reactants. The corresponding rate constants and activation energies were estimated using nonlinear regression analysis. Whereas the rate constant for acrylamide formation varied only slightly with the initial water activity of the model system, the elimination rate constant showed a clear minimum around a water activity of 0.82. The opposite trend, namely, a maximum at a water activity of 0.82, was found for the Maillard reaction rate constant as a function of water activity, which confirms data from literature. The activation energies for the different reactions changed in a comparable way as the corresponding rate constant with water activity.

  7. Low-energy proton stopping power of N2, O2 and water vapor and deviations from Bragg's rule (United States)

    Xu, Y. J.; Khandelwal, G. S.; Wilson, J. W.


    A modified local plasma model, based on the works of Lindhard and Winther; and Bethe, Brown, and Walske, is established. The Gordon-Kim model for molecular electron density is used to calculate stopping power of N2, O2, and water vapor for protons of energy ranging from 40 keV to 2.5 MeV, resulting in good agreement with experimental data. Deviations from Bragg's rule are evaluated and are discussed under the present theoretical model.


    Directory of Open Access Journals (Sweden)

    M.J. Carmo


    Full Text Available Improving adsorptive processes demands a constant search for new adsorbents. In the specific case of ethanol-water separation, A zeolites are successfully being used. The use of nonconventional adsorbents to substitute zeolites, mainly starchy adsorbents in virtue of their known chemical affinity water, has recently been proposed. In this work a thermodynamic and kinetic study has been undertaken on the liquid phase adsorption of water from an ethanol-water mixture using manioc starch pellets as the adsorbent. The fundamental thermodynamic data were obtained by means of the static method, using a thermostated bath at four different temperatures (25, 40, 50 and 60° C, and could be correlated by means of a semi-empirical isotherm. The kinetic data, in turn, were obtained in a finite circulating liquid bath cell, enabling the construction of uptake rate curves, whereby the influence of temperature, interstitial velocity and adsorbent mean particle size on the adsorption rate was analyzed. The effective internal diffusivities at the experimental temperatures were estimated by a pore diffusion model and the results obtained were compared with those for commercial 3A zeolite

  9. Size Effect of Silica Shell on Gas Uptake Kinetics in Dry Water. (United States)

    Li, Yong; Zhang, Diwei; Bai, Dongsheng; Li, Shujing; Wang, Xinrui; Zhou, Wei


    Two kinds of dry water (DW) particles are prepared by mixing water and hydrophobic silica particles with nanometer or micrometer dimensions, and the two DW particles are found to have similar size distributions regardless of the size of the silica shell. The CO2 uptake kinetics of DW with nanometer (nanoshell) and micrometer shells (microshell) are measured, and both uptake rate and capacity show the obvious size effect of the silica shell. The DW with a microshell possesses a larger uptake capacity, whereas the DW with a nanoshell has a faster uptake rate. By comparing the uptake kinetics of soluble NH3 and CO2 further, we found that the microshell enhances the stability and the dispersion degree of DW and the nanoshell offers a shorter path for the transit of guest gas into the water core. Furthermore, molecular dynamics simulation is introduced to illustrate the nanosize effect of the silica shell on the initial step of the gas uptake. It is found that the concentration of gas molecules close to the silica shell is higher than that in the bulk water core. With the increase in the size of the silica shell, the amount of CO2 in the silica shell decreases, and it is easier for the gas uptake to reach steady state.


    Directory of Open Access Journals (Sweden)

    Edyta Anna Kudlek


    Full Text Available The paper presents an assessment of the removal degree of selected polycyclic aromatic hydrocarbons (anthracene, benzo(apyrene, xenoestrogens (octylphenol, pentachlorophenol and pharmaceutical compounds (diclofenac in the process of heterogeneous photocatalysis of their water solutions, which were prepared on the base of deionized water. Titanium dioxide at a dose of 100 mg/dm3 was used as a photocatalyst of the process. The kinetics of the process was determined based on the Langmuir-Hinsherlwood equation, assuming the pseudo-first-order reaction of micropollutants decomposition. Furthermore a toxicological analysis of water samples of test compounds was performed by the use of the Microtox® test. It has been found that the micropollutant concentrations decreased with the increase of process time and their removal degree after 60 minutes exceeds 90%. The analysis of the proces kinetic showed that the oxidation of the compounds occurred with the greatest intensity in the first stage of the process up to 10 min. The preformed toxicological assessment confirmed the incomplete decomposition of pollutants and the generation of by-products, which contribute to the increase of the toxicity of treated water solutions.

  11. Kinetics of marine surfactant adsorption at an air water interface. Baltic Sea studies

    Directory of Open Access Journals (Sweden)

    Stanis³aw J. Pogorzelski


    Full Text Available The paper contains the results of studies of natural surface film adsorption kinetics carried out in inland waters and in shallow offshore regions of the Baltic Sea during 2000-01 under calm sea conditions. The novel approach presented here for the adsorption dynamics is based on the mixed kinetic-diffusion model and analyses of the surface pressure-time plots at short (t ->0 and long( t -> ∞ adsorption time intervals. Values of the effective relative diffusion coefficient Deff / D (= 0.008-0.607 and energy barrier for adsorption Ea / RT (= 0.49-7.10 agree well with the data reported for model non-ionic surfactant solutions of pre-cmc concentrations. Wind speed is one of the factors affecting the adsorption barrier via the increased surface pressure of the natural film exposed to wind shear stress (~ U102, and enters the relation Ea / RT = 1.70 U101/3.

  12. Kinetic, isotherm and thermodynamic studies of amaranth dye biosorption from aqueous solution onto water hyacinth leaves. (United States)

    Guerrero-Coronilla, Imelda; Morales-Barrera, Liliana; Cristiani-Urbina, Eliseo


    The present study explored the kinetics, equilibrium and thermodynamics of amaranth (acid red 27) anionic dye (AD) biosorption to water hyacinth leaves (LEC). The effect of LEC particle size, contact time, solution pH, initial AD concentration and temperature on AD biosorption was studied in batch experiments. AD biosorption increased with rising contact time and initial AD concentration, and with decreasing LEC particle size and solution pH. Pseudo-second-order chemical reaction kinetics provided the best correlation for the experimental data. Isotherm studies showed that the biosorption of AD onto LEC closely follows the Langmuir isotherm, with a maximum biosorption capacity of about 70 mg g(-1). The thermodynamic parameters confirm that AD biosorption by LEC is non-spontaneous and endothermic in nature. Results indicate that LEC is a strong biosorbent capable of effective detoxification of AD-laden wastewaters. Copyright © 2015 Elsevier Ltd. All rights reserved.

  13. Embedding of Hollow Polymer Microspheres with Hydrophilic Shell in Nafion Matrix as Proton and Water Micro-Reservoir

    Directory of Open Access Journals (Sweden)

    Zhaolin Liu


    Full Text Available Assimilating hydrophilic hollow polymer spheres (HPS into Nafion matrix by a loading of 0.5 wt % led to a restructured hydrophilic channel, composed of the pendant sulfonic acid groups (–SO3H and the imbedded hydrophilic hollow spheres. The tiny hydrophilic hollow chamber was critical to retaining moisture and facilitating proton transfer in the composite membranes. To obtain such a tiny cavity structure, the synthesis included selective generation of a hydrophilic polymer shell on silica microsphere template and the subsequent removal of the template by etching. The hydrophilic HPS (100–200 nm possessed two different spherical shells, the styrenic network with pendant sulfonic acid groups and with methacrylic acid groups, respectively. By behaving as microreservoirs of water, the hydrophilic HPS promoted the Grotthus mechanism and, hence, enhanced proton transport efficiency through the inter-sphere path. In addition, the HPS with the –SO3H borne shell played a more effective role than those with the –CO2H borne shell in augmenting proton transport, in particular under low humidity or at medium temperatures. Single H2-PEMFC test at 70 °C using dry H2/O2 further verified the impactful role of hydrophilic HPS in sustaining higher proton flux as compared to pristine Nafion membrane.

  14. Investigations of water bounded in clam mussels (Mytilius edulis) by nuclear magnetic relaxation for protons; Badanie wody zwiazanej w muszlach omulka (Mytillus edulls) metoda magnetycznej relaksacji dla protonow

    Energy Technology Data Exchange (ETDEWEB)

    Haranczyk, H.; Niziol, J. [Inst. Fizyki, Uniwersytet Jagiellonski, Cracow (Poland); Falniowski, A. [Inst. Zoologii, Uniwersytet Jagiellonski, Cracow (Poland)


    The process of water bounding in clam shells has been investigated by nuclear magnetic relaxation of protons measurements. Decomposition of measured relaxation functions have been done using the specially constructed computer program. 4 refs, 4 figs, 3 tabs.

  15. Employing Hot Wire Anemometry to Directly Measure the Water Balance of a Commercial Proton Exchange Membrane Fuel Cell Stack

    DEFF Research Database (Denmark)

    Shakhshir, Saher Al; Berning, Torsten


    and increased degradation rates. Clearly, a fundamental understanding of all aspects of water management in PEMFC is imperative. This includes the fuel cell water balance, i.e. which fraction of the product water leaves the fuel cell via the anode channels versus the cathode channel. Our research group...... is currently developing a novel technique to obtain an ad-hoc and real time electrical signal of the fuel cell water balance by employing hot wire anemometry. In this work, the hot wire sensor is placed in the anode outlet of a commercial air-cooled fuel cell stack by Ballard Power Systems, and the voltage......Proton exchange membrane fuel cells (PEMFC’s) are currently being commercialized for various applications ranging from automotive (e.g. the Toyota Mirai) to stationary such as powering telecom backup units. In PEMFC’s, oxygen from air is internally combined with hydrogen to form water and produce...

  16. Kinetics of SO2-ethanol-water (AVAP®) fractionation of sugarcane straw. (United States)

    You, Xiang; van Heiningen, Adriaan; Sixta, Herbert; Iakovlev, Mikhail


    Kinetics of SO2-ethanol-water (AVAP®) fractionation was determined for sugarcane (SC) straw in terms of pulp composition (non-carbohydrate components, cellulose, hemicelluloses) and properties (kappa number, pulp intrinsic viscosity in CED and cellulose degree of polymerization). Effect of temperature (135-165°C) and time (18-118min) was studied at fixed liquor composition (SO2/ethanol/water=12:22.5:65.5, w/w) and a liquor-to-solid ratio (4Lkg(-1)). Interpretation is given in terms of major fractionation reactions, removal of non-carbohydrate components and xylan, as well as acid hydrolysis of cellulose, and is compared to other lignocellulosic substrates (beech, spruce and wheat straw). Overall, SO2-ethanol-water process efficiently fractionates SC straw by separating cellulose from both non-carbohydrate components and xylan while reducing cellulose DP. Copyright © 2016 Elsevier Ltd. All rights reserved.

  17. Effect of fulvic acid on the kinetics of aluminum fluoride complexation in acidic waters

    Energy Technology Data Exchange (ETDEWEB)

    Plankey, B.J.; Patterson, H.H.


    Both fluoride ion and fulvic acid are important aluminum binding ligands present in soil and surface waters. As such they play a role in the speciation and toxicity of natural waters that have increased aluminum concentration due to acid precipitation. We report here a kinetic study of aluminum complexation in the presence of both of these naturally occurring ligands. An overall mechanism has been identified and rate constants have been obtained for several of the reactions involved. We find that an a priori model of the two ligands in competition for aluminum is incorrect. In fact, the rate of fluoride ion consumption is increased by the presence of fulvic acid. Evidence is presented that this effect is due to several equilibria, some of which involve mixed-ligand species. The important equilibria in this three-component system are identified and discussed, as are aluminum speciation and toxicity in acidic waters.

  18. On the collective network of ionic liquid/water mixtures. IV. Kinetic and rotational depolarization. (United States)

    Schröder, Christian; Sega, Marcello; Schmollngruber, Michael; Gailberger, Elias; Braun, Daniel; Steinhauser, Othmar


    Dielectric spectroscopy is a measure of the collective Coulomb interaction in liquid systems. Adding ionic liquids to an aqueous solution results in a decrease of the static value of the generalized dielectric constant which cannot be attributed to kinetic depolarization models characterized by the static conductivity and rotational relaxation constant. However, a dipolar Poisson-Boltzmann model computing the water depolarization in the proximity of ions is not only successful for simple electrolytes but also in case of molecular ionic liquids. Moreover, our simple geometric hydration model is also capable to explain the dielectric depolarization. Both models compute the dielectric constant of water and obtain the overall dielectric constant by averaging the values of its components, water and the ionic liquid, weighted by their volume occupancies. In this sense, aqueous ionic liquid mixtures seem to behave like polar mixtures.

  19. Studies on kinetics of water quality factors to establish water transparency model in Neijiang River, China. (United States)

    Li, Ronghui; Pan, Wei; Guo, Jinchuan; Pang, Yong; Wu, Jianqiang; Li, Yiping; Pan, Baozhu; Ji, Yong; Ding, Ling


    The basis for submerged plant restoration in surface water is to research the complicated dynamic mechanism of water transparency. In this paper, through the impact factor analysis of water transparency, the suspended sediment, dissolved organic matter, algae were determined as three main impactfactors for water transparency of Neijiang River in Eastern China. And the multiple regression equation of water transparency and sediment concentration, permanganate index, chlorophyll-a concentration was developed. Considering the complicated transport and transformation of suspended sediment, dissolved organic matter and algae, numerical model of them were developed respectively for simulating the dynamic process. Water transparency numerical model was finally developed by coupling the sediment, water quality, and algae model. These results showed that suspended sediment was a key factor influencing water transparency of Neijiang River, the influence of water quality indicated by chemical oxygen demand and algal concentration indicated by chlorophyll a were indeterminate when their concentrations were lower, the influence was more obvious when high concentrations are available, such three factors showed direct influence on water transparency.

  20. Neutron scattering from myelin revisited: bilayer asymmetry and water-exchange kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Denninger, Andrew R. [Boston College, Chestnut Hill, MA 02467 (United States); Demé, Bruno; Cristiglio, Viviana [Institut Laue–Langevin (ILL), CS 20156, F-38042 Grenoble CEDEX 9 (France); LeDuc, Géraldine [European Synchrotron Radiation Facility (ESRF), CS 40220, F-38043 Grenoble CEDEX 9 (France); Feller, W. Bruce [NOVA Scientific Inc., Sturbridge, MA 01566 (United States); Kirschner, Daniel A., E-mail: [Boston College, Chestnut Hill, MA 02467 (United States)


    The structure of internodal myelin in the rodent central and peripheral nervous systems has been determined using neutron diffraction. The kinetics of water exchange in these tissues is also described. Rapid nerve conduction in the central and peripheral nervous systems (CNS and PNS, respectively) of higher vertebrates is brought about by the ensheathment of axons with myelin, a lipid-rich, multilamellar assembly of membranes. The ability of myelin to electrically insulate depends on the regular stacking of these plasma membranes and on the presence of a number of specialized membrane-protein assemblies in the sheath, including the radial component, Schmidt–Lanterman incisures and the axo–glial junctions of the paranodal loops. The disruption of this fine-structure is the basis for many demyelinating neuropathies in the CNS and PNS. Understanding the processes that govern myelin biogenesis, maintenance and destabilization requires knowledge of myelin structure; however, the tight packing of internodal myelin and the complexity of its junctional specializations make myelin a challenging target for comprehensive structural analysis. This paper describes an examination of myelin from the CNS and PNS using neutron diffraction. This investigation revealed the dimensions of the bilayers and aqueous spaces of myelin, asymmetry between the cytoplasmic and extracellular leaflets of the membrane, and the distribution of water and exchangeable hydrogen in internodal multilamellar myelin. It also uncovered differences between CNS and PNS myelin in their water-exchange kinetics.

  1. Kinetics of passivation of a nickel-base alloy in high temperature water

    Energy Technology Data Exchange (ETDEWEB)

    Machet, A. [Laboratoire de Physico-Chimie des Surfaces, CNRS-ENSCP (UMR 7045), Ecole Nationale Superieure de Chimie de Paris, Universite Pierre et Marie Curie, F-75231 Paris cedex 05 (France)]|[Framatome ANP, Tour AREVA, F-92084 Paris-la-Defense (France); Galtayries, A.; Zanna, S.; Marcus, P. [Laboratoire de Physico-Chimie des Surfaces, CNRS-ENSCP (UMR 7045), Ecole Nationale Superieure de Chimie de Paris, Universite Pierre et Marie Curie, F-75231 Paris cedex 05 (France); Jolivet, P.; Scott, P. [Framatome ANP, Tour AREVA, F-92084 Paris-la-Defense (France); Foucault, M.; Combrade, P. [Framatome ANP, Centre Technique, F-71205 Le Creusot (France)


    The kinetics of passivation and the composition of the surface oxide layer, in high temperature and high pressure water, of a nickel-chromium-iron alloy (Alloy 600) have been investigated by X-ray Photoelectron Spectroscopy (XPS). The samples have been exposed for short (0.4 - 8.2 min) and longer (0 - 400 hours) time periods to high temperature (325 deg. C) and high pressure water (containing boron and lithium) under controlled hydrogen pressure. The experiments were performed in two types of autoclaves: a novel autoclave dedicated to short time periods and a classic static autoclave for the longer exposures. In the initial stage of passivation, a continuous ultra-thin layer of chromium oxide (Cr{sub 2}O{sub 3}) is rapidly formed on the surface with an external layer of chromium hydroxide. For longer times of passivation, the oxide layer is in a duplex form with an internal chromium oxide layer and an external layer of nickel hydroxide. The growth of the internal Cr{sub 2}O{sub 3} oxide layer has been fitted by three classical models (parabolic, logarithmic and inverse logarithmic laws) for the short passivation times, and the growth curves have been extrapolated to longer passivation periods. The comparison with the experimental results reveals that the kinetics of passivation of Alloy 600 in high temperature and high pressure water, for passivation times up to 400 hours, is well fitted by a logarithmic growth law. (authors)

  2. Modeling of Polarization Transfer Kinetics in Protein Hydration Using Hyperpolarized Water. (United States)

    Kim, Jihyun; Liu, Mengxiao; Hilty, Christian


    Water-protein interactions play a central role in protein structure, dynamics, and function. These interactions, traditionally, have been studied using nuclear magnetic resonance (NMR) by measuring chemical exchange and nuclear Overhauser effect (NOE). Polarization transferred from hyperpolarized water can result in substantial transient signal enhancements of protein resonances due to these processes. Here, we use dissolution dynamic nuclear polarization and flow-NMR for measuring the pH dependence of transferred signals to the protein trypsin. A maximum enhancement of 20 is visible in the amide proton region of the spectrum at pH 6.0, and of 47 at pH 7.5. The aliphatic region is enhanced up to 2.3 times at pH 6.0 and up to 2.5 times at pH 7.5. The time dependence of these observed signals can be modeled quantitatively using rate equations incorporating chemical exchange to amide sites and, optionally, intramolecular NOE to aliphatic protons. On the basis of these two- and three-site models, average exchange (kex) and cross-relaxation rates (σ) obtained were kex = 12 s-1, σ = -0.33 s-1 for pH 7.5 and kex = 1.8 s-1, σ = -0.72 s-1 for pH 6.0 at a temperature of 304 K. These values were validated using conventional EXSY and NOESY measurements. In general, a rapid measurement of exchange and cross-relaxation rates may be of interest for the study of structural changes of the protein occurring on the same time scale. Besides protein-water interactions, interactions with cosolvent or solutes can further be investigated using the same methods.

  3. Excited-state proton transfer from pyranine to acetate in methanol

    Indian Academy of Sciences (India)


    This is slower by about two orders of magnitude than that in bulk water (8 × 10. 10. M. –1 ... termolecular reactions observed in bulk water. In the .... mode for the diffusion of the proton to the bulk. To analyse the observed decay characteristics of. HPTS in the presence of acetate, we now use a sim- ple kinetic model. 14,15.

  4. Modeling Adsorption Kinetics (Bio-remediation of Heavy Metal Contaminated Water) (United States)

    McCarthy, Chris

    My talk will focus on modeling the kinetics of the adsorption and filtering process using differential equations, stochastic methods, and recursive functions. The models have been developed in support of our interdisciplinary lab group which is conducting research into bio-remediation of heavy metal contaminated water via filtration through biomass such as spent tea leaves. The spent tea leaves are available in large quantities as a result of the industrial production of tea beverages. The heavy metals bond with the surfaces of the tea leaves (adsorption). Funding: CUNY Collaborative Incentive Research Grant.

  5. Kinetics of Cr(III) and Cr(VI) removal from water by two floating macrophytes. (United States)

    Maine, M A; Hadad, H R; Sánchez, G; Caffaratti, S; Pedro, M C


    The aim of this work was to compare Cr(III) and Cr(VI) removal kinetics from water by Pistia stratiotes and Salvinia herzogii. The accumulation in plant tissues and the effects of both Cr forms on plant growth were also evaluated. Plants were exposed to 2 and 6 mg L(-1) of Cr(III) or Cr(VI) during 30 days. At the end of the experiment, Cr(VI) removal percentages were significantly lower than those obtained for Cr(III) for both macrophytes. Cr(III) removal kinetics involved a fast and a slow component. The fast component was primarily responsible for Cr(III) removal while Cr(VI) removal kinetics involved only a slow process. Cr accumulated principally in the roots. In the Cr(VI) treatments a higher translocation from roots to aerial parts than in Cr(III) treatments was observed. Both macrophytes demonstrated a high ability to remove Cr(III) but not Cr(VI). Cr(III) inhibited the growth at the highest studied concentration of both macrophytes while Cr(VI) caused senescence. These results have important implications in the use of constructed wetlands for secondary industrial wastewater treatment. Common primary treatments of effluents containing Cr(VI) consists in its reduction to Cr(III). Cr(III) concentrations in these effluents are normally below the highest studied concentrations in this work.

  6. Kinetics of Exhaled Carbon Monoxide After Water-pipe Smoking Indoors and Outdoors. (United States)

    Juhasz, Agnes; Pap, Dalma; Barta, Imre; Drozdovszky, Orsolya; Egresi, Andrea; Antus, Balazs


    Despite accumulating evidence about its adverse health effects, water-pipe tobacco smoking has become very popular among youth. The aim of this study was to compare smoke exposure and the kinetics of exhaled carbon monoxide (eCO) between water-pipe and cigarette smokers under different conditions. Using a cross-over study design, changes in eCO and urinary cotinine levels were measured in a cohort of 32 healthy university students after sessions of water-pipe smoking indoors and outdoors. An indoor cigarette smoking session with equal amounts of tobacco was conducted for reference purposes. Both active and passive smokers participated in all sessions. In indoor sessions, we found that among active participants, eCO levels were approximately 7.5-fold higher in water-pipe users than cigarette smokers. eCO levels remained significantly elevated even 10 h after discontinuing water-pipe smoking. Notably, eCO levels in passive water-pipe smokers were in the same range as in active cigarette smokers. Compared with indoor sessions, eCO levels in active water-pipe users were reduced in outdoor environments. Nonetheless, levels were still higher in these subjects than those in active cigarette smokers measured in indoor sessions. Urinary cotinine levels were comparable in active water-pipe and cigarette smokers. Our results suggest that water-pipe smoking is associated with significantly higher toxicant exposure than cigarette smoking even in outdoor environments. Furthermore, even passive, indoor water-pipe smoke exposure may have significant health hazards compared with those of active cigarette smoking. Copyright © 2017 American College of Chest Physicians. Published by Elsevier Inc. All rights reserved.

  7. Water renewal in Montevideo's bay: a two compartments model for tritium kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Suarez-Antola, Roberto, E-mail: [Universidad Catolica del Uruguay (UCU), Montevideo (Uruguay)


    During field work about dynamics and renewal of water in Montevideo's Bay, 100 Ci of tritiated water were evenly distributed in the north-east region of the bay, by a continuous injection of a solution, during 5 hours, from a 200 litres tank, using a peristaltic pump. The whole bay was divided in 20 concentration cells, taking into account available bathymetric charts and corrections from field data obtained in situ. Tritium concentrations (activities per unit volume) and other relevant parameters (temperature, electrical conductivity, etc.) were measured in vertical profiles during three weeks, in the mid-point of each cell, first twice a day and the on a daily basis. Remnant total tritium activity was estimated from cells volumes and midpoint cells activity concentrations. Consistency checks were done. A one compartment model was used to estimate a global renewal time of circa 29 hours. However, the details of the measured tritium kinetics, a careful consideration of bathymetric data, water movements in a tidal environment (measured with drogues, fluorescent tracers and current meters), as well as the results of computer fluid dynamics modelling (in depth averaged) suggests that the bay can be meaningfully divided in two main compartments: a North-East and a South-West compartment. The purpose of this paper is threefold: (1) to describe the construction of a two compartments model for water renewal in Montevideo's Bay, (2) to apply experimental data of tritium kinetics to estimate the parameters of the model, and (3) to discuss the validity of the model and its practical applicability. The meaning of the renewal time of each compartment and its relation with the measured tritium kinetics in each cell is discussed. The perturbations in water circulation and renewal produced by civil works already done or the perturbations that could be expected due to civil works to be done, in relation with Montevideo's harbour, is discussed. The tracer model

  8. A Novel Biosorbent, Water-Hyacinth, Uptaking Methylene Blue from Aqueous Solution: Kinetics and Equilibrium Studies

    Directory of Open Access Journals (Sweden)

    Md. Nasir Uddin


    Full Text Available The adsorption of MB dye from aqueous solution onto HCl acid treated water-hyacinth (H-WH was investigated by carried out batch sorption experiments. The effect of process parameters such as pH, adsorbent dosage, concentrations and contact time, and ionic strength were studied. Adsorption of MB onto H-WH was found highly pH dependent and ionic strength shows negative impact on MB removal. To predict the biosorption isotherms and to determine the characteristic parameters for process design, Langmuir, Freundlich, Temkin, and Halsey isotherms models were utilized to equilibrium data. The adsorption kinetics was tested for pseudo-first-order (PFO, pseudo-second-order (PSO, intraparticle diffusion (IPD, and Bangham’s kinetic models. The Langmuir isotherm model showed the goodness-of-fit among the tested models for equilibrium adsorption of MB over H-WH and indicated the maximum adsorption capacity as 63.30 mg/g. Higher coefficient of determination (R2>0.99 and better agreement between the qe (experimental and qe (calculated values predicted that PSO kinetic model showed the goodness-of-fit for kinetic data along with rate constant 1.66×10-3, 4.42×10-3, and 3.57×10-3 mg·g-1min⁡-1/2⁡, respectively, for the studied concentration range. At the initial stage of adsorption, the overall rate of dye uptake was found to be dominated by external mass transfer, and afterwards, it is controlled by IPD mechanism.

  9. Dynamic Kinetics of Nitrogen Cycle in Groundwater-Surface Water Interaction Zone at Hanford Site (United States)

    Liu, Y.; Liu, C.; Liu, Y.; Xu, F.; Yan, A.; Shi, L.; Zachara, J. M.; Gao, Y.; Qian, W.; Nelson, W.; Fredrickson, J.; Zhong, L.; Thompson, C.


    Nitrogen cycle carried out by microbes is an important geobiological process that has global implications for carbon and nitrogen cycling and climate change. This presentation describes a study of nitrogen cycle in groundwater-surface water interaction zone (GSIZ) at the US Department of Energy's Hanford Site. Groundwater at Hanford sites has long been documented with nitrate contamination. Nearby Columbia River stage changes of up to 3 m every day because of daily discharge fluctuation from upstream Priest Rapids Dam; resulting an exchange of groundwater and surface water in a short time period. Yet, nitrogen cycle in the GSIZ at Hanford Site remains unclear. Column studies have been used to identify nitrogen metabolism pathways and investigate kinetics of nitrogen cycle in groundwater saturated zone, surface water saturated zone, and GSIZ. Functional gene and protein abundances were determined by qPCR and PRISM-SRM (high-pressure, high-resolution separations coupled with intelligent selection and multiplexing for sensitive selected reaction monitoring) to identify key enzymatic reactions and metabolic pathways of nitrogen cycle. The results showed that dissimilatory nitrate reduction to ammonium (DNRA) competed with denitrification under anaerobic conditions, reducing 30% of NO3- to NH4+, a cation strongly retained on the sediments. As dissolved oxygen intruded the anaerobic zone with river water, NH4+ was oxidized to NO3-, increasing the mobility of NO3-. Multiplicative Monod models were established to describe nitrogen cycle in columns fed with O2 depleted synthetic groundwater and O2 saturated synthetic river water, respectively. The two models were then coupled to predict the dynamic kinetics of nitrogen cycle in GSIZ.

  10. Effects of Water Molecule on CO Oxidation by OH: Reaction Pathways, Kinetic Barriers, and Rate Constants. (United States)

    Zhang, Linyao; Yang, Li; Zhao, Yijun; Zhang, Jiaxu; Feng, Dongdong; Sun, Shaozeng


    The water dilute oxy-fuel combustion is a clean combustion technology for near-zero emission power; and the presence of water molecule could have both kinetic and dynamic effects on combustion reactions. The reaction OH + CO → CO 2 + H, one of the most important elementary reactions, has been investigated by extensive electronic structure calculations. And the effects of a single water molecule on CO oxidation have been studied by considering the preformed OH(H 2 O) complex reacts with CO. The results show little change in the reaction pathways, but the additional water molecule actually increases the vibrationally adiabatic energy barriers (V a G ). Further thermal rate constant calculations in the temperature range of 200 to 2000 K demonstrate that the total low-pressure limit rate constant for the water assisted OH(H 2 O) + CO → CO 2 + H 2 O + H reaction is 1-2 orders lower than that of the water unassisted one, which is consistent with the change of V a G . Therefore, the hydrated radical OH(H 2 O) would actually slow down the oxidation of CO. Meanwhile, comparisons show that the M06-2X/aug-cc-pVDZ method gives a much better estimation in energy and thus is recommended to be employed for direct dynamics simulations.

  11. Freezing Temperatures, Ice Nanotubes Structures, and Proton Ordering of TIP4P/ICE Water inside Single Wall Carbon Nanotubes. (United States)

    Pugliese, P; Conde, M M; Rovere, M; Gallo, P


    A very recent experimental paper importantly and unexpectedly showed that water in carbon nanotubes is already in the solid ordered phase at the temperature where bulk water boils. The water models used so far in literature for molecular dynamics simulations in carbon nanotubes show freezing temperatures lower than the experiments. We present here results from molecular dynamics simulations of water inside single walled carbon nanotubes using an extremely realistic model for both liquid and icy water, the TIP4P/ICE. The water behavior inside nanotubes of different diameters has been studied upon cooling along the isobars at ambient pressure starting from temperatures where water is in a liquid state. We studied the liquid/solid transition, and we observed freezing temperatures higher than in bulk water and that depend on the diameter of the nanotube. The maximum freezing temperature found is 390 K, which is in remarkable agreement with the recent experimental measurements. We have also analyzed the ice structure called "ice nanotube" that water forms inside the single walled carbon nanotubes when it freezes. The ice forms observed are in agreement with previous results obtained with different water models. A novel finding, a partial proton ordering, is evidenced in our ice nanotubes at finite temperature.

  12. Modelling of the vapour-liquid equilibrium of water and the in situ concentration of H3PO4 in a high temperature proton exchange membrane fuel cell (United States)

    Kazdal, Timur J.; Lang, Sebastian; Kühl, Frank; Hampe, Manfred J.


    The fuel cell technology is a key element for the hydrogen energy economy and therefore crucial for sustainable development. High temperature proton exchange membrane (HT-PEM) fuel cells (FC) can be operated with reformate gas and thus represent an important bridging technology for the energy transition to a renewable energy based system. HT-PEM FCs based on phosphoric acid (PA) are still subject to intense research, investigating the electrolyte behaviour. By enhancing state of the art 2D FEM simulations of FCs with the vapour liquid equilibrium of water-phosphoric acid and evaporation kinetics, a model was created in which the local concentration of PA can be calculated. Knowledge of the concentration field yields the basis for calculating the locally varying ionic conductivity and other physical properties. By describing the volume expansion behaviour of PA it was possible to predict the catalyst particle deactivation due to the swelling of PA. The in situ concentration predicted by the simulation ranges from 96 to 111 wt%. The model was validated using measured data of a single cell design for different temperatures and pressures. By varying the PA content flooding of the simulated fuel cell could be observed and was linked to humidification effects.

  13. Transformation of acetaminophen during water chlorination treatment: kinetics and transformation products identification. (United States)

    Cao, Fei; Zhang, Mengtao; Yuan, Shoujun; Feng, Jingwei; Wang, Qiquan; Wang, Wei; Hu, Zhenhu


    As a high-consumption drug in the world, acetaminophen (AAP) has been widely detected in natural waters and wastewaters. Its reactivity and the transformation products formed during chlorination may greatly threaten the safety of drinking water. The reaction kinetics of AAP during chlorination was investigated in this study. The results showed that the reaction kinetics could be well described with a kinetics model of -d[AAP]/dt = k app[AAP]t (0.63)[Cl2]t (1.37). The values of apparent rate constant (k app) were dependent on reaction temperature, ammonium, and pH. With the increase in reaction temperature from 5.0 ± 1.0 to 40.0 ± 1.0 °C, the removal efficiency of AAP increased from 60 to 100 %. When ammonium was present in the solution at 2.0 mg/L, the transformation of AAP was inhibited due to the rapid formation of chloramines. The maximum of k app was 0.58 × 10(2) M(-1) · min(-1) at pH 9.0, and the minimum was 0.27 M(-1) · min(-1) at pH 11.0. A low mineralization of AAP (about 7.2 %) with chlorination was observed through TOC analysis, implying the formation of plenty of transformation products during chlorination. The main transformation products, hydroquinone and two kinds of chlorinated compounds, monochlorinated acetaminophen and dichlorinated acetaminophen, were detected in gas chromatography-mass spectrometry analysis.

  14. NH4+ adsorption and adsorption kinetics by sediments in a drinking water reservoir

    Directory of Open Access Journals (Sweden)

    Suna Hongyan


    Full Text Available The sorption isotherm and sorption kinetics of NH4+ by the Fen River reservoir sediment were investigated for a better understanding of the NH4+ sorption characteristics and parameters. The results showed that Q (adsorption content increased with the increase of Ceq (equilibrium concentration, sorption isotherms could be described by Freundlich equation (R2 from 0.97 to 0.99. Cation exchange capacity (CEC had a significant correlation with the parameters K and n (R2 was 0.85 and 0.95, respectively. The ENC0 (Ceq as Q was zero of S1, S2, S3 and S4 was 1.25, 0.57, 1.15 and 1.14 mg L-1, respectively, and they were less than the NH4+ concentrations in reservoir water. The sediments released NH4+ to the Fen River reservoir water and acted as a pollution source, in the form of complex and heterogeneous adsorbents. The NH4+ adsorption kinetic process was composed of ‘fast’ and ‘slow’ reaction patterns and could be fitted using both Elovich equation and Pseudo second-equation. More than one-step may be involved in the NH4+ sorption processes, and interior diffusion was not dominant ion action.

  15. Voltage Gated Ion Channel Function: Gating, Conduction, and the Role of Water and Protons (United States)

    Kariev, Alisher M.; Green, Michael E.


    Ion channels, which are found in every biological cell, regulate the concentration of electrolytes, and are responsible for multiple biological functions, including in particular the propagation of nerve impulses. The channels with the latter function are gated (opened) by a voltage signal, which allows Na+ into the cell and K+ out. These channels have several positively charged amino acids on a transmembrane domain of their voltage sensor, and it is generally considered, based primarily on two lines of experimental evidence, that these charges move with respect to the membrane to open the channel. At least three forms of motion, with greatly differing extents and mechanisms of motion, have been proposed. There is a “gating current”, a capacitative current preceding the channel opening, that corresponds to several charges (for one class of channel typically 12–13) crossing the membrane field, which may not require protein physically crossing a large fraction of the membrane. The coupling to the opening of the channel would in these models depend on the motion. The conduction itself is usually assumed to require the “gate” of the channel to be pulled apart to allow ions to enter as a section of the protein partially crosses the membrane, and a selectivity filter at the opposite end of the channel determines the ion which is allowed to pass through. We will here primarily consider K+ channels, although Na+ channels are similar. We propose that the mechanism of gating differs from that which is generally accepted, in that the positively charged residues need not move (there may be some motion, but not as gating current). Instead, protons may constitute the gating current, causing the gate to open; opening consists of only increasing the diameter at the gate from approximately 6 Å to approximately 12 Å. We propose in addition that the gate oscillates rather than simply opens, and the ion experiences a barrier to its motion across the channel that is tuned

  16. An S-N2-model for proton transfer in hydrogen-bonded systems

    DEFF Research Database (Denmark)

    Kuznetsov, A.M.; Ulstrup, Jens


    A new mechanism of proton transfer in donor-acceptor complexes with long hydrogen bonds is suggested. The transition is regarded as totally adiabatic. Two closest water molecules that move synchronously by hindered translation to and from the reaction complex are crucial. The water molecules induce...... a shift of the proton from the donor to the acceptor with simultaneous breaking/formation of hydrogen bonds between these molecules and the proton donor and acceptor. Expressions for the activation barrier and kinetic hydrogen isotope effect are derived. The general scheme is illustrated with the use...

  17. Microbial pesticide removal in rapid sand filters for drinking water treatment--potential and kinetics. (United States)

    Hedegaard, Mathilde J; Albrechtsen, Hans-Jørgen


    Filter sand samples, taken from aerobic rapid sand filters used for treating groundwater at three Danish waterworks, were investigated for their pesticide removal potential and to assess the kinetics of the removal process. Microcosms were set up with filter sand, treated water, and the pesticides or metabolites mecoprop (MCPP), bentazone, glyphosate and p-nitrophenol were applied in initial concentrations of 0.03-2.4 μg/L. In all the investigated waterworks the concentration of pesticides in the water decreased - MCPP decreased to 42-85%, bentazone to 15-35%, glyphosate to 7-14% and p-nitrophenol 1-3% - from the initial concentration over a period of 6-13 days. Mineralisation of three out of four investigated pesticides was observed at Sjælsø waterworks Plant II - up to 43% of the initial glyphosate was mineralised within six days. At Sjælsø waterworks Plant II the removal kinetics of bentazone revealed that less than 30 min was needed to remove 50% of the bentazone at all the tested initial concentrations (0.1-2.4 μg/L). Increased oxygen availability led to greater and faster removal of bentazone in the microcosms. After 1 h, bentazone removal (an initial bentazone concentration of 0.1 μg/L) increased from 0.21%/g filter sand to 0.75%/g filter sand, when oxygen availability was increased from 0.28 mg O2/g filter sand to 1.09 mg O2/g filter sand. Bentazone was initially cleaved in the removal process. A metabolite, which contained the carbonyl group, was removed rapidly from the water phase and slowly mineralised after 24 h, while a metabolite which contained the benzene-ring was still present in the water phase. However, the microbial removal of this metabolite was initiated over seven days. Copyright © 2013 Elsevier Ltd. All rights reserved.

  18. Controlled release formulations of metribuzin: release kinetics in water and soil. (United States)

    Kumar, Jitendra; Nisar, Keyath; Shakil, N A; Walia, Suresh; Parsad, Rajender


    Controlled release (CR) formulations of metribuzin in Polyvinyl chloride [(PVC) (emulsion)], carboxy methyl cellulose (CMC), and carboxy methyl cellulose-kaolinite composite (CMC-KAO), are reported. Kinetics of its release in water and soil was studied in comparison with the commercial formulation (75 DF). Metribuzin from the commercial formulation became non-detectable after 35 days whereas it attained maxima between 35-49 days and became non-detectable after 63 days in the developed products. Amongst the CR formulations, the release in both water and soil was the fastest in CMC and slowest in PVC. The CMC-KAO composite reduced the rate of release as compared to CMC alone. The diffusion exponent (n value) of metribuzin in water and soil ranged from 0.515 to 0.745 and 0.662 to 1.296, respectively in the various formulations. The release was diffusion controlled with half release time (t(1/2)) from different controlled release matrices of 12.98 to 47.63 days in water and 16.90 to 51.79 days in soil. It was 3.25 and 4.66 days, respectively in the commercial formulation. The period of optimum availability of metribuzin in water and soil from controlled released formulations ranged from 15.09 to 31.68 and 17.99 to 34.72 days as against 5.03 and 8.80 days in the commercial formulation.

  19. Faster Proton dynamics of water on SnO2 compared to TiO2.

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Nitin [ORNL; Kent, Paul R [ORNL; Bandura, Andrei V. [St. Petersburg State University, St. Petersburg, Russia; Kubicki, James D. [Pennsylvania State University; Wesolowski, David J [ORNL; Cole, David R [ORNL; Sofo, Jorge O. [Pennsylvania State University


    Proton jump processes in the hydration layer on the iso-structural TiO2 rutile (110) and SnO2 cassiterite (110) surfaces were studied with density functional theory molecular dynamics. We find that the proton jump rate is more than three times faster on cassiterite compared with rutile. A local analysis based on the correlation between the stretching band of the O H vibrations and the strength of H-bonds indicates that the faster proton jump activity on cassiterite is produced by a stronger H-bond formation between the surface and the hydration layer above the surface. The origin of the increased H-bond strength on cassiterite is a combined effect of stronger covalent bonding and stronger electrostatic interactions due to differences of its electronic structure. The bridging oxygens form the strongest H-bonds between the surface and the hydration layer. This higher proton jump rate is likely to affect reactivity and catalytic activity on the surface. A better understanding of its origins will enable methods to control these rates. 2011 American Institute of Physics. [doi:10.1063/1.3509386

  20. High proton conductivity in cyanide-bridged metal-organic frameworks: understanding the role of water

    NARCIS (Netherlands)

    Gao, Y.; Broersen, R.; Hageman, W.; Yan, N.; Mittelmeijer-Hazeleger, M.; Rothenberg, G.; Tanase, S.


    We investigate and discuss the proton conductivity properties of the cyanide-bridged metal–organic framework (MOF) [Nd(mpca)2Nd(H2O)6Mo(CN)8]·nH2O (where mpca is 5-methyl-2-pyrazinecarboxylate). This MOF is one of an exciting class of cyanide-bridged materials that can combine porosity with

  1. Protein conformational modifications and kinetics of water-protein interactions in milk protein concentrate powder upon aging: effect on solubility. (United States)

    Haque, Enamul; Bhandari, Bhesh R; Gidley, Michael J; Deeth, Hilton C; Møller, Sandie M; Whittaker, Andrew K


    Protein conformational modifications and water-protein interactions are two major factors believed to induce instability of protein and eventually affect the solubility of milk protein concentrate (MPC) powder. To test these hypotheses, MPC was stored at different water activities (a(w) 0.0-0.85) and temperatures (25 and 45 degrees C) for up to 12 weeks. Samples were examined periodically to determine solubility, change in protein conformation by Fourier transform infrared (FTIR) spectroscopy and principal component analysis (PCA), and water status (interaction of water with the protein molecule/surface) by measuring the transverse relaxation time (T(2)) with proton nuclear magnetic resonance ((1)H NMR). The solubility of MPC decreased significantly with aging, and this process was enhanced by increasing water activity (a(w)) and storage temperature. Minor changes in protein secondary structure were observed with FTIR, which indicated some degree of unfolding of protein molecules. PCA of the FTIR data was able to discriminate samples according to moisture content and storage period. Partial least-squares (PLS) analysis showed some correlation between FTIR spectral feature and solubility. The NMR T(2) results indicated the presence of three distinct populations of water molecules, and the proton signal intensity and T(2) values of proton fractions varied with storage conditions (humidity, temperature) and aging. Results suggest that protein/protein interactions may be initiated by unfolding of protein molecules that eventually affects solubility.

  2. The Effect of Inhomogeneous Compression on Water Transport in the Cathode of a Proton Exchange Membrane Fuel Cell

    DEFF Research Database (Denmark)

    Olesen, Anders Christian; Berning, Torsten; Kær, Søren Knudsen


    A three-dimensional, multicomponent, two-fluid model developed in the commercial CFD package CFX 13 (ANSYS Inc.) is used to investigate the effect of porous media compression on water transport in a proton exchange membrane fuel cell (PEMFC). The PEMFC model only consist of the cathode channel, gas....... Furthermore, the presence of irreducible liquid water is taken into account. In order to account for compression, porous media morphology variations are specified based on the gas diffusion layer (GDL) through-plane strain and intrusion which are stated as a function of compression. These morphology...... diffusion layer, microporous layer, and catalyst layer, excluding the membrane and anode. In the porous media liquid water transport is described by the capillary pressure gradient, momentum loss via the Darcy-Forchheimer equation, and mass transfer between phases by a nonequilibrium phase change model...

  3. New limit on the proton life-time independent on channel from the neutrino experiments with heavy water

    CERN Document Server

    Tretyak, V I


    Experimental data on the number of neutrons born in the heavy water targets of the large neutrino detectors are used to set the limit on the proton life-time independently on decay mode through the reaction d -> n + ?. The best up-to-date limit tau sub p > 4x10 sup 2 sup 3 yr with 95% C.L. is derived from the measurements with D sub 2 O target (mass 267 kg) installed near the Bugey reactor. This value can be improved by six orders of magnitude with future data accumulated with the SNO detector containing 1000 t of D sub 2 O.

  4. Employing Hot Wire Anemometry to Directly Measure the Water Balance of a Proton Exchange Membrane Fuel Cell

    DEFF Research Database (Denmark)

    Shakhshir, Saher Al; Berning, Torsten

    Proton exchange membrane fuel cells (PEMFC’s) are currently being commercialized for various applications ranging from automotive to stationary such as powering telecom back-up units. In PEMFC’s, oxygen from air is internally combined with hydrogen to form water and produce electricity and waste...... in hot wire anemometry is the description of the Nusselt number as function of the Reynolds number and the Prandtl number, and in the current application it can be shown it is essential to employ a power-law equation instead of the commonly employed Churchill Bernstein equation. It will be shown...

  5. Kinetics of Zinc and Arsenate Co-sorption at the Geothite-water Interface

    Energy Technology Data Exchange (ETDEWEB)

    Grafe,M.; Sparks, D.


    Little or no information is available in the literature about reaction processes of co-sorbing metals and arsenate [As(V)] on variable-charged surfaces or factors influencing these reactions. Arsenic and metal contamination are, however, a common co-occurrence in many contaminated environments. In this study, we investigated the co-sorption kinetics of 250 {micro}M As(V) and zinc [Zn(II)] in 10, 100, and 1000 mg goethite L{sup -1} 0.01 M NaCl solution at pH 7, collected complementary As and Zn K-edge extended X-ray absorption fine structure (EXAFS) data after various aging times, and performed a replenishment desorption/dissolution study at pH 4 and 5.5 after 6 months of aging time. Arsenate and Zn(II) formed adamite-like and koritnigite-like precipitates on goethite in 100- and 10-ppm goethite suspensions, respectively, whereas in 1000-ppm goethite suspensions, As(V) formed mostly double-corner sharing complexes and Zn(II) formed a solid solution on goethite according to EXAFS spectroscopic analyses. In all goethite suspension densities, surface adsorption reactions were part of the initial reaction processes. In 10- and 100-ppm goethite suspensions, a heterogeneous nucleation reaction occurred in which adamite-like precipitates began to form 48 h earlier than koritnigite-like surface precipitates. Arsenate and Zn(II) uptake from solution decreased after 4 weeks. Replenishment desorption studies showed that the precipitates and surface adsorbed complexes on goethite were susceptible to proton-promoted dissolution resulting in many cases in more than 80% loss of Zn(II) and {approx} 60% to 70% loss of arsenate. The molar Zn:As dissolution ratio was dependent on the structure of the precipitate and was cyclic for the adamite and koritnigite-like surface precipitates, reflecting the concentric and plane-layered structures of adamite and koritnigite, respectively.

  6. Hydration kinetics of direct expanded tef flour breakfast cereals in water and milk (United States)

    Solomon, W K


    Hydration kinetics of tef flour breakfast cereals extruded at barrel temperatures of 110, 130, and 150°C was investigated by hydrating them in water and whole milk at 25°C (±1°C). The normalized Weibull model described the rehydration characteristics of the extrudates in water and milk adequately (R2 = 0.98–0.99). Water absorption rate was significantly (P Hydration rate and equilibrium moisture content were higher for samples hydrated in water than those in milk. In view of the values of the shape parameter β, the hydration process is predominantly controlled by diffusion (β = 0.40–0.51) for samples extruded at 110°C whereas external resistance to mass transfer dominated (β = 0.60–0.73) those extruded using 150 and 130°C. Extrudates processed at 130 and 150°C exhibited better hydration characteristics. Thus, these temperature ranges could be used to produce extruded products from tef. PMID:24804063

  7. Degradation of methiocarb by monochloramine in water treatment: kinetics and pathways. (United States)

    Qiang, Zhimin; Tian, Fang; Liu, Wenjun; Liu, Chao


    The micropollution of drinking water sources with pesticides has become a global concern. This work investigated the degradation of methiocarb (MC), a most commonly-used carbamate pesticide, by monochloramine (NH2Cl) under simulated water treatment conditions. Results indicate that the reaction was of first-order in MC and varied orders in NH2Cl depending on water pH. The observed rate constant of MC degradation decreased quickly with either a decrease in the molar ratio of chlorine to ammonia (Cl2:N) or an increase in water pH. The apparent activation energy of the reaction was determined to be 34 kJ mol(-1). The MC degradation pathways also exhibited a strong pH dependence: at pH 6.5, MC was first oxidized by NH2Cl to methiocarb sulfoxide (MCX), and then hydrolyzed to methiocarb sulfoxide phenol (MCXP); while at pH 8.5, MCX, MCXP and methiocarb sulfone phenol (MCNP) were formed successively through either oxidation or hydrolysis reactions. Based on the identified byproducts and their concentrations evolution, the proposed pathways of MC degradation in the presence of NH2Cl were further validated through kinetic model simulations. Copyright © 2013 Elsevier Ltd. All rights reserved.

  8. Kinetics of Eucalyptus globulus delignification in a methanol-water medium

    Energy Technology Data Exchange (ETDEWEB)

    Gilarranz, M.A.; Rodriguez, F.; Santos, A.; Oliet, M.; Garcia-Ochoa, F.; Tijero, J. [Univ. Complutense, Madrid (Spain). Dept. de Ingenieria Quimica


    The kinetics of Eucalyptus Globulus delignification in methanol-water pulping has been studied. A total of 17 isothermal runs at a liquor-to-wood ratio of 50 L/kg were carried out to develop the kinetic model describing the system. In a first series of experiments, eight models were considered to study the influence of temperature on the delignification rate. The most suitable model, which was discriminated according to statistical criteria, describes delignification as the consecutive dissolution of three lignin species: initial, bulk, and residual lignin, their content in wood being 10, 69, and 21%, respectively. Initial and residual delignification were considered as irreversible reactions and bulk delignification as reversible. The influence of hydrogen ion concentration was taken into account by means of a general power-law expression. The model proposed was taken into account by means of a general power-law expression. The model proposed was validated by reproducing the experimental data from four runs carried out under nonisothermal conditions and a liquor-to-wood ratio of 7 L/kg, which are closer to industrial operating conditions.

  9. Evaluation of uptake kinetics during a wastewater diversion into nearshore coastal waters in southern California (United States)

    Kudela, Raphael M.; Howard, Meredith D. A.; Hayashi, Kendra; Beck, Carly


    The global eutrophication of coastal ecosystems from anthropogenic nutrients is one of the most significant issues affecting changes to coastal oceans today. A three-week diversion of wastewater effluent from the normal offshore discharge pipe (7 km offshore, 56 m depth) to a shorter outfall located in 16 m water (2.2 km offshore) as part of the 2012 Orange County Sanitation District Diversion provided an opportunity to evaluate the impacts of anthropogenic nitrogen on phytoplankton community response. Nitrogen uptake kinetic parameters were used to evaluate the short-term physiological response of the phytoplankton community to the diverted wastewater and to determine if potential ammonium suppression of nitrate uptake was observed. Despite expectations, there was a muted response to the diversion in terms of biomass accumulation and ambient nutrients remained low. At ambient nitrogen concentrations, calculated uptake rates strongly favored ammonium. During the diversion based on the kinetic parameters determined during short-term experiments, the phytoplankton community was using all three N substrates at low concentrations, and had the capacity to use urea, then ammonium, and then nitrate at high concentrations. Ammonium suppression of nitrate uptake was evident throughout the experiment, with increasing suppression through time. Despite this interaction, there was evidence for simultaneous utilization of nitrate, ammonium, and urea during the experiment. The general lack of phytoplankton response as evidenced by low biomass during the diversion was therefore not obviously linked to changes in uptake rates, physiological capacity, or ammonium suppression of nitrate uptake.

  10. Sorption of Arsenic from Desalination Concentrate onto Drinking Water Treatment Solids: Operating Conditions and Kinetics

    Directory of Open Access Journals (Sweden)

    Xuesong Xu


    Full Text Available Selective removal of arsenic from aqueous solutions with high salinity is required for safe disposal of the concentrate and protection of the environment. The use of drinking water treatment solids (DWTS to remove arsenic from reverse osmosis (RO concentrate was studied by batch sorption experiments. The impacts of solution chemistry, contact time, sorbent dosage, and arsenic concentration on sorption were investigated, and arsenic sorption kinetics and isotherms were modeled. The results indicated that DWTS were effective in removing arsenic from RO concentrate. The arsenic sorption process followed a pseudo-second-order kinetic model. Multilayer adsorption was simulated by Freundlich equation. The maximum sorption capacities were calculated to be 170 mg arsenic per gram of DWTS. Arsenic sorption was enhanced by surface precipitation onto the DWTS due to the high amount of calcium in the RO concentrate and the formation of ternary complexes between arsenic and natural organic matter (NOM bound by the polyvalent cations in DWTS. The interactions between arsenic and NOM in the solid phase and aqueous phase exhibited two-sided effects on arsenic sorption onto DWTS. NOM in aqueous solution hindered the arsenic sorption onto DWTS, while the high organic matter content in solid DWTS phase enhanced arsenic sorption.

  11. Kinetic study of hydrolysis of xylan and agricultural wastes with hot liquid water. (United States)

    Zhuang, Xinshu; Yuan, Zhenhong; Ma, Longlong; Wu, Chuangzhi; Xu, Mingzhong; Xu, Jingliang; Zhu, Shunni; Qi, Wei


    We investigated the kinetics of hot liquid water (HLW) hydrolysis over a 60-min period using a self-designed setup. The reaction was performed within the range 160-220 degrees C, under reaction conditions of 4.0 MPa, a 1:20 solid:liquid ratio (g/mL), at 500 rpm stirring speed. Xylan was chosen as a model compound for hemicelluloses, and two kinds of agricultural wastes-rice straw and palm shell-were used as typical feedstocks representative of herbaceous and woody biomasses, respectively. The hydrolysis reactions for the three kinds of materials followed a first-order sequential kinetic model, and the hydrolysis activation energies were 65.58 kJ/mol for xylan, 68.76 kJ/mol for rice straw, and 95.19 kJ/mol for palm shell. The activation energies of sugar degradation were 147.21 kJ/mol for xylan, 47.08 kJ/mol for rice straw and 79.74 kJ/mol for palm shell. These differences may be due to differences in the composition and construction of the three kinds of materials. In order to reduce the decomposition of sugars, the hydrolysis time of biomasses such as rice straw and palm shell should be strictly controlled.

  12. Kinetic modelling of molten carbonate fuel cells: Effects of cathode water and electrode materials (United States)

    Arato, E.; Audasso, E.; Barelli, L.; Bosio, B.; Discepoli, G.


    Through previous campaigns the authors developed a semi-empirical kinetic model to describe MCFC performance for industrial and laboratory simulation. Although effective in a wide range of operating conditions, the model was validated for specific electrode materials and dry feeding cathode compositions. The new aim is to prove that with appropriate improvements it is possible to apply the model to MCFC provided by different suppliers and to new sets of reactant gases. Specifically, this paper describes the procedures to modify the model to switch among different materials and identify a new parameter taking into account the effects of cathode water vapour. The new equation is integrated as the kinetic core within the SIMFC (SIMulation of Fuel Cells) code, an MCFC 3D model set up by the PERT group of the University of Genova, for reliability test. Validation is performed using data collected through tests carried out at the University of Perugia using single cells. The results are discussed giving examples of the simulated performance with varying operating conditions. The final formulation average percentage error obtained for all the simulated cases with respect to experimental results is maintained around 1%, despite the difference between the basic and the new conditions and facilities.

  13. Kinetic Release of Alkalinity from Particle-Containing Oil-in-Water Emulsions (United States)

    Muller, K.; Chapra, S. C.; Ramsburg, A.


    Oil-in-water emulsions are typically employed during remediation to promote biotic reduction of contaminants. Emulsions, however, hold promise for encapsulated delivery of many types of active ingredients required for successful site remediation or long-term site stewardship. Our research is currently focused on using alkalinity-containing particles held within oil-in-water emulsions to sustain control of subsurface pH. Here we describe results from laboratory experiments and mathematical modeling conducted to quantify the kinetics associated with the emulsion delivery and alkalinity release process. Kinetically stable oil-in-water emulsions containing (~60 nmCaCO3 or ~100 nm MgO particles) were previously developed using soybean oil and Gum Arabic as a stabilizing agent. Batch and column experiments were employed to assess the accessibility and release of the alkalinity from the emulsion. Successive additions of HCl were used in batch systems to produce several pH responses (pH rebounds) that were subsequently modeled to elucidate release mechanisms and rates for varying emulsion compositions and particle types. Initial results suggest that a linear-driving-force model is generally able to capture the release behavior in the batch system when the temporally-constant, lumped mass-transfer coefficient is scaled by the fraction of particle mass remaining within the droplets. This result suggests that the rate limiting step in the release process may be the interphase transfer of reactive species at the oil-water interface. 1-d column experiments were also completed in order to quantify the extent and rate of alkalinity release from emulsion droplets retained in a sandy medium. Alkalinity release from the retained droplets treated a pH 4 influent water for 25-60 pore volumes (the duration depended on particle type and mass loading), and the cessation in treatment corresponded to exhaustion of the particle mass held within the oil. Column experiments were simulated

  14. Modeling the kinetics of a photochemical water treatment process by means of artificial neural networks

    Energy Technology Data Exchange (ETDEWEB)

    Goeb, S.; Oliveros, E.; Bossmann, S.H.; Braun, A.M. [Lehrstuhl fuer Umweltmesstechnik, Engler-Bunte-Institut, Universitaet Karlsruhe, Karlsruhe (Germany); Guardani, R.; Nascimento, C.A.O. [Process Control and Simulation Laboratory, Chemical Engineering Department, University of Sao Paulo, Sao Paulo (Brazil)


    We have investigated the kinetics of the degradation of 2,4-dimethyl aniline (2,4-xylidine), chosen as a model pollutant, by the photochemically enhanced Fenton reaction. This process, which may be efficiently applied to the treatment of industrial waste waters, involves a series of complex reactions leading eventually to the mineralization of the organic pollutant. A model based on artificial neural networks has been developed for fitting the experimental data obtained in a laboratory batch reactor. The model can describe the evolution of the pollutant concentration during irradiation time under various conditions. It has been used for simulating the behaviour of the reaction system in sensitivity studies aimed at optimizing the amounts of reactants employed in the process - an iron(II) salt and hydrogen peroxide. The results show that the process is much more sensitive to the iron(II) salt concentration than to the hydrogen peroxide concentration, a favorable condition in terms of economic feasibility. (author)

  15. Oxidation kinetics of model compounds of metabolic waste in supercritical water (United States)

    Webley, Paul A.; Holgate, Henry R.; Stevenson, David M.; Tester, Jefferson W.


    In this NASA-funded study, the oxidation kinetics of methanol and ammonia in supercritical water have been experimentally determined in an isothermal plug flow reactor. Theoretical studies have also been carried out to characterize key reaction pathways. Methanol oxidation rates were found to be proportional to the first power of methanol concentration and independent of oxygen concentration and were highly activated with an activation energy of approximately 98 kcal/mole over the temperature range 480 to 540 C at 246 bar. The oxidation of ammonia was found to be catalytic with an activation energy of 38 kcal/mole over temperatures ranging from 640 to 700 C. An elementary reaction model for methanol oxidation was applied after correction for the effect of high pressure on the rate constants. The conversion of methanol predicted by the model was in good agreement with experimental data.

  16. Phenol oxidation kinetics in water solution using iron(3)-oxide-based nano-catalysts. (United States)

    Zelmanov, Grigory; Semiat, Raphael


    The influence of inorganic ions (HCO(3), PO(4)/HPO(4)/H(2)PO(4), Cl, SO(4), Ca, Na and Mg) on the advanced chemical oxidation process of organic compounds dissolved in water is reported here. The catalytic behavior of iron(3)-oxide-based nano-particles was investigated together with inorganic ions and hydrogen peroxide concentrations, and pH level. Phenol was chosen as a typical organic contaminant for this study as a simulating pollutant. The limiting concentrations of radical scavengers making the oxidation process inefficient were identified. The strong effect of concentration of radical scavengers HCO(3), PO(4)/HPO(4)/H(2)PO(4), the nano-catalyst and hydrogen peroxide concentrations, and pH on the phenol oxidation rate and lag time period before reaction starts was determined. It was shown that Cl, SO(4), Ca, Na and Mg ions had no significant effect on the kinetics of phenol oxidation.

  17. Chlorine dioxide oxidation of Escherichia coli in water - A study of the disinfection kinetics and mechanism. (United States)

    Ofori, Isaac; Maddila, Suresh; Lin, Johnson; Jonnalagadda, Sreekantha B


    This study investigated the kinetics and mechanism of chlorine dioxide (ClO2) inactivation of a Gram-negative bacteria Escherichia coli (ATCC 35218) in oxidant demand free (ODF) water in detail as a function of disinfectant concentration (0.5-5.0 mg/L), water pH (6.5-8.5), temperature variations (4-37°C) and bacterial density (105-107 cfu/mL). The effects of ClO2 on bacterial cell morphology, outer membrane permeability, cytoplasmic membrane disruption and intracellular enzymatic activity were also studied to elucidate the mechanism of action on the cells. Increasing temperature and disinfectant concentration were proportional to the rate of cell killing, but efficacy was found to be significantly subdued at 0.5 mg/L and less dependent on the bacterial density. The bactericidal efficiency was higher at alkaline pH of 8 or above as compared to neutral and slightly acidic pH of 7 and 6.5 respectively. The disinfection kinetic curves followed a biphasic pattern of rapid inactivation within the initial 2 min which were followed by a tailing even in the presence of residual biocide. The curves were adequately described by the Cavg Hom model. Transmission Electron Microscopy images of the bacteria cells exposed to lethal concentrations of ClO2 indicated very little observable morphological damage to the outer membranes of the cells. ClO2 however was found to increase the permeability of the outer and cytoplasmic membranes leading to the leakage of membrane components such as 260 nm absorbing materials and inhibiting the activity of the intracellular enzyme β-D-galactosidase. It is suggested that the disruption of the cytoplasmic membrane and subsequent efflux of intracellular components result in the inactivation of the Gram-negative bacteria.

  18. Efficient hydrogen production on MoNi4 electrocatalysts with fast water dissociation kinetics (United States)

    Zhang, Jian; Wang, Tao; Liu, Pan; Liao, Zhongquan; Liu, Shaohua; Zhuang, Xiaodong; Chen, Mingwei; Zschech, Ehrenfried; Feng, Xinliang


    Various platinum-free electrocatalysts have been explored for hydrogen evolution reaction in acidic solutions. However, in economical water-alkali electrolysers, sluggish water dissociation kinetics (Volmer step) on platinum-free electrocatalysts results in poor hydrogen-production activities. Here we report a MoNi4 electrocatalyst supported by MoO2 cuboids on nickel foam (MoNi4/MoO2@Ni), which is constructed by controlling the outward diffusion of nickel atoms on annealing precursor NiMoO4 cuboids on nickel foam. Experimental and theoretical results confirm that a rapid Tafel-step-decided hydrogen evolution proceeds on MoNi4 electrocatalyst. As a result, the MoNi4 electrocatalyst exhibits zero onset overpotential, an overpotential of 15 mV at 10 mA cm−2 and a low Tafel slope of 30 mV per decade in 1 M potassium hydroxide electrolyte, which are comparable to the results for platinum and superior to those for state-of-the-art platinum-free electrocatalysts. Benefiting from its scalable preparation and stability, the MoNi4 electrocatalyst is promising for practical water-alkali electrolysers. PMID:28513620

  19. Microbial pesticide removal in rapid sand filters for drinking water treatment – Potential and kinetics

    DEFF Research Database (Denmark)

    Hedegaard, Mathilde Jørgensen; Albrechtsen, Hans-Jørgen


    Filter sand samples, taken from aerobic rapid sand filters used for treating groundwater at three Danish waterworks, were investigated for their pesticide removal potential and to assess the kinetics of the removal process. Microcosms were set up with filter sand, treated water, and the pesticides...... or metabolites mecoprop (MCPP), bentazone, glyphosate and p-nitrophenol were applied in initial concentrations of 0.03–2.4 μg/L. In all the investigated waterworks the concentration of pesticides in the water decreased – MCPP decreased to 42–85%, bentazone to 15–35%, glyphosate to 7–14% and p-nitrophenol 1....../L) increased from 0.21%/g filter sand to 0.75%/g filter sand, when oxygen availability was increased from 0.28 mg O2/g filter sand to 1.09 mg O2/g filter sand. Bentazone was initially cleaved in the removal process. A metabolite, which contained the carbonyl group, was removed rapidly from the water phase...

  20. Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water (United States)

    van der Grift, B.; Rozemeijer, J. C.; Griffioen, J.; van der Velde, Y.


    The retention of phosphorus in surface waters though co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from groundwater to surface water in an agricultural experimental catchment of a small lowland river. We physically separated tube drain effluent from groundwater discharge before it entered a ditch in an agricultural field. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and ditch water, we investigated Fe(II) oxidation kinetics and P immobilization processes. The oxidation rate inferred from our field measurements closely agreed with the general rate law for abiotic oxidation of Fe(II) by O2. Seasonal changes in climatic conditions affected the Fe(II) oxidation process. Lower pH and lower temperatures in winter (compared to summer) resulted in low Fe oxidation rates. After exfiltration to the surface water, it took a couple of days to more than one week before complete oxidation of Fe(II) is reached. In summer time, Fe oxidation rates were much higher. The Fe concentrations in the exfiltrated groundwater were low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into a ditch. While the Fe oxidation rates reduce drastically from summer to winter, P concentrations remained high in the groundwater and an order of magnitude lower in the surface water throughout the year. This study shows very fast immobilisation of dissolved P during the initial stage of the Fe(II) oxidation proces which results in P-depleted water before Fe(II) is competly depleted. This cannot be explained by surface complexation of phosphate to freshly formed Fe-oxyhydroxides but indicates the formation of Fe(III)-phosphate precipitates. The formation of Fe(III)-phosphates at redox gradients seems an

  1. Applying hot-wire anemometry to directly measure the water balance in a proton exchange membrane fuel cell

    DEFF Research Database (Denmark)

    Al Shakhshir, Saher; Andreasen, Søren Juhl; Berning, Torsten


    In order to better understand and more accurately measure the water balance in a proton exchange membrane fuel cell, our group has recently proposed to apply hot wire anemometry in the fuel cell's anode outlet. It was theoretically shown that the electrical signal obtained from the hot wire sensor...... can be directly converted into the fuel cell water balance. In this work an ex-situ experimental investigation is performed to examine the effect of the wire diameter and the outlet pipe diameter on the voltage signal. For a laboratory fuel cell where the mass flow rate the anode outlet is small......, it is found important to use a small output pipe diameter to obtain a sufficiently strong convection effect and hence clear voltage readings. Depending on the hot wire diameter and the inner pipe diameter, the resulting values for the exponent of the Reynolds number Re in the determination of the Nusselt...

  2. Applying hot wire anemometry to directly measure the water balance in a proton exchange membrane fuel cell - Part 1

    DEFF Research Database (Denmark)

    Berning, Torsten; Al Shakhshir, Saher


    In order to accurately determine the water balance of a proton exchange membrane fuel cell it has recently been suggested to employ constant temperature anemometry (CTA), a frequently used method to measure the velocity of a fluid stream. CTA relies on convective heat transfer around a heated wire...... the equations required to calculate the heat transfer coefficient and the resulting voltage signal as function of the fuel cell water balance. The most critical and least understood part is the determination of the Nusselt number to calculate the heat transfer between the wire and the gas stream. Different...... for all current densities. Therefore, only one curve-fit equation will be required. The voltage curve E0 is an arbitrary calibration curve, and this can be conveniently chosen to be the voltage signal for a dry hydrogen stream at a given temperature and various flow rates which can be easily measured....

  3. The importance of water transit time and mineral dissolution kinetics for the flux of weathering products (United States)

    Erlandsson, Martin; Bishop, Kevin; Köhler, Stephan; Amvrosiadi, Nino


    Soil mineral weathering is one of the major sources of base cations (BC), which play a dual role for a forest ecosystem; they function both as plant nutrients, and for buffering against acidification of catchment runoff. On a long-term basis, the soil weathering rates will determine the highest sustainable forest productivity without causing acidification. It is believed that the hydrologic residence time play a key role in determining weathering rates on a landscape scale. In this study, we investigate the significance of the water transit residence time (WTT) distribution for the transport of base cations to catchment runoff. By modelling hillslope flowpaths with different transit times, using the geochemical computing code PHREEQC, we demonstrate how in-stream dynamics as exemplified by elemental ratios can be explained by mineral dissolution kinetics and equilibria. Specifically, we hypothesize that equilibrium of plagioclase regulates the delivery of base cations and silica to catchment runoff. These patters can be seen in field data from 10 years of sampling from a nested-catchment, where the Na+/BC and the Si/BC-ratios vary systematically with WTT on both a temporal and a spatial scale. This behavior has implications for the total transport of products from mineral dissolution to catchment runoff. As the water entering the stream is a mixture of water with different transit times, the composition of stream water will not only be dependent on the average WTT, but also on the shape of the WTT distribution. For the base cations associated with minerals that becomes supersaturated or with precipitating secondary phases within the range of WTT, i.e. Na+ and K+, the tails of "old water" of the WRT-distribution will not contribute to any extra transport of these elements. Finally, we use the derived relationships to estimate the transport of weathering products from a forested hillslope, given the modelled WRT distribution.

  4. Study on the kinetics and transformation products of salicylic acid in water via ozonation. (United States)

    Hu, Ruikang; Zhang, Lifeng; Hu, Jiangyong


    salicylic acid in water, in terms of transformation products, kinetic, mechanism, as well as degradation pathways. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. Untrapping Kinetically Trapped Ions: The Role of Water Vapor and Ion-Source Activation Conditions on the Gas-Phase Protomer Ratio of Benzocaine Revealed by Ion-Mobility Mass Spectrometry (United States)

    Xia, Hanxue; Attygalle, Athula B.


    The role of water vapor in transforming the thermodynamically preferred species of protonated benzocaine to the less favored protomer was investigated using helium-plasma ionization (HePI) in conjunction with ion-mobility mass spectrometry (IM-MS). The IM arrival-time distribution (ATD) recorded from a neat benzocaine sample desorbed to the gas phase by a stream of dry nitrogen and ionized by HePI showed essentially one peak for the O-protonated species. However, when water vapor was introduced to the enclosed ion source, within a span of about 150 ms the ATD profile changed completely to one dominated by the N-protonated species. Under spray-based ionization conditions, the nature and composition of the solvents have been postulated to play a decisive role in defining the manifested protomer ratios. In reality, the solvent vapors present in the ion source (particularly the ambient humidity) indirectly dictate the gas-phase ratio of the protomers. Evidently, the gas-phase protomer ratio established at the confinement of the ions is readjusted by the ion-activation that takes place during the transmission of ions to the vacuum. Although it has been repeatedly stated that ions can retain a "memory" of their solution structures because they can be kinetically trapped, and thereby represent their solution-based stabilities, we show that the initial airborne ions can undergo significant transformations in the transit through the intermediate vacuum zones between the ion source and the mass detector. In this context, we demonstrate that the kinetically trapped N-protomer of benzocaine can be untrapped by reducing the humidity of the enclosed ion source. [Figure not available: see fulltext.

  6. Determination of kinetic isotopic fractionation of water during bare soil evaporation (United States)

    Quade, Maria; Brüggemann, Nicolas; Graf, Alexander; Rothfuss, Youri


    A process-based understanding of the water cycle in the atmosphere is important for improving meteorological and hydrological forecasting models. Usually only net fluxes of evapotranspiration - ET are measured, while land-surface models compute their raw components evaporation -E and transpiration -T. Isotopologues can be used as tracers to partition ET, but this requires knowledge of the isotopic kinetic fractionation factor (αK) which impacts the stable isotopic composition of water pools (e.g., soil and plant waters) during phase change and vapor transport by soil evaporation and plant transpiration. It is defined as a function of the ratio of the transport resistances in air of the less to the most abundant isotopologue. Previous studies determined αK for free evaporating water (Merlivat, 1978) or bare soil evaporation (Braud et al. 2009) at only low temporal resolution. The goal of this study is to provide estimates at higher temporal resolution. We performed a soil evaporation laboratory experiment to determine the αK by applying the Craig and Gordon (1965) model. A 0.7 m high column (0.48 m i.d.) was filled with silt loam (20.1 % sand, 14.9 % loam, 65 % silt) and saturated with water of known isotopic composition. Soil volumetric water content, temperature and the isotopic composition (δ) of the soil water vapor were measured at six different depths. At each depth microporous polypropylene tubing allowed the sampling of soil water vapor and the measurement of its δ in a non-destructive manner with high precision and accuracy as detailed in Rothfuss et al. (2013). In addition, atmospheric water vapor was sampled at seven different heights up to one meter above the surface for isotopic analysis. Results showed that soil and atmospheric δ profiles could be monitored at high temporal and vertical resolutions during the course of the experiment. αK could be calculated by using an inverse modeling approach and the Keeling (1958) plot method at high temporal

  7. Electrocatalytic Water Oxidation by a Water-Soluble Copper(II) Complex with a Copper-Bound Carbonate Group Acting as a Potential Proton Shuttle. (United States)

    Chen, Fangfang; Wang, Ni; Lei, Haitao; Guo, Dingyi; Liu, Hongfei; Zhang, Zongyao; Zhang, Wei; Lai, Wenzhen; Cao, Rui


    Water-soluble copper(II) complexes of the dianionic tridentate pincer ligand N,N'-2,6-dimethylphenyl-2,6-pyridinedicarboxamidate (L) are catalysts for water oxidation. In [L-Cu II -DMF] (1, DMF = dimethylformamide) and [L-Cu II -OAc] - (2, OAc = acetate), ligand L binds Cu II through three N atoms, which define an equatorial plane. The fourth coordination site of the equatorial plane is occupied by DMF in 1 and by OAc - in 2. These two complexes can electrocatalyze water oxidation to evolve O 2 in 0.1 M pH 10 carbonate buffer. Spectroscopic, titration, and crystallographic studies show that both 1 and 2 undergo ligand exchange when they are dissolved in carbonate buffer to give [L-Cu II -CO 3 H] - (3). Complex 3 has a similar structure as those of 1 and 2 except for having a carbonate group at the fourth equatorial position. A catalytic cycle for water oxidation by 3 is proposed based on experimental and theoretical results. The two-electron oxidized form of 3 is the catalytically active species for water oxidation. Importantly, for these two oxidation events, the calculated potential values of E p,a = 1.01 and 1.59 V vs normal hydrogen electrode (NHE) agree well with the experimental values of E p,a = 0.93 and 1.51 V vs NHE in pH 10 carbonate buffer. The potential difference between the two oxidation events is 0.58 V for both experimental and calculated results. With computational evidence, this Cu-bound carbonate group may act as a proton shuttle to remove protons for water activation, a key role resembling intramolecular bases as reported previously.

  8. Water-assisted self-photoredox of 2-(1-hydroxyethyl)-9,10-anthraquinone through a triplet excited state intra-molecular proton transfer pathway. (United States)

    Dai, Jingze; Han, Juan; Chen, Xuebo; Fang, Weihai; Ma, Jiani; Phillips, David Lee


    Using multi-configurational perturbation theory (CASPT2//CASSCF), a novel self-photoredox reaction for 2-(1-hydroxyethyl)-9,10-anthraquinone was proposed to effectively occur through two steps of triplet excited state intra-molecular proton transfer (ESIPT) reaction aided by water wires without the introduction of an external oxidant or reductant. The photoinduced charge transfer along the desired direction was determined to be the major driving force for the occurrence of the energetically favorable ESIPT in the triplet state, in which the water wires function as an effective proton relay and photocatalyst to lower the reaction barrier. The computational results provide convincing evidence that the deprotonation of the hydroxyl group in the triplet state and connecting water molecule(s) between that hydroxyl group and the carbonyl group that is protonated by a nearby water molecule in the water wire is the initial reaction step that triggers the protonation of the carbonyl group seen in the previously reported time-resolved spectroscopy experiments that produces a protonated carbonyl triplet intermediate that then undergoes a subsequent deprotonation of the methylene C-H in the triplet and ground states to complete the self-photoredox reaction of anthraquinone. Comparison of the theoretical results with previously reported results from time-resolved spectroscopy experiments indicate the photoredox reactions can occur either via a concerted or non-concerted deprotonation-protonation of distal sites of the molecule assisted by the connecting water molecules. These new insights will help provide benchmarks to elucidate the photochemistry of the anthraquinone and benzophenone compounds in acidic and/or neutral aqueous solutions.

  9. A novel kinetic method for the speciation of cadmium in river water by micro solvent extraction with dithizone. (United States)

    Shimizu, Tokuo; Hiraoka, Yoshinori; Kikuchi, Miyuki; Uehara, Nobuo


    Cadmium species in river water were kinetically extracted with dithizone by varying the extraction time. The obtained extraction curve showed a three-stage stepwise profile that reflected the rate of the ligand substitution reaction between the dithizone and cadmium species. Corresponding to each stage, we divided these extracted cadmium species into three groups: "highly labile", "moderately labile" and "slowly labile" species.

  10. Abscisic acid accumulation modulates auxin transport in the root tip to enhance proton secretion for maintaining root growth under moderate water stress. (United States)

    Xu, Weifeng; Jia, Liguo; Shi, Weiming; Liang, Jiansheng; Zhou, Feng; Li, Qianfeng; Zhang, Jianhua


    Maintenance of root growth is essential for plant adaptation to soil drying. Here, we tested the hypothesis that auxin transport is involved in mediating ABA's modulation by activating proton secretion in the root tip to maintain root growth under moderate water stress. Rice and Arabidopsis plants were raised under a hydroponic system and subjected to moderate water stress (-0.47 MPa) with polyethylene glycol (PEG). ABA accumulation, auxin transport and plasma membrane H(+)-ATPase activity at the root tip were monitored in addition to the primary root elongation and root hair density. We found that moderate water stress increases ABA accumulation and auxin transport in the root apex. Additionally, ABA modulation is involved in the regulation of auxin transport in the root tip. The transported auxin activates the plasma membrane H(+)-ATPase to release more protons along the root tip in its adaption to moderate water stress. The proton secretion in the root tip is essential in maintaining or promoting primary root elongation and root hair development under moderate water stress. These results suggest that ABA accumulation modulates auxin transport in the root tip, which enhances proton secretion for maintaining root growth under moderate water stress. © 2012 The Authors. New Phytologist © 2012 New Phytologist Trust.

  11. Coupled 3D neutron kinetics and thermalhydraulic characteristics of the Canadian supercritical water reactor

    Energy Technology Data Exchange (ETDEWEB)

    Hummel, David William, E-mail:; Novog, David Raymond


    Highlights: • A coupled spatial kinetics and thermalhydraulics model of the PT-SCWR was created. • Positive power excursions were demonstrated during accident-like transients. • The reactor will inherently self-shutdown in such transients with some delay. • A fast-acting shutdown system would limit the consequences of the power pulse. - Abstract: The Canadian Supercritical Water-cooled Reactor concept, as an evolution of the CANada Deuterium Uranium (CANDU) reactor, includes both pressure tubes and a low temperature heavy water moderator. The current Pressure Tube type SCWR (PT-SCWR) concept features 64-element fuel assemblies placed within High Efficiency Re-entrant Channels (HERCs) that connect to core inlet and outlet plena. Among current SCWR concepts the PT-SCWR is unique in that the HERC separates multiple coolant and moderator regions, giving rise to coupled neutronic-thermalhydraulic feedbacks beyond those present in CANDU or contemporary Light Water Reactors. The objective of this work was thus to model the coupled neutronic-thermal hydraulic properties of the PT-SCWR to establish the impact of these multiple regions on the core's transient behavior. To that end, the features of the PT-SCWR were first modeled with the neutron transport code DRAGON to create a database of homogenized and condensed cross-sections and thermalhydraulic feedback coefficients. These were used as input to a core-level neutron diffusion model created with the code DONJON. The behavior of the primary heat transport system was modeled with the thermalhydraulic system code CATHENA. A procedure was developed to couple the outputs of DONJON and CATHENA, facilitating three-dimensional spatial neutron kinetics and coupled thermalhydraulic analysis of the PT-SCWR core. Several postulated transients were initiated within the coupled model by changing the core inlet and outlet boundary conditions. Decreasing coolant density around the fuel was demonstrated to produce positive

  12. Biosorption of lead (II) from water using heartwood charcoal of Areca catechu: equilibrium and kinetics studies (United States)

    Haloi, Nabanita; Sarma, H. P.; Chakravarty, P.


    Present study was conducted to investigate the removal of Pb(II) from water by using heartwood charcoal of Areca catechu (HCAC). Batch experiments were conducted to determine the adsorption properties at different contact times (5-30 min), concentrations (0.1-10 mg/L), amounts of adsorbents (0.1-0.6 g), and in a range of pH 2-7. Most favorable biosorption condition was found at pH 5.0, 0.5 g biomass dosage and at 25 min equilibrium time. The experimental results were fitted to the Langmuir and Freundlich isotherm models; the Freundlich isotherm was found to well represent the measured sorption data implying HCAC has heterogeneous surface. Lagergren first-order and pseudo-second-order kinetic model were used to analyze the biosorption data; it was observed that the pseudo-second-order model best represented the relationship. Scanning electron microscopy image and energy dispersive X-ray analysis were also incorporated in support of the study. The result shows that HCAC has the potentiality to remove Pb(II) from water.

  13. Effects of water blanching on polyphenol reaction kinetics and quality of cocoa beans (United States)

    Menon, A. S.; Hii, C. L.; Law, C. L.; Suzannah, S.; Djaeni, M.


    Several studies have been reported on the potential health benefits of cocoa polyphenols. However, drying has an inhibitory effect on the substantial recovery of cocoa polyphenols. This is majorly because of the high degradation of polyphenol compounds as well as the enhanced activity of polyphenol oxidases; a pre-cursor for browning of polyphenols during drying. Pre-treatment technique such as water blanching (80° and 90°C for 5 min, 10 min and 15 min exposure times respectively) can inactivate the polyphenol oxidases enzyme and promote high percent of the polyphenol recovery in dried cocoa bean. The degradation kinetics of cocoa polyphenols during hot water blanching are analyzed; The rate constant for the polyphenol degradation after blanching was found to be ranging from 0.0208 to 0.0340 /min. The results for dried fresh cocoa beans showed an optimal level of polyphenol recovery (118 mg GAE/g) when blanched at 90°C for 5 minutes duration. The antioxidant activity is also analyzed using DPPH scavenging assay.

  14. Plasma Kinetics in Electrical Discharge in Mixture of Air, Water and Ethanol Vapors for Hydrogen Enriched Syngas Production


    Shchedrin, A. I.; Levko, D. S.; Ryabtsev, A. V.; Chernyak, V. Ya.; Yukhymenko, V. V.; Olszewski, S. V.; Naumov, V. V.; Prysiazhnevych, I. V.; Solomenko, E. V.; Demchina, V. P.; Kudryavtsev, V. S.


    The complex theoretical and experimental investigation of plasma kinetics of the electric discharge in the mixture of air and ethanol-water vapors is carried out. The discharge was burning in the cavity, formed by air jets pumping between electrodes, placed in aqueous ethanol solution. It is found out that the hydrogen yield from the discharge is maximal in the case when ethanol and water in the solution are in equal amounts. It is shown that the hydrogen production increases with the dischar...

  15. Energetics and kinetics of photosynthetic water oxidation studied by photothermal beam deflection (PBD) experiments. (United States)

    Klauss, André; Krivanek, Roland; Dau, Holger; Haumann, Michael


    Determination of thermodynamic parameters of water oxidation at the photosystem II (PSII) manganese complex is a major challenge. Photothermal beam deflection (PBD) spectroscopy determines enthalpy changes (ΔH) and apparent volume changes which are coupled with electron transfer in the S-state cycle (Krivanek R, Dau H, Haumann M (2008) Biophys J 94: 1890–1903). Recent PBD results on formation of the Q⁻(A)/Y(•+)(Z) radical pair suggest a value of ΔH similar to the free energy change, ΔG, of -540±40 meV previously determined by the analysis of recombination fluorescence, but presently the uncertainty range of ΔH values determined by PBD is still high (±250 meV). In the oxygen-evolving transition, S₃−−>S₀, the enthalpy change may be close to zero. A prominent non-thermal signal is associated with both Q⁻(A)/Y(•+)(Z) formation (S₀ transition (~1 ms). The observed (apparent) volume expansion (ΔV of about +40 ų per PSII unit) in the S₃−−>S₀ transition seems to revert, at least partially, the contractions on lower S-transitions and may also comprise contributions from O₂ and proton release. The observed volume changes show that the S₃−−>S₀ transition is accompanied by significant nuclear movements, which likely are of importance with respect to energetics and mechanism of photosynthetic water oxidation. Detailed PBD studies on all S-transitions will contribute to the progress in PSII research by providing insights not accessible by other spectroscopic methods. © Springer Science+Business Media B.V. 2009

  16. Numerical simulation and experimental validation of liquid water behaviors in a proton exchange membrane fuel cell cathode with serpentine channels (United States)

    Le, Anh Dinh; Zhou, Biao; Shiu, Huan-Ruei; Lee, Chun-I.; Chang, Wen-Chen

    The volume-of-fluid (VOF) approach is one of the most promising methods of investigating water transport and water management in proton exchange membrane fuel cells (PEMFCs). A general PEMFC model combined with the VOF method has been developed by our group to simulate the mechanisms of fluid flows, mass and heat transport, and electrochemical reactions in a PEMFC, and it is necessary to validate the numerical model through experiments. In this paper, both the numerical model and an experimental visualization that can simulate the motion and transport behavior of liquid water in a cathode flow channel of a PEMFC are presented. Direct optical visualization is used in this work to capture the droplets' motions with high spatial and temporal resolutions. The numerical model and experimental setup have similar geometric dimensions and operating conditions, and the results of the experiment are in good agreement with numerical simulations. Moreover, the physics of droplet and liquid water behavior based on certain material and liquid properties and the operating conditions in the fuel cell channel are also addressed. This analysis also offers some basic understanding of the mechanism of liquid droplet dynamics in numerical and experimental studies of micro-fluidics.

  17. Molecular dynamics simulations of triflic acid and triflate ion/water mixtures: a proton conducting electrolytic component in fuel cells. (United States)

    Sunda, Anurag Prakash; Venkatnathan, Arun


    Triflic acid is a functional group of perflourosulfonated polymer electrolyte membranes where the sulfonate group is responsible for proton conduction. However, even at extremely low hydration, triflic acid exists as a triflate ion. In this work, we have developed a force-field for triflic acid and triflate ion by deriving force-field parameters using ab initio calculations and incorporated these parameters with the Optimized Potentials for Liquid Simulations - All Atom (OPLS-AA) force-field. We have employed classical molecular dynamics (MD) simulations with the developed force field to characterize structural and dynamical properties of triflic acid (270-450 K) and triflate ion/water mixtures (300 K). The radial distribution functions (RDFs) show the hydrophobic nature of CF(3) group and presence of strong hydrogen bonding in triflic acid and temperature has an insignificant effect. Results from our MD simulations show that the diffusion of triflic acid increases with temperature. The RDFs from triflate ion/water mixtures shows that increasing hydration causes water molecules to orient around the SO(3)(-) group of triflate ions, solvate the hydronium ions, and other water molecules. The diffusion of triflate ions, hydronium ion, and water molecules shows an increase with hydration. At λ = 1, the diffusion of triflate ion is 30 times lower than the diffusion of triflic acid due to the formation of stable triflate ion-hydronium ion complex. With increasing hydration, water molecules break the stability of triflate ion-hydronium ion complex leading to enhanced diffusion. The RDFs and diffusion coefficients of triflate ions, hydronium ions and water molecules resemble qualitatively the previous findings using per-fluorosulfonated membranes. Copyright © 2011 Wiley Periodicals, Inc.

  18. A dielectric response study of the electronic stopping power of liquid water for energetic protons and a new I-value for water. (United States)

    Emfietzoglou, D; Garcia-Molina, R; Kyriakou, I; Abril, I; Nikjoo, H


    The electronic stopping power of liquid water for protons over the 50 keV to 10 MeV energy range is studied using an improved dielectric response model which is in good agreement with the best available experimental data. The mean excitation energy (I) of stopping power theory is calculated to be 77.8 eV. Shell corrections are accounted for in a self-consistent manner through analytic dispersion relations for the momentum dependence of the dielectric function. It is shown that widely used dispersion schemes based on the random-phase approximation (RPA) can result in sizeable errors due to the neglect of damping and local field effects that lead to a momentum broadening and shifting of the energy-loss function. Low-energy Born corrections for the Barkas, Bloch and charge-state effects practically cancel out down to 100 keV proton energies. Differences with ICRU Report 49 stopping power values and earlier calculations are found to be at the approximately 20% level in the region of the stopping maximum. The present work overcomes the limitations of the Bethe formula below 1 MeV and improves the accuracy of previous calculations through a more consistent account of the dielectric response properties of liquid water.

  19. Non-noble metal based electro-catalyst compositions for proton exchange membrane based water electrolysis and methods of making (United States)

    Kumta, Prashant N.; Kadakia, Karan Sandeep; Datta, Moni Kanchan; Velikokhatnyi, Oleg


    The invention provides electro-catalyst compositions for an anode electrode of a proton exchange membrane-based water electrolysis system. The compositions include a noble metal component selected from the group consisting of iridium oxide, ruthenium oxide, rhenium oxide and mixtures thereof, and a non-noble metal component selected from the group consisting of tantalum oxide, tin oxide, niobium oxide, titanium oxide, tungsten oxide, molybdenum oxide, yttrium oxide, scandium oxide, cooper oxide, zirconium oxide, nickel oxide and mixtures thereof. Further, the non-noble metal component can include a dopant. The dopant can be at least one element selected from Groups III, V, VI and VII of the Periodic Table. The compositions can be prepared using a surfactant approach or a sol gel approach. Further, the compositions are prepared using noble metal and non-noble metal precursors. Furthermore, a thin film containing the compositions can be deposited onto a substrate to form the anode electrode.

  20. Effect of polymer morphology on proton and water transport through ionomeric polymers. [Perfluorosulfonic ionomer

    Energy Technology Data Exchange (ETDEWEB)

    Fales, J.L.; Springer, T.E.; Vanderborgh, N.E.; Stroeve, P.


    The rate of ionic transport through perfluorosulfonic acid membranes is set by water content within mass transfer channels of the polymer. Consequently, control of water flux is important to control transport rates. Experiments show the influence of cation type on water transport properties and on polymer physical properties. These results support the model that channel geometries are determined by the interaction of coulombic forces within the membrane. Description of these transport processes is accomplished through several mathematical routes.

  1. Synthesis of Indium-Containing Nanoparticles in Aqueous Suspension Using Plasmas in Water for Evaluating Their Kinetics in Living Body. (United States)

    Amano, Takaaki; Sarinont, Thapanut; Koga, Kazunori; Hirata, Miyuki; Tanaka, Akiyo; Shiratani, Masaharu


    Nanoparticles have great potential for medical applications such as cancer therapy, whereas their toxic effects on human body are pointed out. To study kinetics and toxicity of nanoparticles in living body, we synthesized indium-containing nanoparticles in aqueous suspension using pulsed electrical discharge plasmas in water, because no indium compounds exist in the living body in the normal situation and hence indium-containing nanoparticles are useful tracer materials for analyzing kinetics of nanoparticles in living body. The mean size of synthesized primary nanoparticles is 7 nm, whereas the mean size of secondary nanoparticles is 315 nm. EDX and XRD analysis reveal that nanoparticles are indium crystalline and indium hydroxide crystalline with the mass ratio of 8:2. Preliminary subcutaneous administration of nanoparticles to mice shows that indium is transported from subcutaneous to blood. These results show that synthesized indium-containing nanoparticles are useful for analyzing kinetics of nanoparticles in living body.

  2. Dissolution kinetics and mechanisms at dolomite-water interfaces: effects of electrolyte specific ionic strength. (United States)

    Xu, Man; Sullivan, Katie; Vanness, Garrett; Knauss, Kevin G; Higgins, Steven R


    Elucidating dissolution kinetics and mechanisms at carbonate mineral-water interfaces is essential to many environmental and geochemical processes, including geologic CO(2) sequestration in deep aquifers. In the present work, effects of background electrolytes on dolomite (CaMg(CO(3))(2)) reactivity were investigated by measuring step dissolution rates using in situ hydrothermal atomic force microscopy (HAFM) at 90 °C. Cleaved surfaces of dolomite were exposed to sodium chloride and tetramethylammonium chloride (TMACl) aqueous solutions with ionic strengths (I) ranging from 0 to 0.77 m at pH 4 and pH 9. HAFM results demonstrated that dolomite step retreat rates increased with increasing solution ionic strength and decreasing pH. Comparison of [481] and [441] steps revealed that the anisotropy of [481] and [441] step speeds became significant as solution ionic strength increased, with NaCl exerting more pronounced effects than TMACl for the same I. To interpret the different trends observed for NaCl and TMACl, a dissolution mechanism involving orientation-dependent ion adsorption and consequent edge free energy changes is proposed.

  3. Supercritical water oxidation of quinazoline: Reaction kinetics and modeling. (United States)

    Gong, Yanmeng; Guo, Yang; Wang, Shuzhong; Song, Wenhan; Xu, Donghai


    This paper presents a first quantitative kinetic model for supercritical water oxidation (SCWO) of quinazoline that describes the formation and interconversion of intermediates and final products at 673-873 K. The set of 11 reaction pathways for phenol, pyrimidine, naphthalene, NH3, etc, involved in the simplified reaction network proved sufficient for fitting the experimental results satisfactorily. We validated the model prediction ability on CO2 yields at initial quinazoline loading not used in the parameter estimation. Reaction rate analysis and sensitivity analysis indicate that nearly all reactions reach their thermodynamic equilibrium within 300 s. The pyrimidine yielding from quinazoline is the dominant ring-opening pathway and provides a significant contribution to CO2 formation. Low sensitivity of NH3 decomposition rate to concentration confirms its refractory nature in SCWO. Nitrogen content in liquid products decreases whereas that in gaseous phase increases as reaction time prolonged. The nitrogen predicted by the model in gaseous phase combined with the experimental nitrogen in liquid products gives an accurate nitrogen balance of conversion process. Copyright © 2016 Elsevier Ltd. All rights reserved.

  4. Encapsulation of Ethylene Gas into Granular Cold-Water-Soluble Starch: Structure and Release Kinetics. (United States)

    Shi, Linfan; Fu, Xiong; Tan, Chin Ping; Huang, Qiang; Zhang, Bin


    Ethylene gas was introduced into granular cold-water-soluble (GCWS) starches using a solid encapsulation method. The morphological and structural properties of the novel inclusion complexes (ICs) were characterized using scanning electron microscopy, X-ray diffractometry, and Raman spectroscopy. The V-type single helix of GCWS starches was formed through controlled gelatinization and ethanol precipitation and was approved to host ethylene gas. The controlled release characteristics of ICs were also investigated at various temperature and relative humidity conditions. Avrami's equation was fitted to understand the release kinetics and showed that the release of ethylene from the ICs was accelerated by increasing temperature or RH and was decelerated by increased degree of amylose polymerization. The IC of Hylon-7 had the highest ethylene concentration (31.8%, w/w) among the five starches, and the IC of normal potato starch showed the best controlled release characteristics. As a renewable and inexpensive material, GCWS starch is a desirable solid encapsulation matrix with potential in agricultural and food applications.

  5. Virgin volcanic rocks: Kinetics and equilibrium studies for the adsorption of cadmium from water

    Energy Technology Data Exchange (ETDEWEB)

    Alemayehu, Esayas, E-mail: [Institute for Land Use, Rostock University, Justus-Von-Liebig-Weg 6, 18059 Rostock (Germany); Lennartz, Bernd [Institute for Land Use, Rostock University, Justus-Von-Liebig-Weg 6, 18059 Rostock (Germany)


    This study was initiated to investigate the adsorption of cadmium from aqueous solution by two different rock types-Pumice (VPum) and Scoria (VSco), which are readily available in Ethiopia and other countries. The influence of operational conditions, such as particle size, adsorbent/solution ratio, contact time, cadmium initial concentration, and pH was analyzed. The competition between metals was also evaluated. The Cd(II) removal capacity was predominantly affected by the pH conditions, being increased under alkaline conditions. For both adsorbents, when particle size was 0.075-0.425 mm, the maximum Cd(II) adsorption was observed at pH 6.0 (contact time = 24 h, shaking speed = 200 rpm, adsorbent dose = 50 g L{sup -1}). Adsorption process revealed that the initial uptake was very fast during the first 1 h. The kinetics of the interactions follows pseudo second-order. Equilibrium assays confirm that VPum has a larger capacity and affinity for Cd(II) adsorption than VSco. Both Langmuir and Freundlich models described equally well the experimental data. VPum and VSco were found to be promising material for the removal of cadmium from metal bearing water.

  6. Adsorption of lead(II) from water by carbon nanotubes: equilibrium, kinetics, and thermodynamics. (United States)

    Rahbari, Meysam; Goharrizi, Ataallah Soltani


    Adsorption of lead(II) from water on carbon nanotubes (CNTs) was investigated using a series of batch adsorption experiments. The adsorption rate was studied experimentally at various temperatures, contact times, and initial pH and lead(II) concentrations. It was observed that a considerable amount of lead(II) was adsorbed during the first 5 minutes of contact time. The pH of the solution strongly influenced the amount of adsorption, and the best results were obtained when pH value was approximately 6. For the adsorption isotherm, the experimental data were analyzed by three two-parameter isotherms (Langmuir, Freundlich, and Temkin) and four three-parameter isotherms (Redhich-Peterson, Sips, Toth, and Khan). The three kinetic models used to test the experimental data were Lagergren first-order, second-order, and the Elovich equation. The results obtained from the study of the thermodynamic parameters showed that the adsorption of lead(II) onto CNTs was a spontaneous and endothermic process.

  7. On the formation of radical dications of protonated amino acids in a "microsolution" of water or acetonitrile and their reactivity towards the solvent

    DEFF Research Database (Denmark)

    Sørensen, M; Forster, JS; Hvelplund, P


    In high-energy collisions (50 keV) between O2 and protonated amino acids AH+, radical dications AH2+* are formed for A = Phe, His, Met, Tyr, and Trp. When solvated by water or acetonitrile (S), AH2+*(S)1,2 are formed for A = Arg, His, Met, Tyr, and Trp. The stability of the hydrogen-deficient AH2...

  8. Water free proton conducting membranes based on poly-4-vinylpyridinebisulfate for fuel cells (United States)

    Narayanan, Sekharipuram R. (Inventor); Yen, Shiao-Pin S. (Inventor)


    Disclosed are methods for forming a water-free electrolyte membrane useful in fuel cells. Also provided is a water-free electrolyte membrane comprising a quaternized amine salt including poly-4-vinylpyridinebisulfate, a poly-4-vinylpyridinebisulfate silica composite, and a combination thereof and a fuel cell comprising the membrane.

  9. Analyzing water soluble soil organics as Trifluoroacetyl derivatives by liquid state proton nuclear magnetic resonance (United States)

    Felipe Garza Sanchez; Zakiya Holmes Leggett; Sabapathy Sankar


    In forested ecosystems, water soluble organics play an important role in soil processes including carbon and nutrient turnover, microbial activity and pedogenesis. The quantity and quality (i.e., chemistry) of these materials is sensitive to land management practices. Monitoring alterations in the chemistry of water soluble organics resulting from land management...

  10. Peroxone mineralization of chemical oxygen demand for direct potable water reuse: Kinetics and process control. (United States)

    Wu, Tingting; Englehardt, James D


    Mineralization of organics in secondary effluent by the peroxone process was studied at a direct potable water reuse research treatment system serving an occupied four-bedroom, four bath university residence hall apartment. Organic concentrations were measured as chemical oxygen demand (COD) and kinetic runs were monitored at varying O3/H2O2 dosages and ratios. COD degradation could be accurately described as the parallel pseudo-1st order decay of rapidly and slowly-oxidizable fractions, and effluent COD was reduced to below the detection limit (<0.7 mg/L). At dosages ≥4.6 mg L(-1) h(-1), an O3/H2O2 mass ratio of 3.4-3.8, and initial COD <20 mg/L, a simple first order decay was indicated for both single-passed treated wastewater and recycled mineral water, and a relationship is proposed and demonstrated to estimate the pseudo-first order rate constant for design purposes. At this O3/H2O2 mass ratio, ORP and dissolved ozone were found to be useful process control indicators for monitoring COD mineralization in secondary effluent. Moreover, an average second order rate constant for OH oxidation of secondary effluent organics (measured as MCOD) was found to be 1.24 × 10(7) ± 0.64 × 10(7) M(-1) S(-1). The electric energy demand of the peroxone process is estimated at 1.73-2.49 kW h electric energy for removal of one log COD in 1 m(3) secondary effluent, comparable to the energy required for desalination of medium strength seawater. Advantages/disadvantages of the two processes for municipal wastewater reuse are discussed. Copyright © 2015 Elsevier Ltd. All rights reserved.

  11. Local area water removal analysis of a proton exchange membrane fuel cell under gas purge conditions. (United States)

    Lee, Chi-Yuan; Lee, Yu-Ming; Lee, Shuo-Jen


    In this study, local area water content distribution under various gas purging conditions are experimentally analyzed for the first time. The local high frequency resistance (HFR) is measured using novel micro sensors. The results reveal that the liquid water removal rate in a membrane electrode assembly (MEA) is non-uniform. In the under-the-channel area, the removal of liquid water is governed by both convective and diffusive flux of the through-plane drying. Thus, almost all of the liquid water is removed within 30 s of purging with gas. However, liquid water that is stored in the under-the-rib area is not easy to remove during 1 min of gas purging. Therefore, the re-hydration of the membrane by internal diffusive flux is faster than that in the under-the-channel area. Consequently, local fuel starvation and membrane degradation can degrade the performance of a fuel cell that is started from cold.

  12. Measurement of LET (linear energy transfer) spectra using CR-39 at different depths of water irradiated by 171 MeV protons: A comparison with Monte Carlo simulation

    Energy Technology Data Exchange (ETDEWEB)

    Sahoo, G.S. [Health Physics Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Tripathy, S.P., E-mail: [Health Physics Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Homi Bhabha National Institute, Mumbai 400094 (India); Molokanov, A.G.; Aleynikov, V.E. [Joint Institute for Nuclear Research, Dubna 141980 (Russian Federation); Sharma, S.D. [Homi Bhabha National Institute, Mumbai 400094 (India); Radiological Physics & Advisory Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Bandyopadhyay, T. [Health Physics Division, Bhabha Atomic Research Centre, Mumbai 400085 (India); Homi Bhabha National Institute, Mumbai 400094 (India)


    In this work, we have used CR-39 detectors to estimate the LET (linear energy transfer) spectrum of secondary particles due to 171 MeV proton beam at different depths of water including the Bragg peak region. The measured LET spectra were compared with those obtained from FLUKA Monte Carlo simulation. The absorbed dose (D{sub LET}), dose equivalent (H{sub LET}) were estimated using the LET spectra. The values of D{sub LET} and H{sub LET} per incident proton fluence were found to increase with the increase in depth of water and were maximum at Bragg peak. - Highlights: • Measurement of LET spectrometry using CR-39 detectors at different depths of water. • Comparison of measured spectra with FLUKA Monte carlo simulation. • Absorbed dose and dose equivalent was found to increase with depth of water.

  13. Hydroxyl radical induced oxidation of theophylline in water: a kinetic and mechanistic study. (United States)

    Sunil Paul, M M; Aravind, U K; Pramod, G; Saha, A; Aravindakumar, C T


    ring opened compounds (ix-xiv). The kinetic and mechanistic data furnished in the present study serve as a basic frame work for the construction of ˙OH induced water treatment systems as well as to understand the biological implications of compounds of this kind.

  14. Single- and Multiple-Electron Removal Processes in Proton-Water Vapor Collisions (United States)

    Murakami, Mitsuko; Kirchner, Tom; Horbatsch, Marko; Jürgen Lüdde, Hans


    Charge-state correlated cross sections for single- and multiple-electron removal processes due to capture and ionization in proton-H2O collisions are calculated by using the non-perturbative basis generator method adapted for ion-molecule collisions [1]. Orbital-specific cross sections for vacancy production are evaluated using this method to predict the yields of charged fragments (H2O^+, OH^+, H^+, O^+) according to branching ratios known to be valid at high impact energies. At intermediate and low energies, we obtain fragmentation results on the basis of predicted multi-electron removal cross sections, and explain most of the available experimental data [2]. The cross sections for charge transfer and for ionization are also compared with recent multi-center classical-trajectory Monte Carlo calculations [3] for impact energies from 20keV to several MeV. [4pt] [1] H.J. L"udde et al, Phys. Rev. A 80, 060702(R) (2009)[0pt] [2] M. Murakami et al, to be submitted to Phys. Rev. A (2012)[0pt] [3] C. Illescas et al, Phys. Rev. A 83, 052704 (2011)

  15. Adsorption of selected emerging contaminants onto PAC and GAC: Equilibrium isotherms, kinetics, and effect of the water matrix. (United States)

    Real, Francisco J; Benitez, F Javier; Acero, Juan L; Casas, Francisco


    The removal of three emerging contaminants (ECs) (amitriptyline hydrochloride (AH), methyl salicylate (MS) and 2-phenoxyethanol (PE)) dissolved in several water matrices by means of their adsorption onto powdered activated carbon (PAC) and granular activated carbon (GAC) has been investigated. When dissolved in ultrapure water, adsorption of the ECs followed the trend of AH > MS > PE, with a positive effect of the adsorbent dose. According to the analysis of the adsorption isotherms and adsorption kinetics, PAC showed strongly higher adsorption efficiency in both capacity and velocity of the adsorption, in agreement with its higher mesoporosity. Equilibrium isotherm data were fitted by Langmuir and Freundlich models. Pseudo-second order kinetics modeled very successfully the adsorption process. Finally, the effect of the presence of dissolved organic matter (DOM) in the water matrices (ultrapure water, surface water and two effluents from wastewater treatment plants) on the adsorption of the selected ECs onto PAC was established, as well as its performance on the removal of water quality parameters. Results show a negative effect of the DOM content on the adsorption efficiency. Over 50% of organic matter was removed with high PAC doses, revealing that adsorption onto PAC is an effective technology to remove both micro-pollutants and DOM from water matrices.

  16. Synthesis and characterization of carbon dioxide and boiling water stable proton conducting double perovskite-type metal oxides (United States)

    Bhella, Surinderjit Singh; Thangadurai, Venkataraman

    In this paper, we report the synthesis, chemical stability and electrical properties of three new Ta-substituted double perovskite-type Ba 2Ca 2/3Nb 4/3O 6 (BCN). The powder X-ray diffraction (PXRD) confirms the formation of double perovskite-like structure Ba 2(Ca 0.75Nb 0.59Ta 0.66)O 6- δ, Ba 2(Ca 0.75Nb 0.66Ta 0.59)O 6- δ and Ba 2(Ca 0.79Nb 0.66Ta 0.55)O 6- δ. The PXRD of CO 2 treated (800 °C; 7 days) and water boiled (7 days) samples remain the same as the as-prepared samples, suggesting a long-term structural stability against the chemical reaction. The electrical conductivity of the investigated perovskites was found to vary in different atmospheres (air, dry N 2, wet N 2, H 2 and D 2O + N 2). The AC impedance investigations show bulk, grain-boundary and electrode contributions in the frequency range of 0.01 Hz to 7 MHz. Below 600 °C, the bulk conductivity in wet H 2 and wet N 2 was higher than in air, dry H 2 and dry N 2. However, an opposite trend was observed at high temperatures, which may be ascribed to p-type electronic conduction. The electrical conductivity of the investigated perovskites was decreased in D 2O + N 2 compared to that of H 2O + N 2 atmosphere. This clearly shows that the investigated Ta-doped BCN compounds exhibit proton conduction in wet atmosphere which was found to be consistent with water uptake. The water uptake was further confirmed by thermogravimetric analysis (TGA) and Fourier transform infrared spectroscopy (FTIR) characterization. Among the samples investigated, Ba 2(Ca 0.79Nb 0.66Ta 0.55)O 6- δ shows the highest proton conductivity of 4.8 × 10 -4 S cm -1 (at 1 MHz) at 400 °C in wet (3% H 2O) N 2 or H 2, which is about an order of magnitude higher than the recently reported 1% Ca-doped LaNbO 4 at the same atmosphere and at 10 kHz.

  17. Proton inelastic mean free path in a group of bioorganic compounds and water in 0.05-10 MeV range - Including higher-order corrections

    Energy Technology Data Exchange (ETDEWEB)

    Tan Zhenyu, E-mail: [School of Electrical Engineering, Shandong University, Jinan 250061, Shandong (China); Xia Yueyuan; Zhao Mingwen; Liu Xiangdong [School of Physics, Shandong University, Jinan 250100, Shandong (China)


    The systematic calculations of the inelastic mean free paths (MFP) of 0.05-10 MeV protons in a group of eleven important bioorganic compounds, i.e. DNA, five bases, three fatty acids, cellulose and {beta}-carotene, have been performed. The expressions for the calculations are derived from the Ashley's optical-data model and from the higher-order correction terms in stopping power calculations. Especially, the Bloch correction for the inelastic MFP is proposed empirically in this work. The inelastic MFPs for energetic protons in water are also evaluated and compared with other theoretical calculations. The proton inelastic MFPs for these 11 bioorganic compounds in the energy range from 0.05 to 10 MeV are presented here for the first time, and might be useful for studies of various radiation effects in these materials.

  18. The self-consistent charge density functional tight binding method applied to liquid water and the hydrated excess proton: benchmark simulations. (United States)

    Maupin, C Mark; Aradi, Bálint; Voth, Gregory A


    The self-consistent charge density functional tight binding (SCC-DFTB) method is a relatively new approximate electronic structure method that is increasingly used to study biologically relevant systems in aqueous environments. There have been several gas phase cluster calculations that indicate, in some instances, an ability to predict geometries, energies, and vibrational frequencies in reasonable agreement with high level ab initio calculations. However, to date, there has been little validation of the method for bulk water properties, and no validation for the properties of the hydrated excess proton in water. Presented here is a detailed SCC-DFTB analysis of the latter two systems. This work focuses on the ability of the original SCC-DFTB method, and a modified version that includes a hydrogen bonding damping function (HBD-SCC-DFTB), to describe the structural, energetic, and dynamical nature of these aqueous systems. The SCC-DFTB and HBD-SCC-DFTB results are compared to experimental data and Car-Parrinello molecular dynamics (CPMD) simulations using the HCTH/120 gradient-corrected exchange-correlation energy functional. All simulations for these systems contained 128 water molecules, plus one additional proton in the case of the excess proton system, and were carried out in a periodic simulation box with Ewald long-range electrostatics. The liquid water structure for the original SCC-DFTB is shown to poorly reproduce bulk water properties, while the HBD-SCC-DFTB somewhat more closely represents bulk water due to an improved ability to describe hydrogen bonding energies. Both SCC-DFTB methods are found to underestimate the water dimer interaction energy, resulting in a low heat of vaporization and a significantly elevated water oxygen diffusion coefficient as compared to experiment. The addition of an excess hydrated proton to the bulk water resulted in the Zundel cation (H(5)O(2)(+)) stabilized species being the stable form of the charge defect, which

  19. Effects of thermal conduction and convection on temperature profile in a water calorimeter for proton beams

    Energy Technology Data Exchange (ETDEWEB)

    Gargioni, E.; Manfredotti, C. [Torino Univ. (Italy). Dipt. di Fisica; Laitano, R.F.; Guerra, A.S. [Ist. Nazionale di Metrologia delle Radiazioni Ionizzanti, ENEA, Roma (Italy)


    In water calorimetry, in addition to the temperature increase due to beam energy deposition in water, unwanted thermal effects occur during and after calorimeter irradiation. This should be accounted for by applying proper corrections to the experimental results. In order to determine such corrections heat flow calculations were performed using the `finite element` method. This method applies even to complex 3D geometries with not necessarily symmetric conditions. Some preliminary results of these calculations are presented together with a description of the analytical method for the evaluation of the correction factors that should be applied to the experimental results to account for the above thermal effects. (orig.)

  20. Estimation of the nucleation kinetics for the anti-solvent crystallisation of paracetamol in methanol/water solutions (United States)

    Ó'Ciardhá, Clifford T.; Frawley, Patrick J.; Mitchell, Niall A.


    In this work the primary nucleation kinetics have been estimated for the anti-solvent crystallisation of paracetamol in methanol-water solutions from metastable zone widths (MSZW) and induction times at 25 °C. Laser back-scattering via a focused beam reflectance Measurement (FBRM ®) is utilised to detect the onset of nucleation. The theoretical approach of Kubota was employed to estimate the nucleation kinetics, which accounts for the sensitivity of the nucleation detection technique. This approach is expanded in this work to analyse the induction time for an anti-solvent crystallisation process. Solvent composition is known to have a significant impact on the measured induction times and MSZW. The induction time in this paper was measured from 40% to 70% mass water and the MSZW is measured from 40% to 60% mass water. The primary focus of the paper was to gauge the extent of how solvent composition affects nucleation kinetics so that this effect may be incorporated into a population balance model. Furthermore, the effects of solvent composition on the estimated nucleation rates are investigated. The primary nucleation rates were found to decrease with dynamic solvent composition, with the extent of their reduction linked to the gradient of the solubility curve. Finally, both MSZW and induction time methods have been found to produce similar estimates for the nucleation parameters.

  1. Zinc adsorption effects on arsenite oxidation kinetics at the birnessite-water interface (United States)

    Power, L.E.; Arai, Y.; Sparks, D.L.


    Arsenite is more toxic and mobile than As(V) in soil and sediment environments, and thus it is advantageous to explore factors that enhance oxidation of As(III) to As(V). Previous studies showed that manganese oxides, such as birnessite (??-MnO2), directly oxidized As(III). However, these studies did not explore the role that cation adsorption has on As(III) oxidation. Accordingly, the effects of adsorbed and nonadsorbed Zn on arsenite (As(III)) oxidation kinetics at the birnessite-water interface were investigated using batch adsorption experiments (0.1 g L-1; pH 4.5 and 6.0; I = 0.01 M NaCl). Divalent Zn adsorption on synthetic ??-MnO 2 in the absence of As(III) increased with increasing pH and caused positive shifts in electrophoretic mobility values at pH 4-6, indirectly suggesting inner-sphere Zn adsorption mechanisms. Arsenite was readily oxidized on birnessite in the absence of Zn. The initial As(III) oxidation rate constant decreased with increasing pH from 4.5 to 6.0 and initial As(III) concentrations from 100 to 300 ??M. Similar pH and initial As(III) concentration effects were observed in systems when Zn was present (i.e., presorbed Zn prior to As(III) addition and simultaneously added Zn-As(III) systems), but As(III) oxidation reactions were suppressed compared to the respective control systems. The suppression was more pronounced when Zn was presorbed on the ??-MnO 2 surfaces as opposed to added simultaneously with As(III). This study provides further understanding of As(III) oxidation reactions on manganese oxide surfaces under environmentally applicable conditions where metals compete for reactive sites.

  2. Kinetic and Thermodynamics studies for Castor Oil Extraction Using Subcritical Water Technology. (United States)

    Abdelmoez, Wael; Ashour, Eman; Naguib, Shahenaz M; Hilal, Amr; Al Mahdy, Dalia A; Mahrous, Engy A; Abdel-Sattar, Essam


    In this work both kinetic and thermodynamics of castor oil extraction from its seeds using subcritical water technique were studied. It was found that the extraction process followed two consecutive steps. In these steps, the oil was firstly extracted from inside the powder by diffusion mechanism. Then the extracted oil, due to extending the extraction time under high temperature and pressure, was subjected to a decomposition reaction following first order mechanism. The experimental data correlated well with the irreversible consecutive unimolecular-type first order mechanism. The values of both oil extraction rate constants and decomposition rate constants were calculated through non-linear fitting using DataFit software. The extraction rate constants were found to be 0.0019, 0.024, 0.098, 0.1 and 0.117 min(-1), while the decomposition rate constants were 0.057, 0.059, 0.014, 0.019 and 0.17 min(-1) at extraction temperatures of 240, 250, 260, 270 and 280°C, respectively. The thermodynamic properties of the oil extraction process were investigated using Arrhenius equation. The values of the activation energy, Ea, and the frequency factor, A, were 73 kJ mol(-1) and 946, 002 min(-1), respectively. The physicochemical properties of the extracted castor oil including the specific gravity, viscosity, acid value, pH value and calorific value were found to be 0.947, 7.487, 1.094 mg KOH/g, 6.1, and 41.5 MJ/Kg, respectively. Gas chromatography analysis showed that ricinoleic acid (83.6%) appears as the predominant fatty acid in the extracted oil followed by oleic acid (5.5%) and linoleic acid (2.3%).

  3. Produced water re-injection in a non-fresh water aquifer with geochemical reaction, hydrodynamic molecular dispersion and adsorption kinetics controlling: model development and numerical simulation (United States)

    Obe, Ibidapo; Fashanu, T. A.; Idialu, Peter O.; Akintola, Tope O.; Abhulimen, Kingsley E.


    An improved produced water reinjection (PWRI) model that incorporates filtration, geochemical reaction, molecular transport, and mass adsorption kinetics was developed to predict cake deposition and injectivity performance in hydrocarbon aquifers in Nigeria oil fields. Thus, the improved PWRI model considered contributions of geochemical reaction, adsorption kinetics, and hydrodynamic molecular dispersion mechanism to alter the injectivity and deposition of suspended solids on aquifer wall resulting in cake formation in pores during PWRI and transport of active constituents in hydrocarbon reservoirs. The injectivity decline and cake deposition for specific case studies of hydrocarbon aquifers in Nigeria oil fields were characterized with respect to its well geometry, lithology, and calibrations data and simulated in COMSOL multiphysics software environment. The PWRI model was validated by comparisons to assessments of previous field studies based on data and results supplied by operator and regulator. The results of simulation showed that PWRI performance was altered because of temporal variations and declinations of permeability, injectivity, and cake precipitation, which were observed to be dependent on active adsorption and geochemical reaction kinetics coupled with filtration scheme and molecular dispersion. From the observed results and findings, transition time t r to cake nucleation and growth were dependent on aquifer constituents, well capacity, filtration coefficients, particle-to-grain size ratio, water quality, and more importantly, particle-to-grain adsorption kinetics. Thus, the results showed that injectivity decline and permeability damage were direct contributions of geochemical reaction, hydrodynamic molecular diffusion, and adsorption kinetics to the internal filtration mechanism, which are largely dependent on the initial conditions of concentration of active constituents of produced water and aquifer capacity.

  4. Removal of triclosan via peroxidases-mediated reactions in water: Reaction kinetics, products and detoxification

    Energy Technology Data Exchange (ETDEWEB)

    Li, Jianhua; Peng, Jianbiao [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023 (China); Zhang, Ya [Nanjing Institute of Environmental Sciences, Ministry of Environmental Protection of the People’s Republic of China, Nanjing 210042 (China); Ji, Yuefei [College of Resources and Environmental Science, Nanjing Agricultural University, Nanjing 210095 (China); Shi, Huanhuan; Mao, Liang [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023 (China); Gao, Shixiang, E-mail: [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023 (China)


    Highlights: • Enzymatic treatment of triclosan in water by soybean and horseradish peroxidases. • pH, H{sub 2}O{sub 2} concentration and enzyme dosage affected the removal efficiency of TCS. • The removal of TCS by SBP was more efficient than that of HRP. • K{sub CAT} and K{sub CAT}/K{sub M} values for SBP toward TCS were much higher than those for HRP. • Polymers formed via radical coupling mechanism were nontoxic to the growth of alga. - Abstract: This study investigated and compared reaction kinetics, product characterization, and toxicity variation of triclosan (TCS) removal mediated by soybean peroxidase (SBP), a recognized potential peroxidase for removing phenolic pollutants, and the commonly used horseradish peroxidase (HRP) with the goal of assessing the technical feasibility of SBP-catalyzed removal of TCS. Reaction conditions such as pH, H{sub 2}O{sub 2} concentration and enzyme dosage were found to have a strong influence on the removal efficiency of TCS. SBP can retain its catalytic ability to remove TCS over broad ranges of pH and H{sub 2}O{sub 2} concentration, while the optimal pH and H{sub 2}O{sub 2} concentration were 7.0 and 8 μM, respectively. 98% TCS was removed with only 0.1 U mL{sup −1} SBP in 30 min reaction time, while an HRP dose of 0.3 U mL{sup −1} was required to achieve the similar conversion. The catalytic performance of SBP towards TCS was more efficient than that of HRP, which can be explained by catalytic rate constant (K{sub CAT}) and catalytic efficiency (K{sub CAT}/K{sub M}) for the two enzymes. MS analysis in combination with quantum chemistry computation showed that the polymerization products were generated via C−C and C−O coupling pathways. The polymers were proved to be nontoxic through growth inhibition of green alga (Scenedesmus obliquus). Taking into consideration of the enzymatic treatment cost, SBP may be a better alternative to HRP upon the removal and detoxification of TCS in water

  5. Kinetic model for predicting the concentrations of active halogens species in chlorinated saline cooling waters. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Haag, W.R.; Lietzke, M.H.


    A kinetic model has been developed for describing the speciation of chlorine-produced oxidants in seawater as a function of time. The model is applicable under a broad variety of conditions, including all pH range, salinities, temperatures, ammonia concentrations, organic amine concentrations, and chlorine doses likely to be encountered during power plant cooling water chlorination. However, the effects of sunlight are not considered. The model can also be applied to freshwater and recirculating water systems with cooling towers. The results of the model agree with expectation, however, complete verification is not feasible at the present because analytical methods for some of the predicted species are lacking.

  6. Proton pumping in cytochrome c oxidase: energetic requirements and the role of two proton channels. (United States)

    Blomberg, Margareta R A; Siegbahn, Per E M


    Cytochrome c oxidase is a superfamily of membrane bound enzymes catalyzing the exergonic reduction of molecular oxygen to water, producing an electrochemical gradient across the membrane. The gradient is formed both by the electrogenic chemistry, taking electrons and protons from opposite sides of the membrane, and by proton pumping across the entire membrane. In the most efficient subfamily, the A-family of oxidases, one proton is pumped in each reduction step, which is surprising considering the fact that two of the reduction steps most likely are only weakly exergonic. Based on a combination of quantum chemical calculations and experimental information, it is here shown that from both a thermodynamic and a kinetic point of view, it should be possible to pump one proton per electron also with such an uneven distribution of the free energy release over the reduction steps, at least up to half the maximum gradient. A previously suggested pumping mechanism is developed further to suggest a reason for the use of two proton transfer channels in the A-family. Since the rate of proton transfer to the binuclear center through the D-channel is redox dependent, it might become too slow for the steps with low exergonicity. Therefore, a second channel, the K-channel, where the rate is redox-independent is needed. A redox-dependent leakage possibility is also suggested, which might be important for efficient energy conservation at a high gradient. A mechanism for the variation in proton pumping stoichiometry over the different subfamilies of cytochrome oxidase is also suggested. This article is part of a Special Issue entitled: 18th European Bioenergetic Conference. Copyright © 2014 Elsevier B.V. All rights reserved.

  7. Ring-shaped velocity distribution functions in energy-dispersed structures formed at the boundaries of a proton stream injected into a transverse magnetic field: Test-kinetic results

    CERN Document Server

    Voitcu, Gabriel


    In this paper, we discuss the formation of ring-shaped and gyro-phase restricted velocity distribution functions (VDFs) at the edges of a cloud of protons injected into non-uniform distributions of the electromagnetic field. The velocity distribution function is reconstructed using the forward test-kinetic method. We consider two profiles of the electric field: (1) a non-uniform E-field obtained by solving the Laplace equation consistent with the conservation of the electric drift and (2) a constant and uniform E-field. In both cases, the magnetic field is similar to the solutions obtained for tangential discontinuities. The initial velocity distribution function is Liouville mapped along numerically integrated trajectories. The numerical results show the formation of an energy-dispersed structure due to the energy-dependent displacement of protons towards the edges of the cloud by the gradient-B drift. Another direct effect of the gradient-B drift is the formation of ring-shaped velocity distribution functio...

  8. Protons and how they are transported by proton pumps. (United States)

    Buch-Pedersen, M J; Pedersen, B P; Veierskov, B; Nissen, P; Palmgren, M G


    The very high mobility of protons in aqueous solutions demands special features of membrane proton transporters to sustain efficient yet regulated proton transport across biological membranes. By the use of the chemical energy of ATP, plasma-membrane-embedded ATPases extrude protons from cells of plants and fungi to generate electrochemical proton gradients. The recently published crystal structure of a plasma membrane H(+)-ATPase contributes to our knowledge about the mechanism of these essential enzymes. Taking the biochemical and structural data together, we are now able to describe the basic molecular components that allow the plasma membrane proton H(+)-ATPase to carry out proton transport against large membrane potentials. When divergent proton pumps such as the plasma membrane H(+)-ATPase, bacteriorhodopsin, and F(O)F(1) ATP synthase are compared, unifying mechanistic premises for biological proton pumps emerge. Most notably, the minimal pumping apparatus of all pumps consists of a central proton acceptor/donor, a positively charged residue to control pK(a) changes of the proton acceptor/donor, and bound water molecules to facilitate rapid proton transport along proton wires.

  9. Effect of CYP2C19*2 and *17 mutations on pharmacodynamics and kinetics of proton pump inhibitors in Caucasians

    NARCIS (Netherlands)

    Hunfeld, Nicole G.; Mathot, Ron A.; Touw, Daan J.; Van Schaik, Ron H.; Mulder, Paul G.; Franck, Paul F.; Kuipers, Ernst J.; Geus, William P.


    WHAT IS ALREADY KNOWN ABOUT THIS SUBJECT: The influence of CYP2C19 on the kinetics and dynamics of omeprazole, lansoprazole and rabeprazole has been studied in Japanese subjects. * It has been suggested that subjects with *1/*1 genotype might need stronger acid suppression than *1/*2 and *2/*2


    Directory of Open Access Journals (Sweden)



    Full Text Available An experimental and numerical study of decontamination efficiency was carried through to evaluate the application of solar energy in water treatment in Northeast Brazil. The methodology used was the one proposed by Solar Water Disinfection (SODIS. Contaminated water samples were collected at the community of Robalo, Sergipe State, Brazil, which is characterized by poverty, social exclusion and a high incidence of waterborne diseases. The method used for pre- and post-disinfection microbiological analyses was the Colilert® QuantiTray (IDEXX one. The results show that the efficiency of the disinfection process reached 80 to 100%, however a post-treatment increase in colony counts was observed in some samples. The experimental results were treated numerically, to give disinfection kinetics, thus allowing theoretical and experimental data to be compared. This study further presents considerations for the development of an experimental pilot plant for water disinfection using SODIS.

  11. Development of CFD thermal hydraulics and neutron kinetics coupling methodologies for the prediction of local safety parameters for light water reactors

    Energy Technology Data Exchange (ETDEWEB)

    Perez Manes, Jorge


    This dissertation contributes to the development of high-fidelity coupled neutron kinetic and thermal hydraulic simulation tools with high resolution of the spatial discretization of the involved domains for the analysis of Light Water Reactors transient scenarios.

  12. Water vapour solubility and conductivity study of the proton conductor BaCe(0.9 − x)ZrxY0.1O(3 − δ)

    DEFF Research Database (Denmark)

    Ricote, Sandrine; Bonanos, Nikolaos; Caboche, G:


    in the sample. The direct current conductivity has been measured as a function of oxygen partial pressure, at a water vapour partial pressure of 0.015 atm. The total conductivity has been resolved into a p-type and an ionic component using a fitting procedure appropriate to the assumed defect model....... An estimation of the protonic component was made by assuming a conductivity isotope effect between 1.4 and 1.8. The total conductivity, obtained using impedance spectroscopy has been measured as a function of temperature in the water and heavy water exchanged states. The activation energy has been found to be 0...

  13. Crystallization kinetics and excess free energy of H2O and D2O nanoscale films of amorphous solid water. (United States)

    Smith, R Scott; Matthiesen, Jesper; Knox, Jake; Kay, Bruce D


    Temperature-programmed desorption (TPD) and reflection absorption infrared spectroscopy (RAIRS) are used to investigate the crystallization kinetics and measure the excess free energy of metastable amorphous solid water films (ASW) of H(2)O and D(2)O grown using molecular beams. The desorption rates from the amorphous and crystalline phases of ASW are distinct, and as such, crystallization manifests can be observed in the TPD spectrum. The crystallization kinetics were studied by varying the TPD heating rate from 0.001 to 3 K/s. A coupled desorption-crystallization kinetic model accurately simulates the desorption spectra and accurately predicts the observed temperature shifts in the crystallization. Isothermal crystallization studies using RAIRS are in agreement with the TPD results. Furthermore, highly sensitive measurements of the desorption rates were used to determine the excess free energy of ASW near 150 K. The excess entropy obtained from these data is consistent with there being a thermodynamic continuity between ASW and supercooled liquid water. © 2011 American Chemical Society

  14. Kinetics of oxygen exchange between bisulfite ion and water as studied by oxygen-17 nuclear magnetic resonance spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Horner, D.A.


    The nuclear magnetic relaxation times of oxygen-17 have been measured in aqueous sodium bisulfite solutions in the pH range from 2.5 to 5 as a function of temperature, pH, and S(IV) concentration, at an ionic strength of 1.0 m. The rate law for oxygen exchange between bisulfite ion and water was obtained from an analysis of the data, and is consistent with oxygen exchange occurring via the reaction SO/sub 2/ + H/sub 2/O right reversible H/sup +/ + SHO/sub 3//sup -/. The value of k/sub -1/ is in agreement with relaxation measurements. Direct spectroscopic evidence was found for the existence of two isomers of bisulfite ion: one with the proton bonded to the sulfur (HSO/sub 3//sup -/) and the other with the proton bonded to an oxygen (SO/sub 3/H/sup -/). (The symbol SHO/sub 3//sup -/ in the above chemical equation refers to both isomeric forms of bisulfite ion.) The relative amounts of the two isomers were determined as a function of temperature, and the rate and mechanism of oxygen exchange between the two was investigated. One of the two isomers, presumably SO/sub 3/H/sup -/, exchanges oxygens with water much more rapidly than does the other. A two-pulse sequence was developed which greatly diminished the solvent peak in the NMR spectrum.

  15. NMR Study of Spin-Lattice Relaxation of Water Protons by Mn 2+Adsorbed onto Colloidal Silica (United States)

    Roose, P.; Van Craen, J.; Andriessens, G.; Eisendrath, H.

    The magnetic-field dependence of the water-proton spin-lattice relaxation time (referred to as nuclear-magnetic-relaxation dispersion) has been measured in colloidal silica suspensions after addition of calibrated MnCl 2solutions. The NMRD curves always show the diamagnetic dispersion normally observed in a paramagnetic ion-free silica sol but, above pH 7, also reveal a supplementary relaxation peak at high magnetic fields typical for paramagnetic ion complexes adsorbed onto the silica. The paramagnetic contribution increases linearly with ion concentration until a contribution attributed to free Mn 2+aquo-ions is observed as well. The ion adsorption density[formula]is temperature and pH sensitive; e.g., no adsorption is observed at pH 2.4. The paramagnetic contribution to the experimental NMRD curves, due to adsorption of Mn 2+aquo complexes onto the silica, is satisfactorily described by the Solomon-Bloembergen-Morgan equations. The estimated parameters, resulting from least-squares comparisons, are consistent with the assumption that the primary hydration shell of the adsorbed ion is retained.

  16. Energy dispersive X-ray diffraction applied to laboratory investigation on proton exchange membrane water content in working fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Isopo, A.; Rossi Albertini, V. [Istituto di Struttura della Materia - CNR, Roma (Italy); Nobili, F. [Scuola di Scienze e Tecnologie - Sezione Chimica, Universita degli Studi di Camerino (Italy)


    An original method, based on the energy-dispersive X-ray diffraction, has been recently proposed as a possible laboratory tool to accomplish long time resolved investigation of the water content in a proton exchange membrane fuel cell. However, this method has never been applied to a real working fuel cell. Therefore, a clear comprehension of its effectiveness in terms of relevant parameters such as time and space resolution, sensitivity, and reproducibility has not yet been achieved. In this paper, all these aspects are discussed and clarified. In order to focus on the method overall effectiveness and on the extent of possible improvements, a basic experimental configuration for both the electrochemical station and the X-ray equipment has been set. The method is described with particular attention to its operating principle and to the evaluation of the errors introduced in data assessment. Finally, applications to some model experiments, in particular working states of the device, are provided and the obtained results are discussed. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  17. Nuclear halo of a 177 MeV proton beam in water: theory, measurement and parameterization

    CERN Document Server

    Gottschalk, Bernard; Daartz, Juliane; Wagner, Miles S


    The dose distribution of a monoenergetic pencil beam in water consists of an electromagnetic "core", a "halo" from charged nuclear secondaries, and a much larger "aura" from neutral secondaries. These regions overlap, but each has distinct spatial characteristics. We have measured the core/halo using a 177MeV test beam offset in a water tank. The beam monitor was a fluence calibrated plane parallel ionization chamber (IC) and the field chamber, a dose calibrated Exradin T1, so the dose measurements are absolute (MeV/g/p). We performed depth-dose scans at ten displacements from the beam axis ranging from 0 to 10cm. The dose spans five orders of magnitude, and the transition from halo to aura is clearly visible. We have performed model-dependent (MD) and model-independent (MI) fits to the data. The MD fit separates the dose into core, elastic/inelastic nuclear, nonelastic nuclear and aura terms, and achieves a global rms measurement/fit ratio of 15%. The MI fit uses cubic splines and the same ratio is 9%. We re...

  18. Surfactat’s Impact on the Evaporation Intensity and a Vapor Embryos Generation Kinetics within the Water Droplets (United States)

    Anisimov, M. P.; Terekhov, V. I.; Shishkin, N. E.


    The research of water-surfactant droplets evaporation was provided. The sodium dodecylsulfate was taken as a surfactant (SAS). The initial SAS mass contain was ~ 0,15%. Water and water-surfactant solution droplets were evaporated under the dry air flow blowing at temperatures T0 ~ (20 ÷ 90)0C and air linear velocity VO ~ 2 ÷ 5 m/s. The droplet initial diameter (d0) was equal to ~ 2 mm, Reynolds number was within the interval of Re = 500 ÷ 2000. The droplet evaporation rate and their surface temperature were measured by an Infrared Microscope. The measurements display that the temperature heterogeneity on the droplet surface is initiated by the vapor fluctuating bursts at the local centers. A surfactant admixture into the base liquid (water) has a considerable impact on the vapor centre generation kinetics as well as on the time behavior of the droplets evaporating surfaces. The environmental conditions have the weak impact on the vapor formation, but the inner conditions, i.e. droplet’s temperature and pressure in it and physical properties of the base liquid have the considerable impact on the vapor generation kinetics. A surfactant adding makes surface tension higher. That depresses a heat-mass transfer and rises an average temperature of droplets.

  19. Kinetics of Corrosion Inhibition of Aluminum in Acidic Media by Water-Soluble Natural Polymeric Pectates as Anionic Polyelectrolyte Inhibitors

    Directory of Open Access Journals (Sweden)

    Refat M. Hassan


    Full Text Available Corrosion inhibition of aluminum (Al in hydrochloric acid by anionic polyeletrolyte pectates (PEC as a water-soluble natural polymer polysaccharide has been studied using both gasometric and weight loss techniques. The results drawn from these two techniques are comparable and exhibit negligible differences. The inhibition efficiency was found to increase with increasing inhibitor concentration and decrease with increasing temperature. The inhibition action of PEC on Al metal surface was found to obey the Freundlich isotherm. Factors such as the concentration and geometrical structure of the inhibitor, concentration of the corrosive medium, and temperature affecting the corrosion rates were examined. The kinetic parameters were evaluated and a suitable corrosion mechanism consistent with the kinetic results is discussed in the paper.

  20. Kinetics of photocatalytic removal of 2-amino-5-chloropyridine from water

    Directory of Open Access Journals (Sweden)

    Abramović Biljana F.


    Full Text Available Titanium dioxide sensitized photocatalytic degradation of a pyridine pesticide analogue, 2-amino-5-chloropyridine, was investigated by monitoring the pyridine moiety degradation, as well as by monitoring the chloride generated in the process. Effect of the initial substrate concentration on the rate of its degradation is reported. Here we show that the kinetics of both reactions are of the zero-order in the entire investigated concentration range. The Langmuir-Hinshelwood kinetic model successfully described the influence of the initial substrate concentration on the rate of the pyridine moiety degradation. It was found that dechlorination of the substrate takes place by direct photolysis. The differences in the kinetics of pyridine moiety degradation and dechlorination were explained on the basis of the electrostatic potential for the investigated compound.

  1. The biodegradation kinetics of polychlorinated biphenol in water/sediment systems; Cinetica de biodegradacion de bifenilos policlorados en sistemas agua/sedimento

    Energy Technology Data Exchange (ETDEWEB)

    Manzano Quinones, M. A.; Sales Marquez, D.; Quiroga Alonso, J. M.


    This article presents a kinetic study of the biodegradation process of a commercial mixture of polychlorinated biphenol. Aroclor 1242, in water/sediment systems using an acclimated mixed culture. The variables tested were: the sediment mass to water volume ratio (m/V), the addition of a co-substrate, the influence of biostimulation and bio increase and the addition of an ionic tensioactive. The results obtained employing the Middleton or General Bioremediation Model show that the model fits all the cases studied and makes it possible to obtain useful kinetic parameters such as the concentration of biodegradation-resistant substrate and the kinetic rate constant. (Author) 7 refs.

  2. Hysteresis effect of ammonium and water protons by 1H MAS NMR in (NH4)2CuBr4·2H2O (United States)

    Lim, Ae Ran; Cho, Jiung


    The chemical shifts, linewidths, and spin-lattice relaxation times for ammonium and water protons in (NH4)2CuBr4·2H2O were investigated by 1H magic angle spinning nuclear magnetic resonance (MAS NMR) with a focus on the roles of NH4+ and H2O at high temperatures. The changes in the temperature dependence of the data near Td (=360 K) were related to variations of the H environments; the mechanism above Td was related to hydrogen-bond transfer involving breakage of the weak part of the hydrogen bond. The hysteresis effects for the ammonium and water protons in (NH4)2CuBr4·2H2O by MAS NMR were described with respect to heating and cooling.

  3. Modelling of the Water Absorption Kinetics and Determination of the Water Diffusion Coefficient in the Pith of Raffia vinifera of Bandjoun, Cameroon

    Directory of Open Access Journals (Sweden)

    E. Tiaya Mbou


    Full Text Available The present work focuses on the study of the water absorption phenomenon through the pith of Raffia vinifera along the stem. The water absorption kinetics was studied experimentally by the gravimetric method with the discontinuous control of the sampling mass at temperature of 30°C. The samples of 70 mm × 8 mm × 4 mm were taken from twelve sampling zones of the stem of Raffia vinifera. The result shows that the percentage of water absorption of the pith of Raffia vinifera increases from the periphery to the center in the radial position and from the base to the leaves in the longitudinal position. Fick’s second law was adopted for the study of the water diffusion. Eleven models were tested for the modelling of the water absorption kinetics and the model of Sikame Tagne (2014 is the optimal model. The diffusion coefficients of two stages were determined by the solution of the Fick equation in the twelve sampling zones described by Sikame Tagne et al. (2014. The diffusion coefficients decreased from the center to the periphery in the radial position and from the base to the leaves in the longitudinal position.

  4. A Comparison of Alkaline Water and Mediterranean Diet vs Proton Pump Inhibition for Treatment of Laryngopharyngeal Reflux. (United States)

    Zalvan, Craig H; Hu, Shirley; Greenberg, Barbara; Geliebter, Jan


    Laryngopharyngeal reflux (LPR) is a common disorder with protean manifestations in the head and neck. In this retrospective study, we report the efficacy of a wholly dietary approach using alkaline water, a plant-based, Mediterranean-style diet, and standard reflux precautions compared with that of the traditional treatment approach of proton pump inhibition (PPI) and standard reflux precautions. To determine whether treatment with a diet-based approach with standard reflux precautions alone can improve symptoms of LPR compared with treatment with PPI and standard reflux precautions. This was a retrospective medical chart review of 2 treatment cohorts. From 2010 to 2012, 85 patients with LPR that were treated with PPI and standard reflux precautions (PS) were identified. From 2013 to 2015, 99 patients treated with alkaline water (pH >8.0), 90% plant-based, Mediterranean-style diet, and standard reflux precautions (AMS) were identified. The outcome was based on change in Reflux Symptom Index (RSI). Recorded change in the RSI after 6 weeks of treatment. Of the 184 patients identified in the PS and AMS cohorts, the median age of participants in each cohort was 60 years (95% CI, 18-82) and 57 years (95% CI, 18-93), respectively (47 [56.3%] and 61 [61.7%] were women, respectively). The percentage of patients achieving a clinically meaningful (≥6 points) reduction in RSI was 54.1% in PS-treated patients and 62.6% in AMS-treated patients (difference between the groups, 8.05; 95% CI, -5.74 to 22.76). The mean reduction in RSI was 27.2% for the PS group and 39.8% in the AMS group (difference, 12.10; 95% CI, 1.53 to 22.68). Our data suggest that the effect of PPI on the RSI based on proportion reaching a 6-point reduction in RSI is not significantly better than that of alkaline water, a plant-based, Mediterranean-style diet, and standard reflux precautions, although the difference in the 2 treatments could be clinically meaningful in favor of the dietary approach. The

  5. Radiation tests of the EMU spacesuit for the International SpaceStation using energetic protons

    Energy Technology Data Exchange (ETDEWEB)

    Zeitlin, C.; Heilbronn, L.; Miller, J.; Shavers, M.


    Measurements using silicon detectors to characterize theradiation transmitted through the EMU spacesuit and a human phantom havebeen performed using 155 and 250 MeV proton beams at the Loma LindaUniversity Medical Center (LLUMC). The beams simulate radiationencountered in space, where trapped protons having kinetic energies onthe order of 100 MeV are copious. Protons with 100 MeV kinetic energy andabove can penetrate many centimeters of water of other light materials,so that astronauts exposed to such energetic particles will receive dosesto their internal organs. This dose can be enhanced or reduced byshielding - either from the spacesuit or the self-shielding of the body -but minimization of the risk depends on details of the incident particleflux (in particular the energy spectrum) and on the dose responses of thevarious critical organs.

  6. Water management in a single cell proton exchange membrane fuel cells with a serpentine flow field (United States)

    Hassan, Nik Suhaimi Mat; Daud, Wan Ramli Wan; Sopian, Kamaruzzaman; Sahari, Jaafar

    Gas and water management is the key to achieving good performance from a polymer electrolyte membrane fuel cell (PEMFC) stack. Imbalance between production and evaporation rates can result in either flooding of the electrodes or membrane dehydration, both of which severely limit fuel cell performance. In the present study, a mathematical model was developed to evaluate moisture profiles of hydrogen and air flows in the flow field channels of both the anode and the cathode. For model validation, a single fuel cell was designed with an active area of 200 cm 2. Six humidity sensors were installed in the flow fields of both the anode and the cathode at 457 mm, 1266 mm and 2532 mm from the inlets. The experiment was performed using an Arbin Fuel Cell Test Station. The temperature was varied (25 °C, 40 °C, 50 °C and 60 °C), while hydrogen and air velocities were fixed at 3 L min -1 and 6 L min -1, respectively, during the operation of the single cell. The feed relative humidity at the anode was fixed at 1.0, while the feed relative humidity at the cathode was fixed at 0.005 (dry air). All humidity sensor readings were taken at steady state after 2 h of operation. Model predictions were then compared with experimental results by using the least squares algorithm. The moisture content was found to decrease along the flow field at the anode, but to increase at the cathode. The moisture content profile at the anode was shown to depend on the moisture Peclet number, which decreased with temperature. On the other hand, the moisture profile at the cathode was shown to depend on both the Peclet number and the Damkohler number. The trend of the Peclet number in the cathode followed closely that of the anode. The Damkohler number decreased with temperature, indicating increasing moisture mass transfer with temperature. The moisture profile models were successfully validated by the published data of the estimated overall mass transfer coefficient and moisture effective

  7. Spectroscopic signatures of proton transfer dynamics in the water dimer cation

    Energy Technology Data Exchange (ETDEWEB)

    Kamarchik, Eugene; Kostko, Oleg; Bowman, Joel M.; Ahmed, Musahid; Krylov, Anna I.


    Using full dimensional EOM-IP-CCSD/aug-cc-pVTZ potential energy surfaces, the photoelectron spectrum, vibrational structure, and ionization dynamics of the water dimer radical cation, (H2O)+2, were computed. We also report an experimental photoelectron spectrum which is derived from photoionization efficiency measurements and compares favorably with the theoretical spectrum. The vibrational structure is also compared with the recent experimental work of Gardenier et al. [J. Phys. Chem. A 113, 4772 (2009)] and the recent theoretical calculations by Cheng et al. [J. Phys. Chem. A 113 13779 (2009)]. A reduced dimensionality nuclear Hamiltonian was used to compute the ionization dynamics for both the ground state and first excited state of the cation. The dynamics show markedly different behavior and spectroscopic signatures depending on which state of the cation is accessed by the ionization. Ionization to the ground-state cation surface induces a hydrogen transfer which is complete within 50 femtoseconds, whereas ionization to the first excited state results in a much slower process.

  8. Development of gas diffusion layer using water based carbon slurry for proton exchange membrane fuel cells

    Energy Technology Data Exchange (ETDEWEB)

    Lin, J.F.; Liu, X.; Adame, A.; Villacorta, R. [Fuel Cell Research Laboratory, Engineering Technology Department, Arizona State University, Mesa, AZ 85212 (United States); Wertz, J. [Hollingsworth and Vose Co., A.K. Nicholson Research Lab, 219 Townsend Road, West Groton, MA 01472 (United States); Ahmad, R.; Thommes, M. [Quantachrome Instruments, 1900 Corporate Drive, Boynton Beach, FL 33426 (United States); Kannan, A.M., E-mail: amk@asu.ed [Fuel Cell Research Laboratory, Engineering Technology Department, Arizona State University, Mesa, AZ 85212 (United States)


    The micro-porous layer of gas diffusion layers (GDLs) was fabricated with the carbon slurry dispersed in water containing sodium dodecyl sulfate (SDS), by wire rod coating process. The aqueous carbon slurry with micelle-encapsulation was highly consistent and stable without losing any homogeneity even after adding polytetrafluoroethylene (PTFE) binder for hundreds of hours. The surface morphology, contact angle and pore size distribution of the GDLs were examined using SEM, Goniometer and Hg Porosimeter, respectively. GDLs fabricated with various SDS concentrations were assembled into MEAs and evaluated in a single cell PEMFC under diverse operating relative humidity (RH) conditions using H{sub 2}/O{sub 2} and H{sub 2}/air as reactants. The peak power density of the single cell using the GDLs with optimum SDS concentration was 1400 and 500 mW cm{sup -2} with H{sub 2}/O{sub 2} and H{sub 2}/air at 90% RH, respectively. GDLs were also fabricated with isopropyl alcohol (IPA) based carbon slurry for fuel cell performance comparison. It was found that the composition of the carbon slurry, specifically SDS concentration played a critical role in controlling the pore diameter as well as the corresponding pore volumes of the GDLs.

  9. Destruction of hazardous waste in supercritical water. Part 2, A study of high-pressure methanol oxidation kinetics

    Energy Technology Data Exchange (ETDEWEB)

    Schmitt, R.G.; Butler, P.B. [Iowa Univ., Iowa City, IA (United States); Bergan, N.E. [Sandia National Labs., Livermore, CA (United States); Pitz, W.J.; Westbrook, C.K. [Lawrence Livermore National Lab., CA (United States)


    In supercritical water oxidation, dilute aqueous organic wastes are oxidized at temperatures and pressures above the critical point of water. This process has been successfully demonstrated to treat waste streams of interest to the Department of Energy production facilities. In this paper we present a numerical study on the oxidation kinetics of a waste containing 98% water and 2% methanol under supercritical conditions. The plug-flow reactor model is similar to that presented in an earlier publication. We have corrected the chemistry in this model by changing the reaction rates of unimolecular reactions to their high-pressure limits. Our results show that the decomposition step of H{sub 2}O{sub 2} into the OH radical is the dominant reaction step controlling the destruction of methanol under supercritical conditions. Using the corrected chemistry model, we calculate the characteristic destruction times of methanol as a function of reactor inlet conditions.

  10. A Compilation of Rate Parameters of Water-Mineral Interaction Kinetics for Application to Geochemical Modeling (United States)


    Dekkers and Schoonen, 1994; Janzen et al., 2000; Thomas et al., 2001); Realgar (Lengke and Tempel, 2003); and Sphalerite (Weisener et al., 2003...Geochim. Cosmochim. Acta 66, 3281-3291. Lengke M. F. and Tempel R. N. (2003) Natural realgar and amorphous AsS oxidation kinetics. Geochim

  11. Concerted and stepwise proton-coupled electron transfers in aquo/hydroxo complex couples in water: oxidative electrochemistry of [Os(II)(bpy)(2)(py)(OH(2))](2+). (United States)

    Costentin, Cyrille; Robert, Marc; Savéant, Jean-Michel; Teillout, Anne-Lucie


    Successive oxidation of transition metal(II) aqua complexes (M(II)OH(2) to M(III)OH) is a domain in which proton-coupled electron transfer reactions are extremely common. The mechanism of these PCET reactions-concerted or stepwise-is an important issue in the understanding and design of natural or artificial systems catalyzing the formation of dioxygen by four-electron oxidation of water. Concerted proton-coupled electron transfer from an aqua metal(II) to a hydroxo metal(III) complex requires the close proximity of a proton-accepting group with a pK value between those of the aqua complexes. Otherwise, stepwise electron-proton or proton-electron pathways involving high-energy intermediates are followed. Concerted proton-electron pathways involving water as proton-acceptor or proton-donor group are inefficient. Cyclic voltammetry of the title complex in buffered aqueous solution and re-examination of previous results for the same complex attached to an electrode surface are used to establish these conclusions, which provide a starting point on the route to higher degrees of oxidation, such as those involved in the catalysis of water oxidation.

  12. Proton Transfer Dynamics at the Membrane/Water Interface: Dependence on the Fixed and Mobile pH Buffers, on the Size and Form of Membrane Particles, and on the Interfacial Potential Barrier (United States)

    Cherepanov, Dmitry A.; Junge, Wolfgang; Mulkidjanian, Armen Y.


    Crossing the membrane/water interface is an indispensable step in the transmembrane proton transfer. Elsewhere we have shown that the low dielectric permittivity of the surface water gives rise to a potential barrier for ions, so that the surface pH can deviate from that in the bulk water at steady operation of proton pumps. Here we addressed the retardation in the pulsed proton transfer across the interface as observed when light-triggered membrane proton pumps ejected or captured protons. By solving the system of diffusion equations we analyzed how the proton relaxation depends on the concentration of mobile pH buffers, on the surface buffer capacity, on the form and size of membrane particles, and on the height of the potential barrier. The fit of experimental data on proton relaxation in chromatophore vesicles from phototropic bacteria and in bacteriorhodopsin-containing membranes yielded estimates for the interfacial potential barrier for H+/OH− ions of ∼120 meV. We analyzed published data on the acceleration of proton equilibration by anionic pH buffers and found that the height of the interfacial barrier correlated with their electric charge ranging from 90 to 120 meV for the singly charged species to >360 meV for the tetra-charged pyranine. PMID:14747306

  13. Kinetics of uranium uptake in soft water and the effect of body size, bioaccumulation and toxicity to Hyalella azteca

    Energy Technology Data Exchange (ETDEWEB)

    Alves, L.C. [Department of Biology, University of Waterloo, Waterloo, ON N2L 3G1 (Canada); Aquatic Ecosystems Protection Research Division, Environment Canada, P.O. Box 5050, Burlington, ON L7R 4A6 (Canada); Borgmann, U. [Aquatic Ecosystems Protection Research Division, Environment Canada, P.O. Box 5050, Burlington, ON L7R 4A6 (Canada); Dixon, D.G., E-mail: dgdixon@uwaterloo.c [Department of Biology, University of Waterloo, Waterloo, ON N2L 3G1 (Canada)


    The kinetics of uptake and the effect of body size on uranium (U) bioaccumulation and toxicity to Hyalella azteca exposed to water-only U concentrations in soft water were evaluated. The effect of body size on U bioaccumulation was significant with a slope of -0.35 between log body concentration and log body mass. A saturation kinetic model was satisfactory to describe the uptake rate, elimination rate and the effect of gut-clearance on size-corrected U bioaccumulation in H. azteca. The one-week lethal water concentrations causing 50% mortality for juvenile and adult H. azteca were 1100 and 4000 nmol U/L, respectively. The one-week lethal body concentration causing 50% mortality was 140 nmol U/g for juvenile H. azteca and 220 nmol U/g for adult H. azteca. One-week bioaccumulation studies that properly account for body-size and gut-clearance times can provide valuable data on U bioavailability and toxicity in the environment. - Uranium accumulation by Hyalella azteca approaches steady state after one week but is strongly dependent on body size.

  14. Kinetics of uranium uptake in soft water and the effect of body size, bioaccumulation and toxicity to Hyalella azteca. (United States)

    Alves, L C; Borgmann, U; Dixon, D G


    The kinetics of uptake and the effect of body size on uranium (U) bioaccumulation and toxicity to Hyalella azteca exposed to water-only U concentrations in soft water were evaluated. The effect of body size on U bioaccumulation was significant with a slope of -0.35 between log body concentration and log body mass. A saturation kinetic model was satisfactory to describe the uptake rate, elimination rate and the effect of gut-clearance on size-corrected U bioaccumulation in H. azteca. The one-week lethal water concentrations causing 50% mortality for juvenile and adult H. azteca were 1100 and 4000 nmol U/L, respectively. The one-week lethal body concentration causing 50% mortality was 140 nmol U/g for juvenile H. azteca and 220 nmol U/g for adult H. azteca. One-week bioaccumulation studies that properly account for body-size and gut-clearance times can provide valuable data on U bioavailability and toxicity in the environment.

  15. Kinetics of Ultrasound-Assisted Flavonoid Extraction from Agri-Food Solid Wastes Using Water/Glycerol Mixtures

    Directory of Open Access Journals (Sweden)

    Dimitris P. Makris


    Full Text Available Red grape pomace (RGP and onion solid wastes (OSW were used as raw material to produce flavonoid-enriched extracts, using ultrasound-assisted solid-liquid extraction. The extraction medium used was composed of water and glycerol and under the conditions used the extraction of flavonoids from both materials was shown to obey first-order kinetics. Maximum diffusivities (De values were 4.01 × 10−11 and 2.35 × 10−11 m2·s−1, for RGP and OSW extraction, respectively, while the corresponding activation energies (Ea were 14.00 and 15.23 kJ·mol−1.

  16. Iron oxidation kinetics and phosphorus immobilization at the groundwater-surface water interface

    NARCIS (Netherlands)

    van der Grift, Bas; Rozemeijer, Joachim; Griffioen, Jasper; van der Velde, Ype


    Eutrophication of freshwater environments following diffuse nutrient loads is a widely recognized water quality problem in catchments. Fluxes of non-point P sources to surface waters originate from surface runoff and flow from soil water and groundwater into surface water. The availability of P in

  17. Inactivation kinetics of invertase in honey and honey-glucose syrup formulations: effects of temperature and water activity. (United States)

    Sramek, Martin; Woerz, Benjamin; Horn, Helmut; Weiss, Jochen; Kohlus, Reinhard


    The high viscosity and stickiness of honey in its natural state causes handling difficulties, therefore the demand for honey powder is continuously increasing. Powder preparation has to be performed gently because of the thermo- and oxidation- sensitive nature of honey. The aim of this study was to determine the degradation of invertase during drying as an indirect measure of the retention of valuable honey nutrients. The reaction kinetics were estimated in polyfloral honey and honey-glucose syrup (GS) formulation and the impact of temperature (40-70°C) and water activity (a w 0.23-0.81) was established. The honey-GS formulation (55:45 w/w) was intended for the preparation of high-grade honey powders using the vacuum-drying method. Invertase inactivation at temperatures below 60°C followed first-order kinetics. At 60°C high dilution (a w 0.81) and at 70°C, heterogeneous inactivation behaviour was observed. The best fit of invertase heterogeneous inactivation kinetic was achieved with the Cerf two-fraction model. The GS addition showed a stabilizing effect on invertase during thermal degradation. The data on invertase inactivation gathered here can be utilized to select optimal parameters for honey vacuum-drying and other thermal processes in order to achieve maximum invertase retention. © 2016 Society of Chemical Industry. © 2016 Society of Chemical Industry.

  18. Polarity governed selective amplification of through plane proton shuttling in proton exchange membrane fuel cells. (United States)

    Gautam, Manu; Chattanahalli Devendrachari, Mruthyunjayachari; Thimmappa, Ravikumar; Raja Kottaichamy, Alagar; Pottachola Shafi, Shahid; Gaikwad, Pramod; Makri Nimbegondi Kotresh, Harish; Ottakam Thotiyl, Musthafa


    Graphene oxide (GO) anisotropically conducts protons with directional dominance of in plane ionic transport (σ IP) over the through plane (σ TP). In a typical H 2 -O 2 fuel cell, since the proton conduction occurs through the plane during its generation at the fuel electrode, it is indeed inevitable to selectively accelerate GO's σ TP for advancement towards a potential fuel cell membrane. We successfully achieved ∼7 times selective amplification of GO's σ TP by tuning the polarity of the dopant molecule in its nanoporous matrix. The coexistence of strongly non-polar and polar domains in the dopant demonstrated a synergistic effect towards σ TP with the former decreasing the number of water molecules coordinated to protons by ∼3 times, diminishing the effects of electroosmotic drag exerted on ionic movements, and the latter selectively accelerating σ TP across the catalytic layers by bridging the individual GO planes via extensive host guest H-bonding interactions. When they are decoupled, the dopant with mainly non-polar or polar features only marginally enhances the σ TP, revealing that polarity factors contribute to fuel cell relevant transport properties of GO membranes only when they coexist. Fuel cell polarization and kinetic analyses revealed that these multitask dopants increased the fuel cell performance metrics of the power and current densities by ∼3 times compared to the pure GO membranes, suggesting that the functional group factors of the dopants are of utmost importance in GO-based proton exchange membrane fuel cells.

  19. Investigation of kinetics and absorption isotherm models for hydroponic phytoremediation of waters contaminated with sulfate. (United States)

    Saber, Ali; Tafazzoli, Milad; Mortazavian, Soroosh; James, David E


    Two common wetland plants, Pampas Grass (Cortaderia selloana) and Lucky Bamboo (Dracaena sanderiana), were used in hydroponic cultivation systems for the treatment of simulated high-sulfate wastewaters. Plants in initial experiments at pH 7.0 removed sulfate more efficiently compared to the same experimental conditions at pH 6.0. Results at sulfate concentrations of 50, 200, 300, 600, 900, 1200, 1500 and 3000 mg/L during three consecutive 7-day treatment periods with 1-day rest intervals, showed decreasing trends of both removal efficiencies and uptake rates with increasing sulfate concentrations from the first to the second to the third 7-day treatment periods. Removed sulfate masses per unit dry plant mass, calculated after 23 days, showed highest removal capacity at 600 mg/L sulfate for both plants. A Langmuir-type isotherm best described sulfate uptake capacity of both plants. Kinetic studies showed that compared to pseudo first-order kinetics, pseudo-second order kinetic models slightly better described sulfate uptake rates by both plants. The Elovich kinetic model showed faster rates of attaining equilibrium at low sulfate concentrations for both plants. The dimensionless Elovich model showed that about 80% of sulfate uptake occurred during the first four days' contact time. Application of three 4-day contact times with 2-day rest intervals at high sulfate concentrations resulted in slightly higher uptakes compared to three 7-day contact times with 1-day rest intervals, indicating that pilot-plant scale treatment systems could be sized with shorter contact times and longer rest-intervals. Copyright © 2017 Elsevier Ltd. All rights reserved.

  20. Electrochemical degradation of PAH compounds in process water: A kinetic study on model solutions and a proof of concept study on runoff water from harbour sediment purification

    DEFF Research Database (Denmark)

    Muff, Jens; Søgaard, Erik Gydesen


    The present study has investigated the possibility to apply electrochemical oxidation in the treatment of polycyclic aromatic hydrocarbon (PAHs) pollutants in water. The reaction kinetics of naphthalene, fluoranthene, and pyrene oxidation have been studied in a batch recirculation experimental....... Decreased current densities from 200 to 15 mA cm-2 in the NaCl electrolyte also decreased the removal rates, but significantly enhanced the current efficiencies of the PAH oxidation, based on a defined current efficiency constant, kq. This observation is believed to be due to the suppression of the water...... oxidation side reaction at lower applied voltages. A proof of concept study in real polluted water demonstrated the applicability of the electrochemical oxidation technique for larger scale use, where especially the indirect chloride mediated oxidation approach was a promising technique. However, the risk...

  1. Speciative determination of total V and dissolved inorganic vanadium species in environmental waters by catalytic–kinetic spectrophotometric method

    Directory of Open Access Journals (Sweden)

    Ramazan Gürkan


    Full Text Available A kinetic determination of V(V as a catalyst was spectrophotometrically performed by using the indicator reaction of Gallamine blue (GB+ and bromate at pH 2.0. The reaction was followed by measuring absorbance change for a fixed-time of 3 min at 537 nm. The variables such as reagent concentration, pH, buffer concentration, ionic strength and temperature were optimized to improve the selectivity and sensitivity. Under the optimized conditions, the determination of V(V was performed in the range 1–100 μg L−1 with limits of detection and quantification of 0.31 and 0.94 μg L−1. The developed kinetic method is sufficiently sensitive, selective and simple. It was successfully applied to the speciative determination of total V and inorganic dissolved vanadium species, V(V and V(IV in environmental water samples. The oxidizing property of permanganate is used to differentiate between V(IV and V(V species. The V(IV content was found by subtracting the V(V content from those of total V. The recovery is above 95% for V(V spiked samples. Additionally, the accuracy was validated by analysis of a certified water sample, CRM TMDA-53.3, and the results were in good agreement with the certified value.

  2. CFD Simulation of Flow in an Abrasive Water Suspension Jet: The Effect of Inlet Operating Pressure and Volume Fraction on Skin Friction and Exit Kinetic Energy

    Directory of Open Access Journals (Sweden)

    D. Deepak


    Full Text Available Abrasive particles in the suspension mixture in an abrasive water suspension jet (AWSJ machining causes acute skin friction effect thereby effectively changing the jet diameter due to wear, which in turn influences jet exit kinetic energy. This results in lowering the life of the jet for effective machining. In consideration of this aspect, the present work examines the effect of inlet pressure on skin friction coefficient and jet exit kinetic energy. It is inferred from the analysis that an increase in inlet pressure causes a significant increase in skin friction coefficient and also results in proportional increase in the exit kinetic energy of the jet. Further, it is revealed from the analysis that an increase volume fraction of abrasive (abrasive concentration in water results in significant decrease in the skin friction coefficient and jet exit kinetic energy.

  3. Spin-locking vs. chemical exchange saturation transfer MRI for investigating chemical exchange process between water and labile metabolite protons (United States)

    Jin, Tao; Autio, Joonas; Obata, Takayuki; Kim, Seong-Gi


    Chemical exchange saturation transfer (CEST) and spin-locking (SL) experiments were both able to probe the exchange process between protons of non-equivalent chemical environments. To compare the characteristics of the CEST and SL approaches in the study of chemical exchange effects, we performed CEST and SL experiments at varied pH and concentrated metabolites with exchangeable amide, amine, and hydroxyl protons at 9.4 T. Our results show that: i) On-resonance SL is most sensitive to chemical exchanges in the intermediate exchange regime and is able to detect hydroxyl and amine protons on a millimolar concentration scale. Off-resonance SL and CEST approaches are sensitive to slow-exchanging protons when an optimal SL or saturation pulse power matches the exchanging rate, respectively. ii) Offset frequency-dependent SL and CEST spectra are very similar, and can be explained well with an SL model recently developed by Trott and Palmer. iii) The exchange rate and population of metabolite protons can be determined from offset-dependent SL or CEST spectra or from on-resonance SL relaxation dispersion measurements. iv) The asymmetry of the magnetization transfer ratio (MTRasym) is highly dependent on the choice of saturation pulse power. In the intermediate exchange regime, MTRasym becomes complicated and should be interpreted with care. PMID:21500270

  4. Spin-locking versus chemical exchange saturation transfer MRI for investigating chemical exchange process between water and labile metabolite protons. (United States)

    Jin, Tao; Autio, Joonas; Obata, Takayuki; Kim, Seong-Gi


    Chemical exchange saturation transfer (CEST) and spin-locking (SL) experiments were both able to probe the exchange process between protons of nonequivalent chemical environments. To compare the characteristics of the CEST and SL approaches in the study of chemical exchange effects, we performed CEST and SL experiments at varied pH and concentrated metabolite phantoms with exchangeable amide, amine, and hydroxyl protons at 9.4 T. Our results show that: (i) on-resonance SL is most sensitive to chemical exchanges in the intermediate-exchange regime and is able to detect hydroxyl and amine protons on a millimolar concentration scale. Off-resonance SL and CEST approaches are sensitive to slow-exchanging protons when an optimal SL or saturation pulse power matches the exchanging rate, respectively. (ii) Offset frequency-dependent SL and CEST spectra are very similar and can be explained well with an SL model recently developed by Trott and Palmer (J Magn Reson 2002;154:157-160). (iii) The exchange rate and population of metabolite protons can be determined from offset-dependent SL or CEST spectra or from on-resonance SL relaxation dispersion measurements. (iv) The asymmetry of the magnetization transfer ratio (MTR(asym)) is highly dependent on the choice of saturation pulse power. In the intermediate-exchange regime, MTR(asym) becomes complicated and should be interpreted with care. Copyright © 2010 Wiley-Liss, Inc.

  5. Kinetic buffers. (United States)

    Alibrandi, Giuseppe; Fabbrizzi, Luigi; Licchelli, Maurizio; Puglisi, Antonio


    This paper proposes a new type of molecular device that is able to act as an inverse proton sponge to slowly decrease the pH inside a reaction vessel. This makes the automatic monitoring of the concentration of pH-sensitive systems possible. The device is a composite formed of an alkyl chloride, which kinetically produces acidity, and a buffer that thermodynamically modulates the variation in pH value. Profiles of pH versus time (pH-t plots) have been generated under various experimental conditions by computer simulation, and the device has been tested by carrying out automatic spectrophotometric titrations, without using an autoburette. To underline the wide variety of possible applications, this new system has been used to realize and monitor HCl uptake by a di-copper(II) bistren complex in a single run, in a completely automatic experiment. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Protonated nitrosamide

    DEFF Research Database (Denmark)

    Egsgaard, H.; Carlsen, L.; Øgaard Madsen, J.


    The protonated nitrosamide, NH3NO+, has been generated by chemical ionization mass spectrometry. Although a direct search for this species in ammonia flames has proved negative, fast proton transfer to major flame constituents is supported experimentally as well as by MO calculations....

  7. Proton Therapy (United States)

    ... therapy is one of the most precise and advanced forms of radiation treatment available. How Proton Therapy is Delivered The patient is positioned on a table with a head frame or face mask covering the head. As the cyclotron smashes atoms, the protons released are directed toward ...

  8. [Degradation Kinetics and Formation of Disinfection By-products During Linuron Chlorination in Drinking Water]. (United States)

    Ling, Xiao; Hu, Chen-yan; Cheng, Ming; Gu, Jian


    Chlorination degradation of linuron was studied using the common disinfectant sodium hypochlorite, the effects of chlorine dosage, pH value, bromine ion concentrationand temperature were systematically investigated, and the formation characteristics of disinfection by-products (DBPs) during the chlorination reaction was analyzed. The results showed that the chlorination degradation kinetics of linuron by sodium hypochlorite could be well described by the second-order kinetic model. Moreover, pH values had a great impact on the degradation reaction, and the rate constant reached the maximum level at pH 7, and the base elementary reaction rate constants of HOCl and OCl- with linuron were 4.84 x 10(2) L · (mol · h)(-1) and 3.80 x 10(2) L · (mol · h)(-1), respectively. The reaction rate decreased with the addition of bromide ion and increased with increasing temperature. Furthermore, many kinds of disinfection by- products were produced during the chlorination degradation of linuron, including CF, DCAN, TCNM and halogen acetone. Under conditions of different solution pH and different bromide ion concentrations, there would be significant difference in the types and concentrations of disinfection by-products.

  9. Removal of Pb from Water by Adsorption on Apple Pomace: Equilibrium, Kinetics, and Thermodynamics Studies

    Directory of Open Access Journals (Sweden)

    Piar Chand


    Full Text Available The adsorption-influencing factors such as pH, dose, and time were optimized by batch adsorption study. A 0.8 g dose, 4.0 pH, and 80 min of contact time were optimized for maximum adsorption of Pb on AP. The adsorption isotherms (Langmuir and Freundlich were well fitted to the data obtained with values of qmax (16.39 mg/g; r2=0.985 and K (16.14 mg/g; r2=0.998, respectively. The kinetics study showed that lead adsorption follows the pseudo-second-order kinetics with correlation coefficient (r2 of 0.999 for all of the concentration range. FTIR spectra also showed that the major functional groups like polyphenols (–OH and carbonyl (–CO were responsible for Pb binding on AP. The thermodynamic parameters as ΔG, ΔH (33.54 J/mol, and ΔS (1.08 J/mol/K were also studied and indicate that the reaction is feasible, endothermic, and spontaneous in nature.

  10. Experimental study of water desorption isotherms and thin-layer convective drying kinetics of bay laurel leaves (United States)

    Ghnimi, Thouraya; Hassini, Lamine; Bagane, Mohamed


    The aim of this work is to determine the desorption isotherms and the drying kinetics of bay laurel leaves ( Laurus Nobilis L.). The desorption isotherms were performed at three temperature levels: 50, 60 and 70 °C and at water activity ranging from 0.057 to 0.88 using the statistic gravimetric method. Five sorption models were used to fit desorption experimental isotherm data. It was found that Kuhn model offers the best fitting of experimental moisture isotherms in the mentioned investigated ranges of temperature and water activity. The Net isosteric heat of water desorption was evaluated using The Clausius-Clapeyron equation and was then best correlated to equilibrium moisture content by the empirical Tsami's equation. Thin layer convective drying curves of bay laurel leaves were obtained for temperatures of 45, 50, 60 and 70 °C, relative humidity of 5, 15, 30 and 45 % and air velocities of 1, 1.5 and 2 m/s. A non linear regression procedure of Levenberg-Marquardt was used to fit drying curves with five semi empirical mathematical models available in the literature, The R2 and χ2 were used to evaluate the goodness of fit of models to data. Based on the experimental drying curves the drying characteristic curve (DCC) has been established and fitted with a third degree polynomial function. It was found that the Midilli Kucuk model was the best semi-empirical model describing thin layer drying kinetics of bay laurel leaves. The bay laurel leaves effective moisture diffusivity and activation energy were also identified.

  11. Kinetic Requirements for the Measurement of Mesospheric Water Vapor at 6.8 (microns) under Non-LTE Conditions (United States)

    Zhou, Daniel K.; Mlynczak, Martin G.; Lopez-Puertas, Manuel; Russell, James M., III


    We present accuracy requirements for specific kinetic parameters used to calculate the populations and vibrational temperatures of the H2O(010) and H2O(020) states in the terrestrial mesosphere. The requirements are based on rigorous simulations of the retrieval of mesospheric water vapor profiles from measurements of water vapor infrared emission made by limb scanning instruments on orbiting satellites. Major improvements in the rate constants that describe vibration-to- vibration exchange between the H2O(010) and 02(1) states are required in addition to improved specification of the rate of quenching Of O2(1) by atomic oxygen (0). It is also necessary to more accurately determine the yield of vibrationally excited O2(l) resulting from ozone photolysis. A contemporary measurement of the rate of quenching of H2O(010) by N2 and O2 is also desirable. These rates are either highly uncertain or have never before been measured at atmospheric temperatures. The suggested improvements are necessary for the interpretation of water vapor emission measurements at 6.8 microns to be made from a new spaceflight experiment in less than 2 years. The approach to retrieving water vapor under non-LTE conditions is also presented.

  12. Electrochemical proton relay at the single-molecule level

    DEFF Research Database (Denmark)

    Kuznetsov, A. M.; Medvedev, I. G.; Ulstrup, Jens


    A scheme for the experimental study of single-proton transfer events, based on proton-coupled two-electron transfer between a proton donor and a proton acceptor molecule confined in the tunneling gap between two metal leads in electrolyte solution is suggested. Expressions for the electric current...... are derived and compared with formalism for electron tunneling through redox molecules. The scheme allows studying the kinetics of proton and hydrogen atom transfer as well as kinetic isotope effects at the single-molecule level under electrochemical potential control....

  13. Water, a unique medium for organic reactions : kinetic studies of intermolecular interactions in aqueous solutions

    NARCIS (Netherlands)

    Buurma, Niklaas


    Apart from being a chemically interesting solvent, water provides a cheap (both in cost price and in ecotax) alternative for organic solvents, making it environmentally and economically interesting as well. It was with the aim of clarifying water's behaviour in aqueous reactivity and thereby

  14. Kinetics of Acid Hydrolysis of Water-Soluble Spruce O-Acetyl Galactoglucomannans

    NARCIS (Netherlands)

    Xu, C.; Pranovich, A.; Vahasalo, L.; Hemming, J.; Holmbom, B.; Schols, H.A.; Willfor, S.


    Water-soluble O-acetyl galactoglucomannan (GGM) is a softwood-derived polysaccharide, which can be extracted on an industrial scale from wood or mechanical pulping waters and now is available in kilogram scale for research and development of value-added products. To develop applications of GGM,

  15. Faster Proton Transfer Dynamics of Water on SnO2 Compared to TiO2

    Energy Technology Data Exchange (ETDEWEB)

    Kumar, Nitin [ORNL; Kent, Paul R [ORNL; Bandura, Andrei V. [St. Petersburg State University, St. Petersburg, Russia; Kubicki, James D. [Pennsylvania State University; Wesolowski, David J [ORNL; Cole, David R [ORNL; Sofo, Jorge O. [Pennsylvania State University


    Proton jump processes in the hydration layer on the isostructural TiO2 rutile (110) and SnO2 cassiterite (110) surfaces were studied with density functional theory molecular dynamics. We find that the proton jump rate is more than three times faster on cassiterite compared with rutile. A local analysis based on the correlation between the stretching band of the O-H vibrations and the strength of H-bonds indicates that the faster proton jump activity on cassiterite is produced by a stronger H-bond formation between the surface and the hydration layer above the surface. The origin of the increased H-bond strength on cassiterite is a combined effect of stronger covalent bonding and stronger electrostatic interactions due to differences of its electronic structure. The bridging oxygens form the strongest H-bonds between the surface and the hydration layer. This higher proton jump rate is likely to affect reactivity and catalytic activity on the surface. A better understanding of its origins will enable methods to control these rates.

  16. Faster proton transfer dynamics of water on SnO2 compared to TiO2 (United States)

    Kumar, Nitin; Kent, Paul R. C.; Bandura, Andrei V.; Kubicki, James D.; Wesolowski, David J.; Cole, David R.; Sofo, Jorge O.


    Proton jump processes in the hydration layer on the iso-structural TiO2 rutile (110) and SnO2 cassiterite (110) surfaces were studied with density functional theory molecular dynamics. We find that the proton jump rate is more than three times faster on cassiterite compared with rutile. A local analysis based on the correlation between the stretching band of the O-H vibrations and the strength of H-bonds indicates that the faster proton jump activity on cassiterite is produced by a stronger H-bond formation between the surface and the hydration layer above the surface. The origin of the increased H-bond strength on cassiterite is a combined effect of stronger covalent bonding and stronger electrostatic interactions due to differences of its electronic structure. The bridging oxygens form the strongest H-bonds between the surface and the hydration layer. This higher proton jump rate is likely to affect reactivity and catalytic activity on the surface. A better understanding of its origins will enable methods to control these rates.

  17. Faster proton transfer dynamics of water on SnO2 compared to TiO2. (United States)

    Kumar, Nitin; Kent, Paul R C; Bandura, Andrei V; Kubicki, James D; Wesolowski, David J; Cole, David R; Sofo, Jorge O


    Proton jump processes in the hydration layer on the iso-structural TiO(2) rutile (110) and SnO(2) cassiterite (110) surfaces were studied with density functional theory molecular dynamics. We find that the proton jump rate is more than three times faster on cassiterite compared with rutile. A local analysis based on the correlation between the stretching band of the O-H vibrations and the strength of H-bonds indicates that the faster proton jump activity on cassiterite is produced by a stronger H-bond formation between the surface and the hydration layer above the surface. The origin of the increased H-bond strength on cassiterite is a combined effect of stronger covalent bonding and stronger electrostatic interactions due to differences of its electronic structure. The bridging oxygens form the strongest H-bonds between the surface and the hydration layer. This higher proton jump rate is likely to affect reactivity and catalytic activity on the surface. A better understanding of its origins will enable methods to control these rates.

  18. Kinetic and spectroscopic study of catalysts for water-gas shift and nitrogen oxide removal (United States)

    Kispersky, Vincent Frederick

    adsorbed CO2 proved less competitive for NOx sorption sites, explaining the weak reduction of NSC by CO2 on low Ba loadings. Contrary to CO2, H2O exhibited both beneficial and inhibitory effects on the NSC. Over long periods of time, and at high Ba loadings, the addition of H2O in the feed increased the NSC, attributed to enhanced O2 spillover on the hydroxylated Ba surface allowing greater access to available NOx storage sites. When the Ba loading was reduced, the interaction sphere of Pt particles with the Ba storage component required for O2 to spillover to assist in NOx storage was reduced. Thus, despite the enhanced spillover capacity of oxygen on the hydroxylated storage component other NSC decreasing effects of H2O addition, such as Ba agglomeration, became more dominant and reduced the NSC. Recent developments in selective catalytic reduction have shown Cu and Fe/chabazite (CHA) based zeolites to be particularly well suited to sustaining high catalytic rates without degradation in the harsh environment of diesel engine exhaust. Little has been published about these catalysts as the academic community has just recently learned about the materials and their commercial implementation. Using operando X-ray absorption spectroscopy, combined with first-principles thermodynamics simulations and kinetic analysis, we have studied the nature of the Cu active site on Cu/SSZ-13, Cu/SAPO-34 and Cu/ZSM-5. Examining the catalysts under operando standard SCR conditions (300 ppm NO, 300 ppm NH3, 5% O2, 5% H2O and 5% CO2) showed the catalyst to be in a mixed Cu(I)-Cu(II) oxidation state. Neither the amount of Cu(I) nor Cu(II) individually correlated with the different rates measured on the various zeolite catalysts, and so we proposed that the SCR reaction progresses via a redox mechanism requiring both Cu(I) and Cu(II). First principles thermodynamic calculations found that the redox couple of Cu(I)H2O and Cu(II)(OH)2 were the most thermodynamically stable species of any of the Ox

  19. Removal of Anionic Dyes from Water by Potash Alum Doped Polyaniline: Investigation of Kinetics and Thermodynamic Parameters of Adsorption. (United States)

    Patra, Braja N; Majhi, Deola


    Polyaniline was synthesized by the oxidative polymerization method by using ammonium persulfate as an oxidant. The positive charge in the backbone of the polymer was generated by using Potash alum as a dopant. Scanning electron microscopy (SEM), Fourier transform infrared (FTIR), X-ray fluorescence (XRF), and X-ray diffraction (XRD) techniques were used for characterization of doped polyaniline. The doped polyaniline can be used for selective adsorption of various dyes (selectively sulfonated dyes) from aqueous solution. Adsorption studies regarding the effect of contact time, initial dye concentration, pH, doses of adsorbent, and temperature on adsorption kinetics were investigated. The influence of other anions like Cl(-), NO3(-), and SO4(2-) on the adsorption density of dyes onto doped polyaniline was also explored. Langmuir isotherm and pseudo-second-order kinetics were found to be the most appropriate models to describe the removal of anionic dyes from water through adsorption. Thermodynamic parameters such as free energy (ΔG(0)), enthalpy (ΔH(0)), and entropy (ΔS(0)) changes were also evaluated. The interaction of dyes with doped polyaniline was also investigated by FTIR and UV spectroscopy.

  20. Shifts in Nitrification Kinetics and Microbial Community during Bioaugmentation of Activated Sludge with Nitrifiers Enriched on Sludge Reject Water (United States)

    Yu, Lifang; Peng, Dangcong; Pan, Ruiling


    This study used two laboratory-scale sequencing batch reactors (SBRs) to evaluate the shifts in nitrification kinetics and microbial communities of an activated sludge sewage treatment system (main stream) during bioaugmentation with nitrifiers cultivated on real sludge reject water (side stream). Although bioaugmentation exerted a strong influence on the microbial community and the nitrification kinetics in the main stream, there was 58% of maximum ammonia uptake rate (AUR) and 80% of maximum nitrite uptake rate (NUR) loss of the seed source after bioaugmentation. In addition, nitrite accumulation occurred during bioaugmentation due to the unequal and asynchronous increase of the AUR (from 2.88 to 13.36 mg N/L·h) and NUR (from 0.76 to 4.34 mg N/L·h). FISH results showed that ammonia oxidizing bacteria (AOB) was inclined to be washed out with effluent in contrast to nitrite oxidizing bacteria (NOB), and Nitrosococcus mobilis lineage was the dominant AOB, while the dominant NOB in the main stream gradually transferred from Nitrospira to Nitrobacter. Nitrospina and Nitrococcus which existed in the seed source could not be detected in the main stream. It can be inferred that nitrite accumulation occurred due to the mismatch of NOB structure but washed out with effluent. PMID:23091354

  1. Shifts in Nitrification Kinetics and Microbial Community during Bioaugmentation of Activated Sludge with Nitrifiers Enriched on Sludge Reject Water

    Directory of Open Access Journals (Sweden)

    Lifang Yu


    Full Text Available This study used two laboratory-scale sequencing batch reactors (SBRs to evaluate the shifts in nitrification kinetics and microbial communities of an activated sludge sewage treatment system (main stream during bioaugmentation with nitrifiers cultivated on real sludge reject water (side stream. Although bioaugmentation exerted a strong influence on the microbial community and the nitrification kinetics in the main stream, there was 58% of maximum ammonia uptake rate (AUR and 80% of maximum nitrite uptake rate (NUR loss of the seed source after bioaugmentation. In addition, nitrite accumulation occurred during bioaugmentation due to the unequal and asynchronous increase of the AUR (from 2.88 to 13.36 mg N/L·h and NUR (from 0.76 to 4.34 mg N/L·h. FISH results showed that ammonia oxidizing bacteria (AOB was inclined to be washed out with effluent in contrast to nitrite oxidizing bacteria (NOB, and Nitrosococcus mobilis lineage was the dominant AOB, while the dominant NOB in the main stream gradually transferred from Nitrospira to Nitrobacter. Nitrospina and Nitrococcus which existed in the seed source could not be detected in the main stream. It can be inferred that nitrite accumulation occurred due to the mismatch of NOB structure but washed out with effluent.

  2. Removal of copper ions from water using epichlorohydrin cross-linked beta-cyclodextrin polymer: characterization, isotherms and kinetics. (United States)

    Sikder, M Tajuddin; Islam, Md Shariful; Kikuchi, Tohru; Suzuki, Junichi; Saito, Takeshi; Kurasaki, Masaaki


    Beta-cyclodextrin (beta-CD) cross-linked with epichlorohydrin to form water insoluble beta-cyclodextrin polymer (beta-CDP) has been shown to be an effective sorbent for sorption of organic particles, but the sorption of copper (Cu2+) in aqueous solutions by beta-CDP has not been conducted. The objective of this study was to explore the sorption mechanism of beta-CDP for copper. The effects of different experimental conditions such as pH, ionic strength, contact time, and temperature were inspected using a batch method. In addition, binding scheme was estimated by using Fourier transform infrared (FTIR) spectroscopy, Xray photoelectron spectroscopy (XPS), a scanning electron microscope (SEM), and Brunauer-Emmett-Teller (BET) analysis. The adsorption of Cu2+ was observed to be higher at pH 6.0. The kinetic study revealed that the adsorption is fitted well by the pseudo-second-order kinetic model. The maximum binding of Cu2+ was estimated to be 111.11 mg/g through the Langmuir isotherm model--much higher than the existing sorption technologies. Hence, the adsorption-desorption trends of epichlorohydrin cross-linked with beta-CD, along with its good recyclability, establish an alternative, effective, and novel remediation technology for the removal of Cu2+ from aqueous solutions.

  3. Benzotriazole removal from water by Zn-Al-O binary metal oxide adsorbent: behavior, kinetics and mechanism. (United States)

    Xu, Bingbing; Wu, Fengchang; Zhao, Xiaoli; Liao, Haiqing


    In this study, a novel Zn-Al-O binary metal oxide adsorbent was prepared and used to remove the emerging polar contaminant benzotriazole from water. The adsorption behavior, kinetics and mechanism were systemically studied. Results showed that benzotriazole was rapidly and effectively adsorbed by the adsorbent. Instantaneous adsorption was observed under each studied condition, and the adsorption reached equilibrium within 30 min. High initial benzotriazole concentration enhanced the adsorption. The amount of absorbed benzotriazole increased with increasing adsorbent dosage, but decreased with increasing ionic strength. Solution pH had little effect on benzotriazole adsorption. The adsorption isotherm was consistent with S-type. Langmuir isotherm model fitted the equilibrium data better than Freundlich, Dubinin-Radushkevich and Temkin isotherm models. The maximum monolayer adsorptive capacity of benzotriazole with and without electrolytes was 7.30 mg g(-1) and 9.51 mg g(-1), respectively. Elovich and pseudo-second-order models were most suitable for describing the adsorption kinetics. Interactions between the surface sites of the adsorbent and benzotriazole may be a combination of electrostatic interaction, ion exchange and hydrogen bond. Copyright © 2010 Elsevier B.V. All rights reserved.

  4. Platinum Activated IrO2/SnO2 Nanocatalysts and Their Electrode Structures for High Performance Proton Exchange Membrane Water Electrolysis

    DEFF Research Database (Denmark)

    Xu, Junyuan; Li, Qingfeng; Christensen, Erik


    In order to improve proton exchange membrane water electrolysis performance, anode catalyst and catalyst layer were examined in this work. SnO2 supported IrO2 nanocatalyst and its analogue with platinum enhancement were firstly synthesized for the oxygen evolution reaction. The effect of the intr...... improved due to the appropriate porosity and pore size distribution. The highest electrolyser performance of 1.63 V at 2 A cm-2 was achieved at 80 °C for optimized catalyst layers containing platinum activated IrO2/SnO2 catalyst....

  5. Determination of protonation constants of some 3-alkyl(aryl-4-(p-t-butyl(benzyl/benzylidenamino-4,5-dihydro-1H-1,2,4-triazole-5-one derivatives in ethanol-water mixtures

    Directory of Open Access Journals (Sweden)

    Fatih İslamoğlu


    Full Text Available Stoichiometric protonation constants of some 3-alkyl(aryl-4-(p-t-butyl(benzyl/benzylidenamino-4,5-dihydro-1H-1,2,4-triazole-5-one derivatives were determined potentiometrically in 50% (v/v ethanol-water mixtures at 25 oC with an ionic strength of 0.10 M. The calculation of the stoichiometric protonation constants was carried out using a PKAS computer program. The effect of solvents composition on the stoichiometric protonation constants are discussed.

  6. Proton interrogation

    Energy Technology Data Exchange (ETDEWEB)

    Morris, Christopher L [Los Alamos National Laboratory


    Energetic proton beams may provide an attractive alternative when compared to electromagnetic and neutron beams for active interrogation of nuclear threats because: they have large fission cross sections, long mean free paths and high penetration, and proton beams can be manipulated with magnetic optics. We have measured time-dependent cross sections for delayed neutrons and gamma-rays using the 800 MeV proton beam from the Los Alamos Neutron Science Center for a set of bare and shielded targets. The results show significant signals from both unshielded and shielded nuclear materials. Results will be presented.

  7. Biodegradation of hydrocarbon mixtures in surface waters at environmentally relevant levels - Effect of inoculum origin on kinetics and sequence of degradation

    DEFF Research Database (Denmark)

    Birch, Heidi; Hammershøj, Rikke Høst; Comber, Mike


    potentially impacting the observed biodegradation kinetics. In this study we investigated the effect of inoculum origin on the biodegradation kinetics of hydrocarbons for five inocula from surface waters varying in urbanization and thus expected pre-exposure to petroleum hydrocarbons. A new biodegradation...... method for testing mixtures of hydrophobic chemicals at trace concentrations was demonstrated: Aqueous solutions containing 9 hydrocarbons were generated by passive dosing and diluted with surface water resulting in test systems containing native microorganisms exposed to test substances at ng...... in four of the five waters but lower in water from a rural lake. The sequence of degradation between the 9 hydrocarbons showed similar patterns in the five waters indicating the potential for using selected hydrocarbons for benchmarking between biodegradation tests. Degradation half-times were shorter...

  8. Kinetic dissolution of carbonates and Mn oxides in acidic water: Measurement of in situ field rates and reactive transport modeling (United States)

    Brown, J.G.; Glynn, P.D.


    The kinetics of carbonate and Mn oxide dissolution under acidic conditions were examined through the in situ exposure of pure phase samples to acidic ground water in Pinal Creek Basin, Arizona. The average long-term calculated in situ dissolution rates for calcite and dolomite were 1.65??10-7 and 3.64??10-10 mmol/(cm2 s), respectively, which were about 3 orders of magnitude slower than rates derived in laboratory experiments by other investigators. Application of both in situ and lab-derived calcite and dolomite dissolution rates to equilibrium reactive transport simulations of a column experiment did not improve the fit to measured outflow chemistry: at the spatial and temporal scales of the column experiment, the use of an equilibrium model adequately simulated carbonate dissolution in the column. Pyrolusite (MnO2) exposed to acidic ground water for 595 days increased slightly in weight despite thermodynamic conditions that favored dissolution. This result might be related to a recent finding by another investigator that the reductive dissolution of pyrolusite is accompanied by the precipitation of a mixed Mn-Fe oxide species. In PHREEQC reactive transport simulations, the incorporation of Mn kinetics improved the fit between observed and simulated behavior at the column and field scales, although the column-fitted rate for Mn-oxide dissolution was about 4 orders of magnitude greater than the field-fitted rate. Remaining differences between observed and simulated contaminant transport trends at the Pinal Creek site were likely related to factors other than the Mn oxide dissolution rate, such as the concentration of Fe oxide surface sites available for adsorption, the effects of competition among dissolved species for available surface sites, or reactions not included in the model.

  9. The effect of water temperature and flow on respiration in barnacles: patterns of mass transfer versus kinetic limitation. (United States)

    Nishizaki, Michael T; Carrington, Emily


    In aquatic systems, physiological processes such as respiration, photosynthesis and calcification are potentially limited by the exchange of dissolved materials between organisms and their environment. The nature and extent of physiological limitation is, therefore, likely to be dependent on environmental conditions. Here, we assessed the metabolic sensitivity of barnacles under a range of water temperatures and velocities, two factors that influence their distribution. Respiration rates increased in response to changes in temperature and flow, with an interaction where flow had less influence on respiration at low temperatures, and a much larger effect at high temperatures. Model analysis suggested that respiration is mass transfer limited under conditions of low velocity (temperature (20-25°C). In contrast, limitation by uptake reaction kinetics, when the biotic capacity of barnacles to absorb and process oxygen is slower than its physical delivery by mass transport, prevailed at high flows (40-150 cm s(-1)) and low temperatures (5-15°C). Moreover, there are intermediate flow-temperature conditions where both mass transfer and kinetic limitation are important. Behavioral monitoring revealed that barnacles fully extend their cirral appendages at low flows and display abbreviated 'testing' behaviors at high flows, suggesting some form of mechanical limitation. In low flow-high temperature treatments, however, barnacles displayed distinct 'pumping' behaviors that may serve to increase ventilation. Our results suggest that in slow-moving waters, respiration may become mass transfer limited as temperatures rise, whereas faster flows may serve to ameliorate the effects of elevated temperatures. Moreover, these results underscore the necessity for approaches that evaluate the combined effects of multiple environmental factors when examining physiological and behavioral performance. © 2014. Published by The Company of Biologists Ltd.

  10. Modifying Surface Chemistry of Metal Oxides for Boosting Dissolution Kinetics in Water by Liquid Cell Electron Microscopy. (United States)

    Lu, Yue; Geng, Jiguo; Wang, Kuan; Zhang, Wei; Ding, Wenqiang; Zhang, Zhenhua; Xie, Shaohua; Dai, Hongxing; Chen, Fu-Rong; Sui, Manling


    Dissolution of metal oxides is fundamentally important for understanding mineral evolution and micromachining oxide functional materials. In general, dissolution of metal oxides is a slow and inefficient chemical reaction. Here, by introducing oxygen deficiencies to modify the surface chemistry of oxides, we can boost the dissolution kinetics of metal oxides in water, as in situ demonstrated in a liquid environmental transmission electron microscope (LETEM). The dissolution rate constant significantly increases by 16-19 orders of magnitude, equivalent to a reduction of 0.97-1.11 eV in activation energy, as compared with the normal dissolution in acid. It is evidenced from the high-resolution TEM imaging, electron energy loss spectra, and first-principle calculations where the dissolution route of metal oxides is dynamically changed by local interoperability between altered water chemistry and surface oxygen deficiencies via electron radiolysis. This discovery inspires the development of a highly efficient electron lithography method for metal oxide films in ecofriendly water, which offers an advanced technique for nanodevice fabrication.

  11. Dissolution kinetics of synthetic zeolite NaP1 and its implication to zeolite treatment of contaminated waters. (United States)

    Cama, Jordi; Ayora, Carles; Querol, Xavier; Ganor, Jiwchar


    The effect of pH on the dissolution kinetics of NaP1 zeolite, which was produced from the alkaline treatment of coal fly ash and may be used for decontamination of acid mine waters, is studied. The sample contains considerable amounts of accessory phases that partly dissolve during the experiment. Therefore, the dissolution rate was estimated during a stage in which the Al/Si ratio was equal to that of NaP1 (0.6). The release rate of these elements is controlled by the dissolution of the zeolite itself during this stage. The dissolution rate of NaP1 slows down with increasing pH in the acidic range, becomes constant at an intermediate pH, and increases with increasing pH in the basic range. The observed changes in rates were described using a rate law based on a surface speciation model. Using this rate law, we calculated the half-life of NaP1 to be about 2 years at near neutral pH and less than 10 days at pH below 3. For the utilization of NaP1 in the treatment of wastewaters or acid mine waters, these short half-lives bear two implications: (1) The treated waters must be kept at near neutral pH, and NaP1 should be added periodically to the treated waters in order to compensate for zeolite loss. (2) In water treatment applications that require a relatively short reaction time, the zeolite removed from the effluents should be kept dry in order to avoid its decomposition and the consequent release of the adsorbed metal to the environment.

  12. Photocatalytic degradation of water contaminants in multiple photoreactors and evaluation of reaction kinetic constants independent of photon absorption, irradiance, reactor geometry, and hydrodynamics. (United States)

    Grčić, Ivana; Li Puma, Gianluca


    The literature on photocatalytic oxidation of water pollutants often reports reaction kinetic constants, which cannot be unraveled from photoreactor type and experimental conditions. This study addresses this challenging aspect by presenting a general and simple methodology for the evaluation of fundamental "intrinsic" reaction kinetic constants of photocatalytic degradation of water contaminants, which are independent of photoreactor type, catalyst concentration, irradiance levels, and hydrodynamics. The degradation of the model contaminant, oxalic acid (OA) on titanium dioxide (TiO2) aqueous suspensions, was monitored in two annular photoreactors (PR1 and PR2). The photoreactors with significantly different geometries were operated under different hydrodynamic regimes (turbulent batch mode and laminar flow-through recirculation mode), optical thicknesses, catalyst and OA concentrations, and photon irradiances. The local volumetric rate of photon absorption (LVRPA) was evaluated by the six-flux radiation absorption-scattering model (SFM). The SFM was further combined with a comprehensive kinetic model for the adsorption and photodecomposition of OA on TiO2 to determine local reaction rates and, after integration over the reactor volume, the intrinsic reaction kinetic constants. The model could determine the oxidation of OA in both PR1 and PR2 under a wide range of experimental conditions. This study demonstrates a more meaningful way for determining reaction kinetic constants of photocatalytic degradation of water contaminants.

  13. Regulating Water-Reduction Kinetics in Cobalt Phosphide for Enhancing HER Catalytic Activity in Alkaline Solution. (United States)

    Xu, Kun; Ding, Hui; Zhang, Mengxing; Chen, Min; Hao, Zikai; Zhang, Lidong; Wu, Changzheng; Xie, Yi


    Electrochemical water splitting to produce hydrogen renders a promising pathway for renewable energy storage. Considering limited electrocatalysts have good oxygen-evolution reaction (OER) catalytic activity in acid solution while numerous economical materials show excellent OER catalytic performance in alkaline solution, developing new strategies that enhance the alkaline hydrogen-evolution reaction (HER) catalytic activity of cost-effective catalysts is highly desirable for achieving highly efficient overall water splitting. Herein, it is demonstrated that synergistic regulation of water dissociation and optimization of hydrogen adsorption free energy on electrocatalysts can significantly promote alkaline HER catalysis. Using oxygen-incorporated Co 2 P as an example, the synergistic effect brings about 15-fold enhancement of alkaline HER activity. Theory calculations confirm that the water dissociation free energy of Co 2 P decreases significantly after oxygen incorporation, and the hydrogen adsorption free energy can also be optimized simultaneously. The finding suggests the powerful effectiveness of synergetic regulation of water dissociation and optimization of hydrogen adsorption free energy on electrocatalysts for alkaline HER catalysis. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. SU-F-T-153: Experimental Validation and Calculation Benchmark for a Commercial Monte Carlo Pencil Beam Scanning Proton Therapy Treatment Planning System in Water

    Energy Technology Data Exchange (ETDEWEB)

    Lin, L; Huang, S; Kang, M; Ainsley, C; Solberg, T; McDonough, J; Simone, C [University of Pennsylvania, Philadelphia, PA (United States); Hiltunen, P; Vanderstraeten, R; Lindberg, J; Siljamaki, S; Wareing, T; Davis, I; Barnett, A; McGhee, J [Varian Medical Systems, Inc., Palo Alto, CA (United States)


    Purpose: Eclipse proton Monte Carlo AcurosPT 13.7 was commissioned and experimentally validated for an IBA dedicated PBS nozzle in water. Topas 1.3 was used to isolate the cause of differences in output and penumbra between simulation and experiment. Methods: The spot profiles were measured in air at five locations using Lynx. PTW-34070 Bragg peak chamber (Freiburg, Germany) was used to collect the relative integral Bragg peak for 15 proton energies from 100 MeV to 225 MeV. The phase space parameters (σx, σθ, ρxθ) number of protons per MU, energy spread and calculated mean energy provided by AcurosPT were identically implemented into Topas. The absolute dose, profiles and field size factors measured using ionization chamber arrays were compared with both AcurosPT and Topas. Results: The beam spot size, σx, and the angular spread, σθ, in air were both energy-dependent: in particular, the spot size in air at isocentre ranged from 2.8 to 5.3 mm, and the angular spread ranged from 2.7 mrad to 6 mrad. The number of protons per MU increased from ∼9E7 at 100 MeV to ∼1.5E8 at 225 MeV. Both AcurosPT and TOPAS agree with experiment within 2 mm penumbra difference or 3% dose difference for scenarios including central axis depth dose and profiles at two depths in multi-spot square fields, from 40 to 200 mm, for all the investigated single-energy and multi-energy beams, indicating clinically acceptable source model and radiation transport algorithm in water. Conclusion: By comparing measured data and TOPAS simulation using the same source model, the AcurosPT 13.7 was validated in water within 2 mm penumbra difference or 3% dose difference. Benchmarks versus an independent Monte Carlo code are recommended to study the agreement in output, filed size factors and penumbra differences. This project is partially supported by the Varian grant under the master agreement between University of Pennsylvania and Varian.

  15. Novel sulfonated poly(ether ether ketone ketone)s for direct methanol fuel cells usage: Synthesis, water uptake, methanol diffusion coefficient and proton conductivity (United States)

    Zhang, Gang; Fu, Tiezhu; Shao, Ke; Li, Xianfeng; Zhao, Chengji; Na, Hui; Zhang, Hong

    A novel series of sulfonated poly(ether ether ketone ketone)s (SPEEKKs) with different degrees of sulfonation (Ds) were synthesized from 1,3-bis(3-sodium sulfonate-4-fluorobenzoyl)benzene (1,3-SFBB-Na), 1,3-bis(4-fluorobenzoyl)benzene (1,3-FBB) and 3,3‧,5,5‧-tetramethyl-4,4‧-biphenol (TMBP) by aromatic nucleophilic polycondensation. The chemical structures of SPEEKKs were confirmed by FT-IR spectroscopy and the Ds values of the polymers were calculated by 1H NMR and titration methods, respectively. The thermal stabilities of the SPEEKKs in acid and sodium forms were characterized by thermogravimetric analysis (TGA), which showed that SPEEKKs had excellent thermal properties at high temperatures. All the SPEEKK polymers were easily solution cast into tough membranes. Water uptakes, proton conductivities and methanol diffusion coefficients of the SPEEKK membranes were measured. Water uptake increased with Ds and temperature. Compared to Nafion, the SPEEKK-60, -70 and -80 membranes showed higher proton conductivities at 80 °C, while the other SPEEKK membranes showed relatively lower proton conductivities. This may be due to the different distribution of ion-conducting domains in membrane. However, these membranes showed lower methanol diffusions in the range of 8.32 × 10 -9 to 1.14 × 10 -7 cm 2 s -1 compared with that of Nafion (2 × 10 -6 cm 2 s -1) at the same temperature. The membranes also showed excellent mechanical properties (with a Young's modulus > 1 GPa and a tensile strength > 40 MPa). These results indicate that the SPEEKK membranes are promising materials for use in direct methanol fuel cell (DMFC) applications.

  16. Coupling Key Transport and Reaction Kinetics to Evaluate the Nitrate Source-Sink Function of Groundwater-Surface Water Environments (United States)

    Zarnetske, J. P.


    Groundwater-surface water exchange environments, including groundwater discharge to coastal ecosystems, are characterized by strong hydrological and biogeochemical gradients. These gradients control the fate and transport of important ecosystem solutes, such as biologically-available nitrogen (N) and carbon. However, it is difficult to quantify the spatiotemporal coupling of these physical and biogeochemical gradients. Our recent investigations of N in groundwater-surface water environments (GSEs) help determine the relative role of these physical and biogeochemical controls across a range of temporal and spatial scales. For example, we used an advection, dispersion, and residence time model coupled with multiple Monod kinetic models to simulate the GSE concentrations of oxygen (O2), ammonium (NH4), nitrate (NO3), and dissolved organic carbon (DOC). This modeling showed how physical transport and biogeochemical reaction kinetics couple in GSEs to control the fate of NO3. Further, we examined coupled nitrification-denitrification (N source-sink) dynamics across many scales of transport and reaction conditions with global Monte Carlo sensitivity analyses and a nondimensional form of the models. Results demonstrated that the residence time of water in the GSE and the uptake rate of O2 from either respiration and/or nitrification determined whether the GSE was a source or a sink of NO3 to the surface waters. We further show that whether the GSE is a net NO3 source or net NO3 sink is determined by the ratio of the characteristic transport time to the characteristic reaction time of O2 (i.e., the Damköhler number, DaO2), where GSEs with DaO2 > 1 will be net denitrification environments. Previous investigations of N dynamics variously identified stream GSEs as either a net source or sink of NO3. Our coupling of the hydrological and biogeochemical limitations of N transformations across different temporal and spatial scales within the GSE of streams allows us to explain

  17. Brønsted acid-promoted C-H bond cleavage via electron transfer from toluene derivatives to a protonated nonheme iron(IV)-oxo complex with no kinetic isotope effect. (United States)

    Park, Jiyun; Lee, Yong-Min; Nam, Wonwoo; Fukuzumi, Shunichi


    The reactivity of a nonheme iron(IV)-oxo complex, [(N4Py)Fe(IV)(O)](2+) (N4Py = N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine), was markedly enhanced by perchloric acid (70% HClO4) in the oxidation of toluene derivatives. Toluene, which has a high one-electron oxidation potential (Eox = 2.20 V vs SCE), was oxidized by [(N4Py)Fe(IV)(O)](2+) in the presence of HClO4 in acetonitrile (MeCN) to yield a stoichiometric amount of benzyl alcohol, in which [(N4Py)Fe(IV)(O)](2+) was reduced to [(N4Py)Fe(III)(OH2)](3+). The second-order rate constant (kobs) of the oxidation of toluene derivatives by [(N4Py)Fe(IV)(O)](2+) increased with increasing concentration of HClO4, showing the first-order dependence on [HClO4]. A significant kinetic isotope effect (KIE) was observed when mesitylene was replaced by mesitylene-d12 in the oxidation with [(N4Py)Fe(IV)(O)](2+) in the absence of HClO4 in MeCN at 298 K. The KIE value drastically decreased from KIE = 31 in the absence of HClO4 to KIE = 1.0 with increasing concentration of HClO4, accompanied by the large acceleration of the oxidation rate. The absence of KIE suggests that electron transfer from a toluene derivative to the protonated iron(IV)-oxo complex ([(N4Py)Fe(IV)(OH)](3+)) is the rate-determining step in the acid-promoted oxidation reaction. The detailed kinetic analysis in light of the Marcus theory of electron transfer has revealed that the acid-promoted C-H bond cleavage proceeds via the rate-determining electron transfer from toluene derivatives to [(N4Py)Fe(IV)(OH)](3+) through formation of strong precursor complexes between toluene derivatives and [(N4Py)Fe(IV)(OH)](3+).

  18. Concerted hydrogen-bond dynamics in the transport mechanism of the hydrated proton: a first-principles molecular dynamics study. (United States)

    Berkelbach, Timothy C; Lee, Hee-Seung; Tuckerman, Mark E


    First-principles molecular dynamics calculations performed in a fully converged basis set are used to reveal new details about the mechanism of the anomalous proton-transport process in water, a fundamental question dating back over 200 years. By separating actual structural diffusion from simple rattling events, wherein a proton shuttles forth and back in a hydrogen bond, it is found that the former are driven by a concerted mechanism in which hydronium begins to accept a hydrogen bond from a donor water molecule while the proton-receiving water molecule simultaneously loses one of its acceptor hydrogen bonds. The kinetics of the process are found to be in good agreement with recent experiments.

  19. Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water

    NARCIS (Netherlands)

    van der Grift, B.; Rozemeijer, J. C.|info:eu-repo/dai/nl/304838403; Griffioen, J.; van der Velde, Y.


    The retention of phosphorus in surface waters though co-precipitation of phosphate with Fe-oxyhydroxides during exfiltration of anaerobic Fe(II) rich groundwater is not well understood. We developed an experimental field set-up to study Fe(II) oxidation and P immobilization along the flow-path from

  20. Systematic classification of tablet disintegrants by water uptake and force development kinetics. (United States)

    Quodbach, Julian; Kleinebudde, Peter


    Water uptake and force development of disintegrating tablets provide a high degree of information about the disintegration mechanisms and process itself. An apparatus for the simultaneous measurement of water uptake and force development of tablets is presented, and the gathered data are analysed. Flat faced, 10 mm, dibasic calcium phosphate tablets containing 2% disintegrant are investigated with the newly constructed apparatus. The force is determined with a texture analyser, whereas the water uptake is recorded by a balance. Different measurement regimes are compared with each other. Measured curves are analysed according to their shape and fitted with a modified Hill equation. Known disintegration mechanisms can be confirmed with the newly constructed apparatus - swelling for sodium starch glycolate and croscarmellose sodium, and shape recovery for crospovidone disintegrants. Different brands of polacrilin potassium act by different mechanisms. All curves could be fitted successfully with a modified Hill equation. A novel classification to facilitate the appropriate disintegrant selection is presented on basis of the fit parameters. The new apparatus allows the acquisition of water uptake and force data simultaneously. Parameters calculated with the modified Hill equation provide a simple way to classify disintegrants according to their behaviour. © 2014 Royal Pharmaceutical Society.

  1. Coalescence kinetics of oil-in-water emulsions studied with microfluidics

    NARCIS (Netherlands)

    Krebs, T.; Schroen, C.G.P.H.; Boom, R.M.


    We report the results of experiments on the coalescence dynamics in flowing oil-in-water emulsions using an integrated microfluidic device. The microfluidic circuit permits direct observation of shear-induced collisions and coalescence events between emulsion droplets. Three mineral oils with a

  2. Removal of Fluoride from Water by Adsorption onto Fired Clay Pots: Kinetics and Equilibrium Studies

    Directory of Open Access Journals (Sweden)

    G. P. Kofa


    Full Text Available Excessive fluoride in potable water is a serious health problem in rural areas of many developing countries. Hence, there is a need to find a simple and cost-effective method for water defluoridation in such areas. In the northern part of Cameroon, clay pots are used for cooking food and water storage. The firing of these pots consists of intensive burning using fire wood. They were tested as a potential adsorbent for removing excess fluoride from water. Experiments were carried out in a jar test at room temperature (25 ± 2°C. Effects of contact time (0–90 min, pH (4, 5, 7, 8, and 9, stirring speed (60, 90, 120, and 200 rpm, and ionic strength (0–1000 mg/L were investigated. Results showed that equilibrium was attained in 10 min whatever the pH. Pseudo-second-order and pore diffusion models described well the adsorption process. The highest amount of fluoride adsorbed (1.6 mg/g was obtained at pH 4-5 and the optimum stirring speed is 120 rpm. Ionic strength has a significant effect on fluoride adsorption.

  3. Fe(II) oxidation kinetics and Fe hydroxyphosphate precipitation upon aeration of anaerobic (ground)water

    NARCIS (Netherlands)

    van der Grift, B.|info:eu-repo/dai/nl/373433484; Griffioen, J.|info:eu-repo/dai/nl/091129265; Behrends, T.|info:eu-repo/dai/nl/30484358X; Wassen, M.J.|info:eu-repo/dai/nl/07165710X; Schot, P.P.|info:eu-repo/dai/nl/08071563X; Osté, Leonard


    Exfiltration of anaerobic Fe-rich groundwater into surface water plays an important role in controlling the transport of phosphate (P) from agricultural areas to the sea. Previous laboratory and field studies showed that Fe(II) oxidation upon aeration leads to effective immobilization of dissolved P

  4. Microfluidic methods to assess demulsification kinetics for oil-water-separation

    NARCIS (Netherlands)

    Krebs, T.; Schroën, C.G.P.H.; Boom, R.M.


    The control of emulsion stability is of crucial importance in the process of crude/oil water separation, which is a key step in industrial oil production. Separation is enhanced if coalescence between droplets takes place, the extent of which will depend on the flow parameters as well as on the

  5. Fabrication BaZrO3/PBI-based nanocomposite as a new proton conducting membrane for high temperature proton exchange membrane fuel cells (United States)

    Hooshyari, Khadijeh; Javanbakht, Mehran; Shabanikia, Akbar; Enhessari, Morteza


    Novel PBI (polybenzimidazole)-BaZrO3 (PBZ) nanocomposite membranes have been prepared for the high temperature proton exchange membrane (HT-PEM) fuel cells. The results showed that the water uptake, acid doping level and proton conductivity of the PBZ nanocomposite membranes were higher than that of virgin PBI membrane due to the presence of perovskite structure BaZrO3 nanoparticles, which as protonic conductor can perform as a special pathway for hydrogen transport. The proton conductivity of the PBZ nanocomposite membranes with 13 mol phosphoric acid per PBI repeat unit was obtained 125 mS/cm at 180 °C and 5% relative humidity. It was found that the performance of the fuel cells increases by increasing temperature; this was explained by faster reaction kinetic and higher proton conductivity. The power density and current density at 0.5 V 180 °C with 5% relative humidity were observed 0.56 W/cm2 and 1.12 A/cm2, respectively for PBZ nanocomposite membranes containing 4 wt% of the nanofillers. The results suggested that PBZ nanocomposite membranes are promising electrolytes for HT-PEM fuel cells with improved proton conductivity.

  6. Hangman Catalysis for Photo–and Photoelectro–Chemical Activation of Water Proton-Coupled Electron Transfer Mechanisms of Small Molecule Activation

    Energy Technology Data Exchange (ETDEWEB)

    Nocera, Daniel G. [Harvard Univ., Cambridge, MA (United States)


    The weakest link for the large-scale deployment of solar energy and for that matter, any renewable energy source, is its storage. The energy needs of future society demands are so large that storage must be in the form of fuels owing to their high energy density. Indeed, society has intuitively understood this disparity in energy density as it has developed over the last century as all large-scale energy storage in our society is in the form of fuels. But these fuels are carbon-based. The imperative for the discipline of chemistry, and more generally science, is to develop fuel storage methods that are easily scalable, carbon-neutral and sustainable. These methods demand the creation of catalysts to manage the multi-electron, multi-proton transformations of the conversion of small molecules into fuels. The splitting of water using solar light is a fuel-forming reaction that meets the imperative of large scale energy storage. As light does not directly act on water to engender its splitting into its elemental components, we have designed “hangman” catalysts to effect the energy conversion processes needed for the fuel forming reactions. The hangman construct utilizes a pendant acid/base functionality within the secondary coordination sphere that is “hung” above the redox platform onto which substrate binds. In this way, we can precisely control the delivery of a proton to the substrate, thus ensuring efficient coupling between the proton and electron. An emphasis was on the coupling of electron and proton in the hydrogen evolution reaction (HER) on Ni, Co and Fe porphyrin platforms. Electrokinetic rate laws were developed to define the proton-coupled electron transfer (PCET) mechanism. The HER of Co and Fe porphyrins was metal-centered. Surprisingly, HER this was not the case for Ni porphyrins. In this system, the PCET occurred at the porphyrin platform to give rise to a phlorin. This is one of the first examples of an HER occurring via ligand non

  7. Long-Term Uptake of Phenol-Water Vapor Follows Similar Sigmoid Kinetics on Prehydrated Organic Matter- and Clay-Rich Soil Sorbents. (United States)

    Borisover, Mikhail; Bukhanovsky, Nadezhda; Lado, Marcos


    Typical experimental time frames allowed for equilibrating water-organic vapors with soil sorbents might lead to overlooking slow chemical reactions finally controlling a thermodynamically stable state. In this work, long-term gravimetric examination of kinetics covering about 4000 h was performed for phenol-water vapor interacting with four materials pre-equilibrated at three levels of air relative humidity (RHs 52, 73, and 92%). The four contrasting sorbents included an organic matter (OM)-rich peat soil, an OM-poor clay soil, a hydrophilic Aldrich humic acid salt, and water-insoluble leonardite. Monitoring phenol-water vapor interactions with the prehydrated sorbents, as compared with the sorbent samples in phenol-free atmosphere at the same RH, showed, for the first time, a sigmoid kinetics of phenol-induced mass uptake typical for second-order autocatalytic reactions. The apparent rate constants were similar for all the sorbents, RHs and phenol activities studied. A significant part of sorbed phenol resisted extraction, which was attributed to its abiotic oxidative coupling. Phenol uptake by peat and clay soils was also associated with a significant enhancement of water retention. The delayed development of the sigmoidal kinetics in phenol-water uptake demonstrates that long-run abiotic interactions of water-organic vapor with soil may be overlooked, based on short-term examination.

  8. Proton conducting polymeric materials for hydrogen based electrochemical energy conversion technologies

    DEFF Research Database (Denmark)

    Aili, David

    the membrane well hydrated. However, some of the main issues of the conventional PFSA based PEM fuel cells and water electrolyzers are directly or indirectly related to their relatively low operating temperature. An elevated operating temperature results in better electrode kinetics in general and improved...... and water electrolyzers. This thesis gives an overview of the principles and the current state-of-the-art technology of the hydrogen based electrochemical energy conversion technologies, with special emphasis on the PEM based water electrolyzers and fuel cells (Chapter 1). The fundamental thermodynamics...... of water electrolyzers and fuel cells is also explained. A detailed literature review is given that covers proton conducting polymeric materials and composite membrane concepts as well as the mechanisms of proton conduction in these types of structures. The experimental part of this thesis has focused...

  9. Experimental and Kinetic Modeling Studies on the Conversion of Sucrose to Levulinic Acid and 5-Hydroxymethylfurfural Using Sulfuric Acid in Water

    NARCIS (Netherlands)

    Tan-Soetedjo, Jenny N. M.; van de Bovenkamp, Henk H.; Abdilla, Ria M.; Rasrendra, Carolus B.; van Ginkel, Jacob; Heeres, Hero J.


    We here report experimental and kinetic modeling studies on the conversion of sucrose to levulinic acid (LA) and 5-hydroxymethylfurfural (HMF) in water using sulfuric acid as the catalyst. Both compounds are versatile building blocks for the synthesis of various biobased (bulk) chemicals. A total of

  10. Experimental and Kinetic Modeling Studies on the Sulfuric Acid Catalyzed Conversion of D-Fructose to 5-Hydroxymethylfurfural and Levulinic Acid in Water

    NARCIS (Netherlands)

    Fachri, Boy A.; Abdilla, Ria M.; van de Bovenkamp, Henk H.; Rasrendra, Carolus B.; Heeres, Hero J.


    Levulinic acid (LA) and 5-hydroxymethylfurfural (HMF) have been identified as promising biomass-derived platform chemicals. A kinetic study on the conversion of D-fructose to HMF and LA in water using sulfuric acid as the catalyst has been performed in batch setups. The experiments were carried out

  11. Role of Re in Pt-Re/TiO2 catalyst for water gas shift reaction: A mechanistic and kinetic study.

    NARCIS (Netherlands)

    Azzam, K.G.H.; Babych, Igor V.; Seshan, Kulathuiyer; Lefferts, Leonardus


    Transient kinetic studies and in situ FTIR spectroscopy were used to follow the reaction sequences that occur during water gas shift (WGS) reaction over Pt–Re/TiO2 catalyst. Results pointed to contributions of an associative formate route with redox regeneration and two classical redox routes

  12. New membrane structures with proton conducting properties

    DEFF Research Database (Denmark)

    Nørgaard, Casper Frydendal

    temperature and high relative humidity can cause excessive swelling of the membranes, yielding insufficient mechanical properties and breakdown of membrane function. Moreover, in the case of the Direct Methanol Fuel Cell (DMFC), their significant methanol permeability causes loss of efficiency. Higher...... operating temperatures (>100 °C) are desired as they improve reaction kinetics and reduce the problem of CO poisoning the catalyst, thus allowing reduced noble metal loading in the catalyst layers of the membrane electrode assembly of the fuel cell. Moreover water and heat management can be simplified......Perfluorosulfonic acid membranes (e.g. Nafion®) are the most widely applied electrolytes in Polymer Electrolyte Membrane Fuel Cells (PEMFCs) because of their good chemical stability, mechanical properties and high proton conductivity, when well hydrated. The upper limit of operating temperature...

  13. Water management history affects GHG kinetics and microbial communities composition of an Italian rice paddy (United States)

    Lagomarsino, Alessandra; Agnelli, Allessandroelio; Pastorelli, Roberta; Pallara, Grazia; Rasse, Daniel; Silvennoinen, Hanna


    The water management system of cultivated soils is one of the most important factors affecting the respective magnitudes of CH4 and N2O emissions. We hypothesized an effect of past management on soil microbial communities and greenhouse gas (GHG) production potential The objective of this study were to i) assess the influence of water management history on GHG production potential and microbial community structure, ii) relate GHGs fluxes to the microbial communities involved in CH4 and N2O production inhabiting the different soils. Moreover, the influence of different soil conditioning procedures on GHG potential fluxes was determined. To reach this aim, four soils with different history of water management were compared, using dried and sieved, pre-incubated and fresh soils. Soil conditioning procedures strongly affected GHG emissions potential: drying and sieving determined the highest emission rates and the largest differences among soil types, probably through the release of labile substrates. Conversely, soil pre-incubation tended to homogenize and level out the differences among soils. Microbial communities composition drove GHG emissions potential and was affected by past management. The water management history strongly affected microbial communities structure and the specific microbial pattern of each soil was strictly linked to the gas (CH4 or N2O) emitted. Aerobic soil stimulated N2O peaks, given a possible major contribution of coupled nitrification/denitrification process. As expected, CH4 was lower in aerobic soil, which showed a less abundant archeal community. This work added evidences to support the hypothesis of an adaptation of microbial communities to past land management that reflected in the potential GHG fluxes.

  14. Kinetics of aqueous chlorination of some pharmaceuticals and their elimination from water matrices. (United States)

    Acero, Juan L; Benitez, F Javier; Real, Francisco J; Roldan, Gloria


    Apparent rate constants for the reactions of four selected pharmaceutical compounds (metoprolol, naproxen, amoxicillin, and phenacetin) with chlorine in ultra-pure (UP) water were determined as a function of the pH. It was found that amoxicillin (in the whole pH range 3-12), and naproxen (in the low pH range 2-4) presented high reaction rates, while naproxen (in the pH range 5-9), and phenacetin and metoprolol (in the pH range 2.5-12 for phenacetin, and 3-10 for metoprolol) followed intermediate and slow reaction rates. A mechanism is proposed for the chlorination reaction, which allowed the evaluation of the intrinsic rate constants for the elementary reactions of the ionized and un-ionized species of each selected pharmaceutical with chlorine. An excellent agreement is obtained between experimental and calculated rate constants by this mechanism.The elimination of these substances in several waters (a groundwater, a surface water from a public reservoir, and two effluents from municipal wastewater treatment plants) was also investigated at neutral pH. The efficiency of the chlorination process with respect to the pharmaceuticals elimination and the formation THMs was also established. It is generally observed that the increasing presence of organic and inorganic matter in the water matrices demand more oxidant agent (chlorine), and therefore, less chlorine is available for the oxidation of these compounds. Finally, half-life times and oxidant exposures (CT) required for the removal of 99% of the four pharmaceuticals are also evaluated. These parameters are useful for the establishment of safety chlorine doses in oxidation or disinfection stages of pharmaceuticals in treatment plants.

  15. Effect of material flexibility on the thermodynamics and kinetics of hydrophobically induced evaporation of water. (United States)

    Altabet, Y Elia; Haji-Akbari, Amir; Debenedetti, Pablo G


    The evaporation of water induced by confinement between hydrophobic surfaces has received much attention due to its suggested functional role in numerous biophysical phenomena and its importance as a general mechanism of hydrophobic self-assembly. Although much progress has been made in understanding the basic physics of hydrophobically induced evaporation, a comprehensive understanding of the substrate material features (e.g., geometry, chemistry, and mechanical properties) that promote or inhibit such transitions remains lacking. In particular, comparatively little research has explored the relationship between water's phase behavior in hydrophobic confinement and the mechanical properties of the confining material. Here, we report the results of extensive molecular simulations characterizing the rates, free energy barriers, and mechanism of water evaporation when confined between model hydrophobic materials with tunable flexibility. A single-order-of-magnitude reduction in the material's modulus results in up to a nine-orders-of-magnitude increase in the evaporation rate, with the corresponding characteristic time decreasing from tens of seconds to tens of nanoseconds. Such a modulus reduction results in a 24-orders-of-magnitude decrease in the reverse rate of condensation, with time scales increasing from nanoseconds to tens of millions of years. Free energy calculations provide the barriers to evaporation and confirm our previous theoretical predictions that making the material more flexible stabilizes the confined vapor with respect to liquid. The mechanism of evaporation involves surface bubbles growing/coalescing to form a subcritical gap-spanning tube, which then must grow to cross the barrier.

  16. Estimation of Oxidation Kinetics and Oxide Scale Void Position of Ferritic-Martensitic Steels in Supercritical Water

    Directory of Open Access Journals (Sweden)

    Li Sun


    Full Text Available Exfoliation of oxide scales from high-temperature heating surfaces of power boilers threatened the safety of supercritical power generating units. According to available space model, the oxidation kinetics of two ferritic-martensitic steels are developed to predict in supercritical water at 400°C, 500°C, and 600°C. The iron diffusion coefficients in magnetite and Fe-Cr spinel are extrapolated from studies of Backhaus and Töpfer. According to Fe-Cr-O ternary phase diagram, oxygen partial pressure at the steel/Fe-Cr spinel oxide interface is determined. The oxygen partial pressure at the magnetite/supercritical water interface meets the equivalent oxygen partial pressure when system equilibrium has been attained. The relative error between calculated values and experimental values is analyzed and the reasons of error are suggested. The research results show that the results of simulation at 600°C are approximately close to experimental results. The iron diffusion coefficient is discontinuous in the duplex scale of two ferritic-martensitic steels. The simulation results of thicknesses of the oxide scale on tubes (T91 of final superheater of a 600 MW supercritical boiler are compared with field measurement data and calculation results by Adrian’s method. The calculated void positions of oxide scales are in good agreement with a cross-sectional SEM image of the oxide layers.

  17. Influence of water on clumped-isotope bond reordering kinetics in calcite (United States)

    Brenner, Dana C.; Passey, Benjamin H.; Stolper, Daniel A.


    Oxygen self-diffusion in calcite and many other minerals is considerably faster under wet conditions relative to dry conditions. Here we investigate whether this "water effect" also holds true for solid-state isotope exchange reactions that alter the abundance of carbonate groups with multiple rare isotopes ('clumped' isotope groups) via the process of solid-state bond reordering. We present clumped-isotope reordering rates for optical calcite heated under wet, high-pressure (100 MPa) conditions. We observe only modest increases in reordering rates under such conditions compared with rates for the same material reacted in dry CO2 under low-pressure conditions. Activation energies under wet, high-pressure conditions are indistinguishable from those for dry, low-pressure conditions, while rate constants are resolvably higher (up to ∼3 times) for wet, high-pressure relative to dry, low-pressure conditions in most of our interpretations of experimental results. This contrasts with the water effect for oxygen self-diffusion in calcite, which is associated with lower activation energies, and diffusion coefficients that are ≥103 times higher compared with dry (pure CO2) conditions in the temperature range of this study (385-450 °C). The water effect for clumped-isotopes leads to calculated apparent equilibrium temperatures ("blocking temperatures") for typical geological cooling rates that are only a few degrees higher than those for dry conditions, while O self-diffusion blocking temperatures in calcite grains are ∼150-200 °C lower in wet conditions compared with dry conditions. Since clumped-isotope reordering is a distributed process that occurs throughout the mineral volume, our clumped-isotope results support the suggestion of Labotka et al. (2011) that the water effect in calcite does not involve major changes in bulk (volume) diffusivity, but rather is primarily a surface phenomenon that facilitates oxygen exchange between the calcite surface and external

  18. Protons in near earth orbit

    CERN Document Server

    Alcaraz, J; Alpat, B; Ambrosi, G; Anderhub, H; Ao, L; Arefev, A; Azzarello, P; Babucci, E; Baldini, L; Basile, M; Barancourt, D; Barão, F; Barbier, G; Barreira, G; Battiston, R; Becker, R; Becker, U; Bellagamba, L; Béné, P; Berdugo, J; Berges, P; Bertucci, B; Biland, A; Bizzaglia, S; Blasko, S; Bölla, G; Boschini, M; Bourquin, Maurice; Bruni, G; Buénerd, M; Burger, J D; Burger, W J; Cai, X D; Cavalletti, R; Camps, C; Cannarsa, P; Capell, M; Casadei, D; Casaus, J; Castellini, G; Chang, Y H; Chen, H F; Chen, H S; Chen, Z G; Chernoplekov, N A; Chiarini, A; Tzi Hong Chiueh; Chuang, Y L; Cindolo, F; Commichau, V; Contin, A; Cotta-Ramusino, A; Crespo, P; Cristinziani, M; Da Cunha, J P; Dai, T S; Deus, J D; Dinu, N; Djambazov, L; D'Antone, I; Dong, Z R; Emonet, P; Engelberg, J; Eppling, F J; Eronen, T; Esposito, G; Extermann, Pierre; Favier, Jean; Feng, C C; Fiandrini, E; Finelli, F; Fisher, P H; Flaminio, R; Flügge, G; Fouque, N; Galaktionov, Yu; Gervasi, M; Giusti, P; Grandi, D; Gu, W Q; Hangarter, K; Hasan, A; Hermel, V; Hofer, H; Huang, M A; Hungerford, W; Ionica, M; Ionica, R; Jongmanns, M; Karlamaa, K; Karpinski, W; Kenney, G; Kenny, J; Kim, W; Klimentov, A; Kossakowski, R; Koutsenko, V F; Laborie, G; Laitinen, T; Lamanna, G; Laurenti, G; Lebedev, A; Lee, S C; Levi, G; Levchenko, P M; Liu, C L; Liu Hong Tao; Lolli, M; Lopes, I; Lu, G; Lü, Y S; Lübelsmeyer, K; Luckey, D; Lustermann, W; Maña, C; Margotti, A; Massera, F; Mayet, F; McNeil, R R; Meillon, B; Menichelli, M; Mezzanotte, F; Mezzenga, R; Mihul, A; Molinari, G; Mourão, A M; Mujunen, A; Palmonari, F; Pancaldi, G; Papi, A; Park, I H; Pauluzzi, M; Pauss, Felicitas; Perrin, E; Pesci, A; Pevsner, A; Pilastrini, R; Pimenta, M; Plyaskin, V; Pozhidaev, V; Postema, H; Postolache, V; Prati, E; Produit, N; Rancoita, P G; Rapin, D; Raupach, F; Recupero, S; Ren, D; Ren, Z; Ribordy, M; Richeux, J P; Riihonen, E; Ritakari, J; Röser, U; Roissin, C; Sagdeev, R; Santos, D; Sartorelli, G; Schultz von Dratzig, A; Schwering, G; Seo, E S; Shoutko, V; Shoumilov, E; Siedling, R; Son, D; Song, T; Steuer, M; Sun, G S; Suter, H; Tang, X W; Ting, Samuel C C; Ting, S M; Tornikoski, M; Torromeo, G; Torsti, J; Trümper, J E; Ulbricht, J; Urpo, S; Usoskin, I; Valtonen, E; Van den Hirtz, J; Velcea, F; Velikhov, E P; Verlaat, B; Vetlitskii, I; Vezzu, F; Vialle, J P; Viertel, Gert M; Vitè, Davide F; Von Gunten, H P; Waldmeier-Wicki, S; Wallraff, W; Wang, B C; Wang, J Z; Wang, Y H; Wiik, K; Williams, C; Wu, S X; Xia, P C; Yan, J L; Yan Lu Guang; Yang, C G; Yang, M; Ye Shu Wei; Yeh, P; Xu, Z Z; Zhang, H Y; Zhang, Z P; Zhao, D X; Zhu, G Y; Zhu, W Z; Zhuang, H L; Zichichi, A


    The proton spectrum in the kinetic energy range 0.1 to 200 GeV was measuredby the Alpha Magnetic Spectrometer (AMS) during space shuttle flight STS-91 atan altitude of 380 km. Above the geomagnetic cutoff the observed spectrum isparameterized by a power law. Below the geomagnetic cutoff a substantial secondspectrum was observed concentrated at equatorial latitudes with a flux ~ 70m^-2 sec^-1 sr^-1. Most of these second spectrum protons follow a complicatedtrajectory and originate from a restricted geographic region.

  19. Analysis of proton-density bias corrections based on T1 measurement for robust quantification of water content in the brain at 3 Tesla. (United States)

    Abbas, Zaheer; Gras, Vincent; Möllenhoff, Klaus; Keil, Fabian; Oros-Peusquens, Ana-Maria; Shah, Nadim J


    Estimating tissue water content using high field MRI, such as 3 Tesla (T), is challenging due to the difficulty in dissociating the radio frequency inhomogeneity pattern from the signal arising from tissue intrinsic proton density (PD) variations. To overcome this problem the longitudinal relaxation time T1 can be combined with an initial guess of the PD to yield the desired PD bias correction. However, it is necessary to know whether T1 effects, i.e., any effect contributing to T1 while being independent of tissue hydration, influence the estimated correction. Twenty-five healthy subjects underwent a quantitative 3T MRI protocol enabling acquisition of 64 slices with 1 mm in-plane resolution and 2 mm slice thickness in 14 min. Influence of T1 effects on the estimated water content map is evaluated using a dedicated method including T1 and T2 * information and region of interest-based water content values are compared with the literature. Our analysis indicates that the PD bias correction based on T1 is largely insensitive to T1 effects. Besides, water content results are in good agreement with literature values obtained at 1.5T. This study demonstrates the applicability of a PD bias correction based on T1 to yield tissue water content at 3T. © 2014 Wiley Periodicals, Inc.

  20. Dosimetric verification in water of a Monte Carlo treatment planning tool for proton, helium, carbon and oxygen ion beams at the Heidelberg Ion Beam Therapy Center (United States)

    Tessonnier, T.; Böhlen, T. T.; Ceruti, F.; Ferrari, A.; Sala, P.; Brons, S.; Haberer, T.; Debus, J.; Parodi, K.; Mairani, A.


    The introduction of ‘new’ ion species in particle therapy needs to be supported by a thorough assessment of their dosimetric properties and by treatment planning comparisons with clinically used proton and carbon ion beams. In addition to the latter two ions, helium and oxygen ion beams are foreseen at the Heidelberg Ion Beam Therapy Center (HIT) as potential assets for improving clinical outcomes in the near future. We present in this study a dosimetric validation of a FLUKA-based Monte Carlo treatment planning tool (MCTP) for protons, helium, carbon and oxygen ions for spread-out Bragg peaks in water. The comparisons between the ions show the dosimetric advantages of helium and heavier ion beams in terms of their distal and lateral fall-offs with respect to protons, reducing the lateral size of the region receiving 50% of the planned dose up to 12 mm. However, carbon and oxygen ions showed significant doses beyond the target due to the higher fragmentation tail compared to lighter ions (p and He), up to 25%. The Monte Carlo predictions were found to be in excellent geometrical agreement with the measurements, with deviations below 1 mm for all parameters investigated such as target and lateral size as well as distal fall-offs. Measured and simulated absolute dose values agreed within about 2.5% on the overall dose distributions. The MCTP tool, which supports the usage of multiple state-of-the-art relative biological effectiveness models, will provide a solid engine for treatment planning comparisons at HIT.

  1. Photocatalytic removal of perfluoroalkyl substances from water and wastewater: Mechanism, kinetics and controlling factors. (United States)

    Xu, Bentuo; Ahmed, Mohammad Boshir; Zhou, John L; Altaee, Ali; Wu, Minghong; Xu, Gang


    This review focuses on heterogeneous photocatalysis of perfluoroalkyl substances (PFAS) which are of worldwide concern as emerging persistent organic contaminants. Heterogeneous photocatalysis is an effective and advanced technology for PFAS removal from water with relatively high efficacy. During photocatalysis, various short chain perfluorocarboxylic acids (PFCA) are produced as intermediates and the efficacy is related to the photo-generated hole (h+) and photo-generated electron (e-). PFAS photodegradation in water under UV irradiation is most effective by using In2O3 as the catalyst, followed by Ga2O3 and TiO2. Significantly, modifying the chemical composition or morphology of the catalyst can improve its efficacy for PFAS removal. In2O3 porous nanoplates were found to have the best performance of 100% PFAS decomposition under UV light with rate constant (kt) and half-time (τ1/2) of 0.158 min-1 and 4.4 min, respectively. Catalysts perform well in acidic solution and increasing temperature to a certain extent. The photocatalytic performance is reduced when treating wastewater due to the presence of dissolved organic matter (DOM), with the catalysts following the order: needle-like Ga2O3 > In2O3 > TiO2. Future studies should focus on the development of novel photocatalysts, and their immobilization and application for PFAS removal in wastewater. Copyright © 2017 Elsevier Ltd. All rights reserved.

  2. Prototropic studies in vitreous and in solid phases: Pyranine and 2-naphthol excited state proton transfer

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Fátima Aparecida das Chagas [Departamento de Química Fundamental, Faculdade de Ciências Farmacêuticas, Universidade de São Paulo, SP (Brazil); Rezende, Eduardo Triboni [Universidade Nove de Julho, São Paulo, SP (Brazil); Filho, Décio Briotto [Departamento de Bioquímica Instituto de Química, Faculdade de Ciências Farmacêuticas, Universidade de São Paulo, SP (Brazil); Brito Rezende, Daisy de [Departamento de Química Fundamental, Faculdade de Ciências Farmacêuticas, Universidade de São Paulo, SP (Brazil); Cuccovia, Iolanda Midea [Departamento de Bioquímica Instituto de Química, Faculdade de Ciências Farmacêuticas, Universidade de São Paulo, SP (Brazil); Gome, Ligia Ferreira [Departamento de Análises Clínicas, Faculdade de Ciências Farmacêuticas, Universidade de São Paulo, SP (Brazil); Silva, Mauro Francisco Pinheiro da [Departamento de Química Fundamental, Faculdade de Ciências Farmacêuticas, Universidade de São Paulo, SP (Brazil); and others


    Excited state proton transfer processes in vitreous glasses and in solid mixtures are investigated by steady state fluorimetry and laser flash photolysis kinetic studies with the photoacids pyranine and 2-naphthol. Glasses were derived from TEOS by the sol–gel condensation process and hydrated solid mixtures from NaCl or KH{sub 2}PO{sub 4}/K{sub 2}HPO{sub 4} crystals. The extent of the water content necessary for the reaction is determined. Shrinkage of TEOS derived monoliths from water loss leads to an increase in proton transfer extent due to the increase in local concentrations of accepting and donor buffer species, but the concomitant increase in the ionic strength actuates in an opposite direction. Furthermore, water losses by aging of air-exposed gel goes to a critical 20% weight fraction, beyond it proton transfer reactions are hindered. Similar studies with solid NaCl or solid phosphate buffer mixtures demonstrated the same critical water level indicating that free water molecules are crucial for the proton to escape from the original cage where the geminate ion pair [–||RO{sup −⁎}H{sup +}||–] is formed and can undergo coupled proton transfer reactions. -- Highlights: • Pyranine and 2-naphthol excited state proton transfer in SiO{sub 2} gel, solid phosphate buffer and NaCl. • Sol–gel formation leads to contraction and concentration of donor and accepting species. • 20% weight fraction water is required for the ESPT to go forward.

  3. Preparation of protic ionic liquids with minimal water content and (15)N NMR study of proton transfer. (United States)

    Burrell, Geoffrey L; Burgar, Iko M; Separovic, Frances; Dunlop, Noel F


    Low-molecular-weight Brønsted acids and amine bases were used to reproducibly prepare very dry, high-purity room-temperature protic ionic liquids (PILs). A series of eight amine bases and six Brønsted acids were combined to produce 48 mixtures, of which 18 were liquid at room temperature. The phase transitions and thermal decomposition temperatures were determined for each mixture; whereas viscosity, density and conductivity were determined for the room-temperature liquids. By utilising (15)N NMR it was possible to distinguish between neutral and ionised amine bases (ammonia vs. ammonium-type ion), which indicated that the protic ionic liquids were completely ionised when made as a stoichiometric mixture. However, a Walden plot comparison of fluidity and molar conductivity indicated the majority of PILs had much lower conductivity than predicted by viscosity unless the base contained excess proton-donating groups. This disparity is indicative of protic ionic molecules forming neutral aggregates or non-Newtonian fluid hydrogen-bonded networks with a secondary Grotthuss proton-hopping mechanism arising from polyprotic bases.

  4. Influence of supplementary cementitious materials on water transport kinetics and mechanical properties of hydrated lime and cement mortars

    Directory of Open Access Journals (Sweden)

    Ince, C.


    Full Text Available The purpose of this paper is an investigation of the possible role of supplementary cementitious materials (SCMs on water transport kinetics and mechanical properties of hydrated lime (CL90 and Portland cement (PC mortars. The properties of hydrated lime are significantly different from those of cement and therefore modifying fresh and hardened properties of these mortars are vital for mortar/substrate optimisation in masonry construction. The parameters investigated in this paper often are the main barriers to the use of hydrated lime in construction practice. The results show that transfer sorptivity and time to dewater freshly-mixed hydrated lime mortars can be modified when binder is partially replaced with SCMs. Compressive strength of CL90 mortars is increased systematically with the increased replacement levels of SCMs and the results are supported with the microstructural images. The ability to modify the water transport kinetics and mechanical properties allows compatibility between the mortar and the substrate unit in masonry construction.El objetivo de este artículo es investigar el papel de los materiales cementantes suplementarios (SCMs en la cinética de transporte del agua y en las propiedades mecánicas de los morteros de cal hidratada (CL90 y cemento Portland. Las propiedades de la cal hidratada son significativamente diferentes a las del cemento y por lo tanto el control de las propiedades de los morteros frescos y endurecidos es fundamental en la optimización mortero/substrato en albañilería. Los parámetros estudiados en este trabajo son a menudo las principales barreras para el uso de la cal hidratada en la práctica de la construcción. Los resultados indican que la absortividad y el tiempo necesario para deshidratar morteros de cal hidratada recién mezclados pueden ser controlados cuando el conglomerante es parcialmente remplazado por SCMs. La resistencia a compresión de los morteros CL90 aumenta sistem

  5. Oxidation Chemistry and Kinetics of Model Compounds in Supercritical Water: Glucose, Acetic Acid, and Methylene Chloride (United States)


    daughter, Jerin. I’m coming home. U I I I UDe~afon vii I II I I I - Trust in the Lord with all thine heart; and lean not unto thine own understanding...Introduction Supercritical water oxidation (SCWO) is a resourceful method that can be used to destroy 3 harmful wastes without producing unsafe...mol/cm3 X I0Ś mo/ cnmi mfona % ex Closure 247A 550±1 1.00±.03 2.03±.07 8.0±0.4 98.0±0.3 .0.71 99.1 248 475±1 1.06±.03 2.13±.08 7.9±0.4 14.1±3.6

  6. Hydrogen-bond dynamics and proton transfer in nanoconfinement

    NARCIS (Netherlands)

    van der Loop, T.H.


    Proton transfer is of fundamental importance to both biology and chemistry. Much is known about proton transfer in large water volumes but often proton transfer reactions take place in very small nanometer sized volumes for example between lipid layers and in proton channels in mitochondria and

  7. Proton transfer in methylmalonyl-CoA epimerase from Propionibacterium shermanii. The reaction of (2R)-methylmalonyl-CoA in tritiated water. (United States)

    Fuller, J Q; Leadlay, P F


    The reaction catalysed by methylmalonyl-CoA epimerase from Propionibacterium shermanii was studied in tritiated water, in the direction with (2R)-methylmalonyl-CoA as substrate, under 'irreversible' conditions. After partial reaction, even when most of the substrate had been converted into product (isolated as propionyl-CoA) essentially no solvent tritium appeared in residual (2R)-methylmalonyl-CoA. The product, however, did contain tritium, and the specific radioactivity of the (2S)-epimer was deduced to be 0.33 times that of the solvent. These results provide further support for the mechanism proposed for the epimerase-catalysed reaction in the accompanying paper [Leadlay & Fuller (1983) Biochem. J. 213, 635-642], in which two enzyme bases act respectively as proton donor and acceptor. The observed low discrimination against solvent tritium entering the product can be accounted for by a mechanism in which the release of product is slow, and the re-protonation step on the enzyme is reversible, without leading to isotopic exchange with the solvent. PMID:6311170

  8. Proton MR spectroscopy of normal breasts: Association of risk factors for breast cancer with water and lipid composition of the breast. (United States)

    Wang, Jane; Wang, Ming-Yang; Kuo, Wen-Hung; Chen, Kuan-Lin; Shih, Tiffany Ting-Fang


    To investigate the water and lipid composition of normal women breasts on proton MR spectroscopy ((1)H-MRS), and the association of breast cancer risk factors with (1)H-MRS parameters. Three groups of participants were included: group 1, women without a family history of breast cancer (n=49); group 2, women with at least one affected first-degree relative (n=77); group 3, contralateral normal breasts of women with newly diagnosed unilateral breast cancer (n=84). (1)H-MRS parameters were shown below: water fraction 1 (WF1)=(water integral)/(water integral+integral for methylene peak); lipid line width for methylene resonance (LW1) and lipid line width for methyl peaks (LW2) were measured. The association of breast cancer risk factors - age, breast density, body mass index (BMI), menopausal status, group with (1)H-MRS parameters - was analyzed by multiple linear regression. In age-adjusted multiple linear regression, breast density was positively associated with WF1 (P=0.009, 0.001, and associated with LW1 in groups 1 (P=0.040) and 3 (P=0.005). In group 3, premenopausal breasts had lower LW2 than their postmenopausal counterparts (P=0.033). Group 3 had narrower LW2 than group 2 (P=0.007). The risk factors for breast cancer were associated with (1)H-MRS parameters. Copyright © 2015 Elsevier Inc. All rights reserved.

  9. The influence of humidification and temperature differences between inlet gases on water transport through the membrane of a proton exchange membrane fuel cell (United States)

    Huang, Kuan-Jen; Hwang, Sheng-Jye; Lai, Wei-Hsiang


    This paper discusses the effects of humidification and temperature differences of the anode and cathode on water transport in a proton exchange membrane fuel cell. Heaters are used to cause a difference in gas temperature between two electrodes before the gases enter the fuel cell. The results show that when the temperature of the cathode is higher than that of the anode, the electro-osmotic drag is suppressed. In contrast, when the temperature of the anode is higher than that of cathode, it is enhanced. These effects are more significant when the temperature difference between the anode and cathode is greater. The same trends are seen with back diffusion. Three cases are tested, and the results show that the suppression due to the temperature difference occurs even when the relative humidity is low at the hotter side. The water transport tendencies of electro-osmotic drag and back diffusion in different situations can be expressed as dominant percentages calculated by the water masses collected at the anode and cathode. The suppression effect due to the temperature difference is relatively insignificant with regard to back diffusion compared to electro-osmosis, so water tends to accumulate on the anode rather than the cathode side.

  10. Photochemical transformation of terbutaline (pharmaceutical) in simulated natural waters: degradation kinetics and mechanisms. (United States)

    Yang, Wenli; Ben Abdelmelek, Sihem; Zheng, Zheng; An, Taicheng; Zhang, Danny; Song, Weihua


    In this study, varied nature organic matter isolates were employed to investigate the indirect photo transformation of terbutaline, which is a major feed additive medicine to increase the proportion of lean meat in the livestock. In the indirect photolysis of terbutaline under solar simulated irradiation, (1)O2 plays an important role among the •OH and (3)DOM*. The reaction rate constant of (1)O2 was determined as (7.1 ± 0.3) × 10(6) M(-1) s(-1) at pH 7.0, while the reaction rate constant of •OH was (6.87 ± 0.43) × 10(9) M(-1) s(-1). The contribution of singlet oxygen to the indirect photolysis of terbutaline (19-44%) was higher than that of the hydroxyl radical (1-7%). The pseudo first order rate constants for the photodegradation of terbutaline increase with increasing pH, which indicates that pH mainly affects the reaction rate of the singlet oxygen with the phenolic part of the terbutaline. The Quinone was identified as the main photosensitized product through LC-MS/MS analysis. It is also proposed that the degradation pathway of terbutaline involves reaction between the phenolic part of terbutaline and singlet oxygen. This finding strongly suggests that singlet oxygen was important factor for the photodegradation of terbutaline in natural waters. Copyright © 2013 Elsevier Ltd. All rights reserved.

  11. Kinetic Model for Simultaneous Adsorption/Photodegradation Process of Alizarin Red S in Water Solution by Nano-TiO2 under Visible Light

    Directory of Open Access Journals (Sweden)

    Rita Giovannetti


    Full Text Available The simultaneous adsorption and visible light photodegradation of Alizarin Red S in water solutions were studied in real time mode by using nano-TiO2, such as Anatase and Aeroxide P-25, supported on polypropylene strips. Kinetic results of the overall process were compared with those obtained from separated steps of adsorption and photodegradation previously studied; kinetic advantages were evidenced with the simultaneous approach. From the study of different dye concentrations, a kinetic model has been proposed which describes the overall process. This model considered two consecutive processes: The adsorption of dye on TiO2 surface and its photodegradation. The obtained results were in good agreement with experimental data and can predict the profiles of free dye, dye adsorbed on TiO2 and photoproduct concentrations during the total process.

  12. Dipolar electrostatic energy effect on relaxation process of monolayers at air-water interface: analysis of thermodynamics and kinetics. (United States)

    Ou-Yang, Wei; Weis, Martin; Lee, Keanchuan; Manaka, Takaaki; Iwamoto, Mitsumasa


    In order to understand the effect of electrostatic energy on phase transition from monolayer to multilayer, isobaric relaxation process of Langmuir monolayers composed of stearic acid or ferroelectric polyvinylidene fluoride and trifluoroethylene copolymer with various vinylidene fluoride (VDF) ratios is investigated in terms of thermodynamic and kinetic analysis. A monotonous decreasing tendency of material loss with respect to temperature is observed for stearic acid monolayer, which is due to thermal activation effect on phase transition from monolayer to multilayer. In contrast, for the ferroelectric monolayer it presents a nonmonotonous behavior of losing materials with a peak position near the Curie temperature, which is not only owing to thermal activation but also dipole moment change. This observation is confirmed for the copolymer monolayers with other VDF content ratios. Amazingly, for the ferroelectric monolayers a good correspondence is found for critical temperatures evaluated from several independent methods including the analysis on slow collapse. This finding again tells the fact that the relaxation process, namely phase transition from monolayer to multilayer, is greatly influenced by dipolar electrostatic energy. Moreover, the study of time dependent relaxation process reveals a diffusionlike behavior of multilayer structure formation, which cannot be interpreted by classical models. Hence a new model based on diffusion-driven material transfer is proposed and diffusivity of the copolymer molecules is estimated with a value of 0.4x10(-5) cm(2)/s. As a whole, this research reflects the importance of dipolar electrostatic energy for phase transition of monolayers at air-water interface.

  13. Thionine-Bromate as a New Reaction System for Kinetic Spectrophotometric Determination of Hydrazine in Cooling Tower Water Samples

    Directory of Open Access Journals (Sweden)

    Masoud Reza Shishehbore


    Full Text Available A simple, selective, and inexpensive kinetic method was developed for the determination of hydrazine based on its inhibitory effect on the thionine-bromate system in sulfuric acid media. The reaction was monitored spectrophotometrically at 601 nm by a fixed time method. The effect of different parameters such as concentration of reactants, ionic strength, temperature, and time on the rate of reaction was investigated, and the optimum conditions were obtained. Under optimum conditions, the calibration curve was linear in the concentration range from 0.8–23.0 μg mL−1 of hydrazine, and the detection limit of the method was 0.22 μg mL−1. The relative standard deviation for five replicate determinations of 1.0 μg mL−1 of hydrazine was 0.74%. The potential of interfering effect of foreign species on the hydrazine determination was studied. The proposed method was successfully applied for the determination of hydrazine in different water samples.

  14. Removal of Arsenite from Water by Ce-Al-Fe Trimetal Oxide Adsorbent: Kinetics, Isotherms, and Thermodynamics

    Directory of Open Access Journals (Sweden)

    Cuizhen Sun


    Full Text Available Ce-Al-Fe trimetal oxide adsorbent was prepared. The morphology characteristics of the new adsorbent were analysed by the transmission electron microscope (SEM method. The SEM results implied its ability in the adsorption of As (III. To verify the analyses, bench-scale experiments were performed for the removal of As (III from water. In the experiments of adsorption, As (III adsorption capacity of the trimetal oxide adsorbent was presented significantly higher than activated aluminium oxide and activated carbon. As (III adsorption kinetics resembled pseudo-second-order adsorption mode. When initial As (III concentration was 3, 8, and 10 mg·L−1, the maximum adsorption capacity achieved was 1.48, 3.73, and 5.12 mg·g−1, respectively. In addition, the experimental adsorption data were described well by the Freundlich adsorption isotherm model at 20, 30, and 40°C. The enthalpy change (ΔS, the standard free energy (ΔG, and entropy change (ΔH indicated that the nature of As (III adsorption was exothermic and spontaneous with increasing randomness on the interface of solid and liquid. And the adsorption mechanism can be interpreted as chemisorption with As (III multilayer coverage formation on the adsorbent surface.

  15. Effect of water content and temperature on inactivation kinetics of myrosinase in broccoli (Brassica oleracea var. italica). (United States)

    Oliviero, T; Verkerk, R; Van Boekel, M A J S; Dekker, M


    Broccoli belongs to the Brassicaceae plant family consisting of widely eaten vegetables containing high concentrations of glucosinolates. Enzymatic hydrolysis of glucosinolates by endogenous myrosinase (MYR) can form isothiocyanates with health-promoting activities. The effect of water content (WC) and temperature on MYR inactivation in broccoli was investigated. Broccoli was freeze dried obtaining batches with WC between 10% and 90% (aw from 0.10 to 0.96). These samples were incubated for various times at different temperatures (40-70°C) and MYR activity was measured. The initial MYR inactivation rates were estimated by the first-order reaction kinetic model. MYR inactivation rate constants were lower in the driest samples (10% WC) at all studied temperatures. Samples with 67% and 90% WC showed initial inactivation rate constants all in the same order of magnitude. Samples with 31% WC showed intermediate initial inactivation rate constants. These results are useful to optimise the conditions of drying processes to produce dried broccoli with optimal MYR retention for human health. Copyright © 2014 Elsevier Ltd. All rights reserved.

  16. Stomatal clustering in Begonia associates with the kinetics of leaf gaseous exchange and influences water use efficiency. (United States)

    Papanatsiou, Maria; Amtmann, Anna; Blatt, Michael R


    Stomata are microscopic pores formed by specialized cells in the leaf epidermis and permit gaseous exchange between the interior of the leaf and the atmosphere. Stomata in most plants are separated by at least one epidermal pavement cell and, individually, overlay a single substomatal cavity within the leaf. This spacing is thought to enhance stomatal function. Yet, there are several genera naturally exhibiting stomata in clusters and therefore deviating from the one-cell spacing rule with multiple stomata overlaying a single substomatal cavity. We made use of two Begonia species to investigate whether clustering of stomata alters guard cell dynamics and gas exchange under different light and dark treatments. Begonia plebeja, which forms stomatal clusters, exhibited enhanced kinetics of stomatal conductance and CO2 assimilation upon light stimuli that in turn were translated into greater water use efficiency. Our findings emphasize the importance of spacing in stomatal clusters for gaseous exchange and plant performance under environmentally limited conditions. © The Author 2017. Published by Oxford University Press on behalf of the Society for Experimental Biology.

  17. Kinetics and mechanism of 17β-estradiol chlorination in a pilot-scale water distribution systems. (United States)

    Li, Cong; Dong, Feilong; Crittenden, John C; Luo, Feng; Chen, Xinbo; Zhao, Taotao


    The kinetics and mechanisms of 17β-estradiol (E2) chlorination in water distribution systems (WDS) were studied. We examined the impacts of different factors, including pH, temperature, humic acid concentration and type, and flow velocity. The experimental results showed that the rate constants in beaker tests and WDS were described by a pseudo-first-order model. pH had the greatest impact on E2 chlorination in the beaker tests. However, temperature had the greatest impact on E2 chlorination in WDS. Mechanistic analysis of E2 chlorination showed that chlorine attacked E2 in three stages: 1) halogenation of the aromatic ring, 2) cleavage of the benzene moiety and chlorine or bromine substitution formation, and 3) formation of trihalomethanes (THMs) and halogenated acetic acids (HAAs) from phenolic intermediates through benzene ring opening with chlorine and/or bromine substitution of hydrogen on the carbon atoms. In the third stage, the concentrations of THMs and HAAs increased rapidly. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Removal of cationic pollutants from water by xanthated corn cob: optimization, kinetics, thermodynamics, and prediction of purification process. (United States)

    Kostić, Miloš; Đorđević, Miloš; Mitrović, Jelena; Velinov, Nena; Bojić, Danijela; Antonijević, Milan; Bojić, Aleksandar


    The removal of Cr(III) ions and methylene blue (MB) from aqueous solutions by xanthated corn cob (xCC) in batch conditions was investigated. The sorption capacity of xCC strongly depended of the pH, and increase when the pH rises. The kinetics was well fitted by pseudo-second-order and Chrastil's model. Sorption of Cr(III) ions and MB on xCC was rapid during the first 20 min of contact time and, thereafter, the biosorption rate decrease gradually until reaching equilibrium. The maximum sorption capacity of 17.13 and 83.89 mg g-1 for Cr(III) ions and MB, respectively, was obtained at 40 °C, pH 5, and sorbent dose 4 g dm-3 for removal of Cr(III) ions and 1 g dm-3 for removal of MB. The prediction of purification process was successfully carried out, and the verification of theoretically calculated amounts of sorbent was confirmed by using packed-bed column laboratory system with recirculation of the aqueous phase. The wastewater from chrome plating industry was successfully purified, i.e., after 40 min concentration of Cr(III) ions was decreased lower than 0.1 mg dm-3. Also, removal of MB from the river water was successfully carried out and after 40 min, removal efficiency was about 94%.

  19. Adsorption Equilibrium and Kinetics at Goethite-Water and Related Interfaces

    Energy Technology Data Exchange (ETDEWEB)

    Katz, Lynn Ellen [Univ. of Texas, Austin, TX (United States)


    This research study is an important component of a broader comprehensive project, “Geochemistry of Interfaces: From Surfaces to Interlayers to Clusters,” which sought to identify and evaluate the critical molecular phenomena at metal-oxide interfaces that control many geochemical and environmental processes. The primary goal of this research study was to better understand and predict adsorption of metal ions at mineral/water surfaces. Macroscopic data in traditional batch experiments was used to develop predictive models that characterize sorption in complex systems containing a wide range of background solution compositions. Our studies focused on systems involving alkaline earth metal (Mg2+, Ca2+, Sr2+, Ba2+) and heavy metal (Hg2+, Co2+, Cd2+, Cu2+, Zn2+, Pb2+) cations. The anions we selected for study included Cl-, NO3-, ClO4-, SO42-, CO32- and SeO32- and the background electrolyte cations we examined included (Na+, K+, Rb+ and Cs+) because these represent a range of ion sizes and have varying potentials for forming ion-pairs or ternary complexes with the metal ions studied. The research led to the development of a modified titration congruency approach for estimating site densities for mineral oxides such as goethite. The CD-MUSIC version of the surface complexation modeling approach was applied to potentiometric titration data and macroscopic adsorption data for single-solute heavy metals, oxyanions, alkaline earth metals and background electrolytes over a range of pH and ionic strength. The model was capable of predicting sorption in bi-solute systems containing multiple cations, cations and oxyanions, and transition metal cations and alkaline earth metal ions. Incorporation of ternary

  20. Survival Kinetics of Salmonella enterica and Enterohemorrhagic Escherichia coli on a Plastic Surface at Low Relative Humidity and on Low-Water Activity Foods. (United States)

    Hokunan, Hidekazu; Koyama, Kento; Hasegawa, Mayumi; Kawamura, Shuso; Koseki, Shigenobu


    We investigated the survival kinetics of Salmonella enterica and enterohemorrhagic Escherichia coli under various water activity (aw) conditions to elucidate the net effect of aw on pathogen survival kinetics and to pursue the development of a predictive model of pathogen survival as a function of aw. Four serotypes of S. enterica (Stanley, Typhimurium, Chester, and Oranienburg) and three serotypes of enterohemorrhagic E. coli ( E. coli O26, E. coli O111, and E. coli O157:H7) were examined. These bacterial strains were inoculated on a plastic plate surface at a constant relative humidity (RH) (22, 43, 58, 68, or 93% RH, corresponding to the aw) or on a surface of almond kernels (aw 0.58), chocolate (aw 0.43), radish sprout seeds (aw 0.58), or Cheddar cheese (aw 0.93) at 5, 15, or 25°C for up to 11 months. Under most conditions, the survival kinetics were nonlinear with tailing regardless of the storage aw, temperature, and bacterial strain. For all bacterial serotypes, there were no apparent differences in pathogen survival kinetics on the plastic surface at a given storage temperature among the tested RH conditions, except for the 93% RH condition. Most bacterial serotypes were rapidly inactivated on Cheddar cheese when stored at 5°C compared with their inactivation on chocolate, almonds, and radish sprout seeds. Distinct trends in bacterial survival kinetics were also observed between almond kernels and radish sprout seeds, even though the aws of these two foods were not significantly different. The survival kinetics of bacteria inoculated on the plastic plate surface showed little correspondence to those of bacteria inoculated on food matrices at an identical aw. Thus, these results demonstrated that, for low-aw foods and/or environments, aw alone is insufficient to account for the survival kinetics of S. enterica and enterohemorrhagic E. coli .

  1. Kinetic and Equilibrium Studies of Sorption of Ammonium in the Soil-Water Environment in Agricultural Areas of Central Poland

    Directory of Open Access Journals (Sweden)

    Anna Sieczka


    Full Text Available Sorption characteristics of nitrogen compounds is necessary in ascertaining their fate in the soil-water environment. This paper presents a laboratory “batch” experiment for determining the sorption parameters of ammonium in the soil-water environment. Three agricultural soils (silt loam, loam, and sand with different contents of the clay fraction, significantly affecting the range of the adsorption of contaminants on the surface of solid particles, were chosen as research material. Considering the composition of ammonium nitrate (a commonly used fertilizer in Poland, ammonium solutions with a concentration of 0–52 mg NH4+/L were used as markers. Pseudo-first order, pseudo-second order, and intra-particle diffusion kinetic models were used to describe the mechanisms of ammonium adsorption. Experimental data obtained from the equilibrium tests have been analysed using two-parameter (Freundlich, Langmuir, Temkin and three-parameter (Redlich-Peterson, Hill, Sips models. In order to adjust the parameters of the considered isotherms to the experimental data, the method of minimization of the sum of squared errors was used. Additionally, the maximum sorption capacities and reduction ratios of ammonium versus time were assessed. It was observed that the presence of silt loam and loam in the soil profile can increase the possibility of ammonium adsorption up to almost 20%. Taking into consideration the results of the batch tests, it was concluded that ammonium adsorption attains equilibrium within 48 h. Experimental data was best followed by the pseudo-second order equation and the adsorption isotherm conformed to the Redlich-Peterson model for loam and sand.

  2. Theoretical investigation of the thermodynamic structures and kinetic water-exchange reactions of aqueous Al(III)-salicylate complexes (United States)

    Shi, Wenjing; Jin, Xiaoyan; Dong, Shaonan; Bi, Shuping


    Density functional theory (DFT) calculations were performed on the structures and water-exchange reactions of aqueous Al(III)-salicylate complexes. Based on the four models (gas phase (GP); polarizable continuum model (PCM), which estimates the bulk solvent effect; supermolecule model (SM), which considers the explicit solvent effect, and supermolecule-polarizable continuum model (SM-PCM), which accounts for both types of solvent effects), we systematically conducted this study by examining three different properties of the complexes. (1) The microscopic properties of the aqueous Al(III)-salicylate complexes were studied by optimizing their various structures (including the possible 1:1 mono- and bidentate complexes, cis and trans isomers of the 1:2 bidentate complexes and 1:3 bidentate complexes) at the B3LYP/6-311+G(d, p) level. (2) The 27Al and 13C NMR chemical shifts were calculated using the GIAO method at the HF/6-311+G(d, p) level. The calculation results show that the values obtained with the SM-PCM models are in good agreement with the experimental data available in the literature, indicating that the models we employed are appropriate for Al(III)-salicylate complexes. (3) The water-exchange reactions of 1:1 mono- and bidentate Al(III)-salicylate complexes were simulated using supermolecule models at the B3LYP/6-311+G(d, p) level. The logarithm of the water-exchange rate constant (log kex) of the 1:1 bidentate complex predicted using the "log kex-dAl-OH2" correlation is 4.0, which is in good agreement with the experimental value of 3.7, whereas the calculated range of log kex of the 1:1 monodentate complexes is 1.3-1.9. By effectively combining the results for the thermodynamic static structures with the simulations of the kinetic water-exchange reactions, this work promotes further understanding of the configurations and formation mechanism of Al(III)-salicylate complexes.

  3. Applying hot-wire anemometry to directly measure the water balance in a proton exchange membrane fuel cell for a pre-humidified hydrogen stream

    DEFF Research Database (Denmark)

    Berning, Torsten; Shakhshir, Saher Al


    In a recent publication it has been shown how the water balance in a proton exchange membrane fuel cell can be determined employing hot wire anemometry. The hot wire sensor has to be placed into the anode outlet pipe of the operating fuel cell, and the voltage signal E that is read from the sensor....... Finally, it will be shown how previously developed dew point diagrams for the anode side in a fuel cell can be corrected for a humidified hydrogen inlet stream....... has to be divided by a pre-determined voltage signal E0 that has been obtained for a stream of dry hydrogen where the molar flow rate corresponds to a total current I of the fuel cell stack and a stoichiometric flow ratio, ξ. Because the last two properties are usually continuously known in fuel cell...

  4. A comparative study of a bio fuel cell with two different proton exchange membrane for the production of electricity from waste water

    Directory of Open Access Journals (Sweden)

    Amrita Shahi


    Full Text Available In the present study, electricity generation with waste water as substrate was investigated in a two compartment biofuel cell with two different combinations of electrodes and membrane. Two proton exchange membranes namely nafion and agar salt bridge and aluminum as electrode were used in the biofuel cell. It was found that biofuel cells operated with nafion produce maximum voltage 0.504 V with a current density of 0.1 A/m2 whereas in case of agar salt bridge maximum voltage of 0.145 V with a current density of 0.05 A/m2 was obtained. The more voltage produced in case of nafion is attributed to its low resistance for hydrogen ion transport.

  5. Salmonella Survival Kinetics on Pecans, Hazelnuts, and Pine Nuts at Various Water Activities and Temperatures. (United States)

    Santillana Farakos, Sofia; Pouillot, Régis; Keller, Susanne E


    The impact of temperature, water activity (a w ), and nut composition on Salmonella survival on tree nuts has not been thoroughly examined. The aim of this study was to determine the effect of temperature, a w , and nut composition on the survival of Salmonella on tree nuts and develop predictive models. Pecans, hazelnuts, and pine nuts were chosen based on differences in their typical fat content. Nuts were inoculated with a cocktail of five Salmonella serotypes (11 log CFU/mL) and then were dried and stored at 4, 10, and 25°C at 0.41 ± 0.06 and 0.60 ± 0.05 a w for 1 year. Ten-gram quantities were removed at different intervals up to 364 days to test for surviving Salmonella populations (plating on selective and nonselective media) and a w . Experiments were carried out in triplicate. Salmonella populations were relatively stable over a year at 4 and 10°C at both a w levels with Salmonella survival at 4 and 10°C was a log-linear model with a D-value for each tree nut and a w combination. Significant declines in Salmonella levels were observed at 25°C, where the best fit was a Weibull model with a fixed ρ for all tree nuts (ρ = 0.86), a δ value for each tree nut and a w combination, and a random factor to account for variability among replicates. The time for the first log reduction at 25°C and 0.37 ± 0.009 a w was estimated at 24 ± 2 weeks for hazelnuts, 34 ± 3 weeks for pecans, and 52 ± 7 weeks for pine nuts. At the same temperature, but with 0.54 ± 0.009 a w , the mean estimated time for the first log reduction decreased to 9 ± 1 weeks for hazelnuts, 10 ± 1 weeks for pecans, and 16 ± 1 weeks for pine nuts. Tree nut, a w , and temperature were shown to have a statistically significant effect on survival (P survival was observed. The results of this study can be used to predict changes in Salmonella levels on pecans, hazelnuts, and pine nuts after storage at the different temperatures and a w values.

  6. Exploration of the Singlet O2 Oxidation of 8-Oxoguanine by Guided-Ion Beam Scattering and Density Functional Theory: Changes of Reaction Intermediates, Energetics, and Kinetics upon Protonation/Deprotonation and Hydration. (United States)

    Sun, Yan; Lu, Wenchao; Liu, Jianbo


    8-Oxo-7,8-dihydro-2'-deoxyguanosine (8-oxodGuo) is one of the most common DNA lesions resulting from reactive oxygen species and ionizing radiation, and is involved in mutagenesis, carcinogenesis, and cell death. Notably, 8-oxodGuo is more reactive toward singlet (a(1)Δg) O2 than the undamaged guanosine, and the lesions arising from the secondary oxidation of 8-oxodGuo are more mutagenic. Herein the (1)O2 oxidation of free base 8-oxoguanine (8-oxoG) was investigated at different initial conditions including protonated [8-oxoG + H](+), deprotonated [8-oxoG - H](-), and their monohydrates. Experiment was carried out on a guided-ion beam scattering tandem mass spectrometer. Measurements include the effects of collision energy (Ecol) on reaction cross sections over a center-of-mass Ecol range from 0.1 to 0.5 eV. The aim of this study is to quantitatively probe the sensitivity of the early stage of 8-oxoG oxidation to ionization and hydration. Density functional theory and Rice-Ramsperger-Kassel-Marcus calculations were performed to identify the intermediates and the products along reaction pathways and locate accessible reaction potential energy surfaces, and to rationalize reaction outcomes from energetic and kinetic points of view. No product was observed for the reaction of [8-oxoG + H](+)·W0,1 (W = H2O) because insurmountable barriers block the addition of (1)O2 to reactant ions. Neither was [8-oxoG - H](-) reactive with (1)O2, in this case due to the rapid decay of transient intermediates to starting reactants. However, the nonreactivity of [8-oxoG - H](-) was inverted by hydration; as a result, 4,5-dioxetane of [8-oxoG - H](-) was captured as the main oxidation product. Reaction cross section for [8-oxoG - H](-)·W + (1)O2 decreases with increasing Ecol and becomes negligible above 0.3 eV, indicating that the reaction is exothermic and has no barriers above reactants. The contrasting oxidation behaviors of [8-oxoG + H](+)·W0,1 and [8-oxoG - H](-)·W0,1, which

  7. Restrained Proton Indicator in Combined Quantum-Mechanics/Molecular-Mechanics Dynamics Simulations of Proton Transfer through a Carbon Nanotube. (United States)

    Duster, Adam W; Lin, Hai


    Recently, a collective variable "proton indicator" was purposed for tracking an excess proton solvated in bulk water in molecular dynamics simulations. In this work, we demonstrate the feasibility of utilizing the position of this proton indicator as a reaction coordinate to model an excess proton migrating through a hydrophobic carbon nanotube in combined quantum-mechanics/molecular-mechanics simulations. Our results indicate that applying a harmonic restraint to the proton indicator in the bulk solvent near the nanotube pore entrance leads to the recruitment of water molecules into the pore. This is consistent with an earlier study that employed a multistate empirical valence bond potential and a different representation (center of excess charge) of the proton. We attribute this water recruitment to the delocalized nature of the solvated proton, which prefers to be in high-dielectric bulk solvent. While water recruitment into the pore is considered an artifact in the present simulations (because of the artificially imposed restraint on the proton), if the proton were naturally restrained, it could assist in building water wires prior to proton transfer through the pore. The potential of mean force for a proton translocation through the water-filled pore was computed by umbrella sampling, where the bias potentials were applied to the proton indicator. The free energy curve and barrier heights agree reasonably with those in the literature. The results suggest that the proton indicator can be used as a reaction coordinate in simulations of proton transport in confined environments.

  8. Water induced protonation of amine-terminated micelles for direct syntheses of ZnO quantum dots and their cytotoxicity towards cancer (United States)

    Zhang, Yinzhu; Wang, Huangping; Jiang, Hui; Wang, Xuemei


    This work designs a new strategy for the direct synthesis of different zinc oxide (ZnO) nanostructures at low temperatures. Micelles of dodecylamine (DDA) assembled in an ethanol-water system have been explored as a template to direct the growth of the ZnO nanostructures. The key species for the formation of the ZnO nanostructures, OH-, can be provided by the water-induced protonation of DDA. The pH of the reaction micro-environment can be regulated by changing the input amount of water and DDA. By controlling the reaction temperature and pH, various ZnO nanostructures, i.e. quantum dots with green or yellow-green emissions, have been prepared. The relationship of the optical properties and the synthetic conditions has been further discussed. This strategy realizes the convenient preparation of ZnO QDs, indicating the potential prospects in the nanotechnology field for their low-cost synthesis. Meanwhile, the cellular toxicity study of ZnO nanoparticles toward cancer cells, including leukemia K562 and K562/A02 cells as well as HepG2 cells, indicates a selective cytotoxic effect of ZnO QDs against a broad range of human cancer cell lines.

  9. Redox Kinetics and Nonstoichiometry of Ce0.5Zr0.5O2−δ for Water Splitting and Hydrogen Production

    KAUST Repository

    Zhao, Zhenlong


    Water splitting and chemical fuel production as a promising carbon-neutral energy solution relies critically on an efficient electrochemical process over catalyst surfaces. The fundamentals within the surface redox pathways, including the complex interactions of mobile ions and electrons between the bulk and the surface, along with the role of adsorbates and electrostatic fields remain yet to be understood quantitatively. This work presents a detailed kinetics study and nonstoichiometry characterization of Ce0.5Zr0.5O2−δ (CZO), one of the most recognized catalysts for water splitting. The use of CZO leads to >60% improvement in the kinetic rates as compared with undoped ceria with twice the total yield at 700 °C, resulting from the improved reducibility. The peak H2 production rate is 95 μmol g–1 s–1 at 700 °C, and the total production is 750 μmol g–1. A threshold temperature of 650 °C is required to achieve significant H2 production at fast rates. The redox kinetics is modeled using two-step surface chemistry with bulk-to-surface transport equilibrium. Kinetics and equilibrium parameters are extracted, and the model predictions show good agreement with the measurements. The enthalpy of bulk defect formation for CZO is found to be 262 kJ/mol, >40% lower than that of undoped ceria. As oxygen vacancy is gradually filled up, the surface H2O splitting chemistry undergoes a transition from exothermic to endothermic, with the crossover around δ = 0.04 to 0.05, which constrains the further ion incorporation process. Our kinetics study reveals that the H2O splitting process with CZO is kinetics limited at low temperature and transitions to partial-equilibrium with significantly enhanced backward reaction at high temperature. The charge-transfer step is found to be the rate-limiting step for H2O splitting. The detailed kinetics and nonstoichiometric equilibria should be helpful in guiding the design and optimization of CZO as a catalyst, oxygen storage

  10. Quantitative determination of some water-soluble B vitamins by kinetic analytical method based on the perturbation of an oscillatory reaction


    Maksimović,Jelena P.; Kolar-Anić,Ljiljana Z.; Anić,Slobodan R.; Ribić,Dragana D.; Pejić,Nataša D.


    A novel procedure for kinetic determination of some water-soluble vitamins of the B-group (thiamine (B1), riboflavin (B2), niacin (B3) and pyridoxine (B6)) by the concentration perturbations of the Bray-Liebhafsky (BL) oscillatory chemical system involving the catalytic decomposition of hydrogen peroxide in the presence of both hydrogen and iodate ions is proposed and validated. The method uses a Pt electrode for potentiometric monitoring of the concentration perturbations of the BL matrix in...

  11. Separation of oily materials in radioactive waste waters by flotation. Flotation kinetics; Separacion de materiales oleosos en aguas residuales radiactivas por flotacion. Cinetica de flotacion

    Energy Technology Data Exchange (ETDEWEB)

    Flores E, R.M.; Ortiz O, H.B. [ININ, 52045 Ocoyoacac, Estado de Mexico (Mexico)]. e-mail:


    The rate of separation of oil and total cobalt in the oleaginous residual water previously treated by coagulation/flocculation with a quaternary ammonium amine (25 mgL{sup -1}) and with modified anionic polyacrylamide (1.5 mgL{sup -1}) (pH = 7, G{sub 1} = 300 s{sup -1} and G{sub 2} = 30 s{sup -1}) was determined. The experimental essays to determine the flotation kinetics, its were carried out using as operation and control parameters the air/solids relationship (G/S 0.35), pressure (P =620 kPa) and volume of air-water mixture (V = 37% of V{sub f}), obtained in previous essays, at two different pressure levels and volume of discharged mixture. The kinetic studies of flotation obtained for the flotation system with conventional air dissolved (DAF) its suggest a first order kinetics that it can be represented by the SCC model. At the same time its show that the separation of the present pollutants in the residual water is governed by the removal velocity of the oil. Meanwhile, the concentration of total Co below 1 mgL{sup -1}, on the other hand, the concentration of the {sup 60} Co at the end of the flotation process resulted smaller than 0.008 Bq/ml, as long as the one {sup 54} Mn were not detectable. (Author)

  12. Effect of the adsorbate (Bromacil) equilibrium concentration in water on its adsorption on powdered activated carbon. Part 2: Kinetic parameters. (United States)

    Al Mardini, Fadi; Legube, Bernard


    The application of several monosolute equilibrium models has previously shown that Bromacil adsorption on SA-UF (Norit) powdered activated carbon (PAC) is probably effective on two types of sites. High reactivity sites were found to be 10-20 less present in a carbon surface than lower reactivity sites, according to the q(m) values calculated by isotherm models. The aims of this work were trying, primarily, to identify the kinetic-determinant stage of the sorption of Bromacil at a wide range of initial pesticide concentrations (approximately 5 to approximately 500 microg L(-1) at pH 7.8), and secondly, to specify the rate constants and other useful design parameters for the application in water treatment. It was therefore not possible to specify a priori whether the diffusion or surface reaction is the key step. It shows that many of the tested models which describe the stage of distribution or the surface reaction are correctly applied. However, the diffusivity values (D and D(0)) were found to be constant only constants for some specific experimental concentrations. The HSDM model of surface diffusion in pores was also applied but the values of the diffusion coefficient of surface (D(s)) were widely scattered and reduce significantly with the initial concentration or the equilibrium concentration in Bromacil. The model of surface reaction of pseudo-second order fitted particularly well and led to constant values which are independent of the equilibrium concentration, except for the low concentrations where the constants become significantly more important. This last observation confirms perfectly the hypothesis based on two types of sites as concluded by the equilibrium data (part 1).

  13. Photolysis of model emerging contaminants in ultra-pure water: kinetics, by-products formation and degradation pathways. (United States)

    Benitez, F Javier; Acero, Juan L; Real, Francisco J; Roldan, Gloria; Rodriguez, Elena


    The photolysis of five frequent emerging contaminants (Benzotriazole, Chlorophene, N,N-diethyl-m-toluamide or DEET, Methylindole, and Nortriptyline HCl) was investigated in ultrapure water under monochromatic ultraviolet radiation at 254 nm and by a combination of UV and hydrogen peroxide. The results revealed that the photolysis rates followed first-order kinetics, with rate constant values depending on the nature of the specific compound, the pH, and the presence or absence of the scavenger tert-butanol. Quantum yields were also determined and values in the range of 53.8 × 10⁻³ - 9.4 × 10⁻³ mol E⁻¹ for Benzotriazole, 525 × 10⁻³ - 469 × 10⁻³ mol E⁻¹ for Chlorophene, 2.8 × 10⁻³ - 0.9 × 10⁻³ mol E⁻¹ for DEET, 108 × 10⁻³ - 165 × 10⁻³ mol E⁻¹ for Methylindole, and 13.8 × 10⁻³ - 15.0 × 10⁻³ mol E⁻¹ for Nortriptyline were obtained. The study also found that the UV/H₂O₂ process enhanced the oxidation rate in comparison to direct photolysis. High-performance liquid chromatography coupled to electrospray ionization quadrupole time-of-flight mass spectrometry (HPLC-ESI-QTOF-MS) technique was applied to the concentrations evaluation and further identification of the parent compounds and their by-products, which allowed the proposal of the degradation pathways for each compound. Finally, in order to assess the aquatic toxicity in the photodegradation of these compounds, the Vibrio fischeri acute toxicity test was used, and the results indicated an initial increase of this parameter in all cases, followed by a decrease in the specific case of Benzotriazole, DEET, Methylindole, and Chlorophene. Copyright © 2012 Elsevier Ltd. All rights reserved.

  14. Zirconium oxide-coated sand based batch and column adsorptive removal of arsenic from water: Isotherm, kinetic and thermodynamic studies

    Directory of Open Access Journals (Sweden)

    Saif Ali Chaudhry


    Full Text Available This paper reports zirconium oxide-coated sand preparation, characterization by SEM, EDX, XRD, FT-IR and thermoanalytical techniques, and use as an adsorbent for the removal of most toxic form of arsenic, As(III, from aqueous solution in both batch and column methods. Batch experimental parameters such as contact time, concentration, dose of adsorbent, pH of As(III solution and temperature were optimized. The adsorption data was fitted to Langmuir, Freundlich, Temkin and Dubinin-Radushkevich isotherms at 303, 308 and 313 K. The maximum Langmuir monolayer adsorption capacity was found to be 136.98 μg/g at 313 K. Values of ΔH°, ΔG° and ΔS° were found to be −12.90, −8.74 to –8.28 and 0.014 kJ/mol, suggesting exothermic and spontaneous adsorption process with slight increase in entropy. The adsorption process followed pseudo-second order kinetics and was controlled by film diffusion step. The column studies showed that when flow rate was increased from 3.0 to 5.0 mL/min, the arsenic adsorption capacity of ZrOCS increased from 33.104 to 42.231 μg/g and breakthrough, and exhaustion times got reduced reduced. The results indicated that zirconium oxide-coated sand (ZrOCS is an excellent adsorbent for the removal of As(III from water.

  15. Numerical simulation of flood inundation using a well-balanced kinetic scheme for the shallow water equations with bulk recharge and discharge (United States)

    Ersoy, Mehmet; Lakkis, Omar; Townsend, Philip


    The flow of water in rivers and oceans can, under general assumptions, be efficiently modelled using Saint-Venant's shallow water system of equations (SWE). SWE is a hyperbolic system of conservation laws (HSCL) which can be derived from a starting point of incompressible Navier-Stokes. A common difficulty in the numerical simulation of HSCLs is the conservation of physical entropy. Work by Audusse, Bristeau, Perthame (2000) and Perthame, Simeoni (2001), proposed numerical SWE solvers known as kinetic schemes (KSs), which can be shown to have desirable entropy-consistent properties, and are thus called well-balanced schemes. A KS is derived from kinetic equations that can be integrated into the SWE. In flood risk assessment models the SWE must be coupled with other equations describing interacting meteorological and hydrogeological phenomena such as rain and groundwater flows. The SWE must therefore be appropriately modified to accommodate source and sink terms, so kinetic schemes are no longer valid. While modifications of SWE in this direction have been recently proposed, e.g., Delestre (2010), we depart from the extant literature by proposing a novel model that is "entropy-consistent" and naturally extends the SWE by respecting its kinetic formulation connections. This allows us to derive a system of partial differential equations modelling flow of a one-dimensional river with both a precipitation term and a groundwater flow model to account for potential infiltration and recharge. We exhibit numerical simulations of the corresponding kinetic schemes. These simulations can be applied to both real world flood prediction and the tackling of wider issues on how climate and societal change are affecting flood risk.

  16. Proton Pump Inhibitors in Pediatrics: Relevant Pharmacokinetics and Pharmacodynamics

    National Research Council Canada - National Science Library

    Kearns, Gregory L; Winter, Harland S


    A marked discordance between the disposition of proton pump inhibitors (PPIs) in plasma and the kinetics of effect suggests the need for new approaches to characterize the clinical pharmacology of PPIs in infants and children...

  17. A Fano cavity test for Monte Carlo proton transport algorithms

    Energy Technology Data Exchange (ETDEWEB)

    Sterpin, Edmond, E-mail: [Université catholique de Louvain, Center of Molecular Imaging, Radiotherapy and Oncology, Institut de Recherche Experimentale et Clinique, Avenue Hippocrate 54, 1200 Brussels (Belgium); Sorriaux, Jefferson; Souris, Kevin [Université catholique de Louvain, Center of Molecular Imaging, Radiotherapy and Oncology, Institut de Recherche Experimentale et Clinique, Avenue Hippocrate 54, 1200 Brussels, Belgium and Université catholique de Louvain, ICTEAM institute, Chemin du cyclotron 6, 1348 Louvain-la-Neuve (Belgium); Vynckier, Stefaan [Université catholique de Louvain, Center of Molecular Imaging, Radiotherapy and Oncology, Institut de Recherche Experimentale et Clinique, Avenue Hippocrate 54, 1200 Brussels, Belgium and Département de Radiothérapie, Cliniques Universitaires Saint-Luc, Avenue Hippocrate 54, 1200 Brussels (Belgium); Bouchard, Hugo [Département de radio-oncologie, Centre hospitalier de l’Université de Montréal (CHUM), 1560 Sherbrooke est, Montréal, Québec H2L 4M1 (Canada)


    Purpose: In the scope of reference dosimetry of radiotherapy beams, Monte Carlo (MC) simulations are widely used to compute ionization chamber dose response accurately. Uncertainties related to the transport algorithm can be verified performing self-consistency tests, i.e., the so-called “Fano cavity test.” The Fano cavity test is based on the Fano theorem, which states that under charged particle equilibrium conditions, the charged particle fluence is independent of the mass density of the media as long as the cross-sections are uniform. Such tests have not been performed yet for MC codes simulating proton transport. The objectives of this study are to design a new Fano cavity test for proton MC and to implement the methodology in two MC codes: Geant4 and PENELOPE extended to protons (PENH). Methods: The new Fano test is designed to evaluate the accuracy of proton transport. Virtual particles with an energy ofE{sub 0} and a mass macroscopic cross section of (Σ)/(ρ) are transported, having the ability to generate protons with kinetic energy E{sub 0} and to be restored after each interaction, thus providing proton equilibrium. To perform the test, the authors use a simplified simulation model and rigorously demonstrate that the computed cavity dose per incident fluence must equal (ΣE{sub 0})/(ρ) , as expected in classic Fano tests. The implementation of the test is performed in Geant4 and PENH. The geometry used for testing is a 10 × 10 cm{sup 2} parallel virtual field and a cavity (2 × 2 × 0.2 cm{sup 3} size) in a water phantom with dimensions large enough to ensure proton equilibrium. Results: For conservative user-defined simulation parameters (leading to small step sizes), both Geant4 and PENH pass the Fano cavity test within 0.1%. However, differences of 0.6% and 0.7% were observed for PENH and Geant4, respectively, using larger step sizes. For PENH, the difference is attributed to the random-hinge method that introduces an artificial energy

  18. Woody biomass: Niche position as a source of sustainable renewable chemicals and energy and kinetics of hot-water extraction/hydrolysis. (United States)

    Liu, Shijie


    The conversion of biomass to chemicals and energy is imperative to sustaining our way of life as known to us today. Fossil chemical and energy sources are traditionally regarded as wastes from a distant past. Petroleum, natural gas, and coal are not being regenerated in a sustainable manner. However, biomass sources such as algae, grasses, bushes and forests are continuously being replenished. Woody biomass represents the most abundant and available biomass source. Woody biomass is a reliably sustainable source of chemicals and energy that could be replenished at a rate consistent with our needs. The biorefinery is a concept describing the collection of processes used to convert biomass to chemicals and energy. Woody biomass presents more challenges than cereal grains for conversion to platform chemicals due to its stereochemical structures. Woody biomass can be thought of as comprised of at least four components: extractives, hemicellulose, lignin and cellulose. Each of these four components has a different degree of resistance to chemical, thermal and biological degradation. The biorefinery concept proposed at ESF (State University of New York - College of Environmental Science and Forestry) aims at incremental sequential deconstruction, fractionation/conversion of woody biomass to achieve efficient separation of major components. The emphasis of this work is on the kinetics of hot-water extraction, filling the gap in the fundamental understanding, linking engineering developments, and completing the first step in the biorefinery processes. This first step removes extractives and hemicellulose fractions from woody biomass. While extractives and hemicellulose are largely removed in the extraction liquor, cellulose and lignin largely remain in the residual woody structure. Xylo-oligomers and acetic acid in the extract are the major components having the greatest potential value for development. Extraction/hydrolysis involves at least 16 general reactions that could

  19. SU-E-T-571: Microdosimetric Characterization of Proton Biological Effectiveness

    Energy Technology Data Exchange (ETDEWEB)

    Guardiola, C; Carabe-Fernandez, A; Tuttle, S [Hospital of the University of Pennsylvania, Philadelphia, PA (United States)


    Purpose: The knowledge of cell repair kinetics is critical in order to understand relevant aspects of proton therapy such optimal fractionation. High LET radiation induces larger proportions of more complex DSBs that might not be resolved in standard interfractional times (24h). We propose a method to characterize the cell repair kinetic at different positions within the spread-out Bragg peak (i.e. as a function of proton LETd) and use this information to model normal tissue complication probabilities (NTCP) as a function of LETd Methods: Repair kinetics curves will be obtained using U251-glioblastoma cells plating over microscope slides that are immersed in culture-medium that will be exposed along the axis of a proton-beam (10cm in range, 2cm modulation) of 1Gy. Culture is immersed within a solid-water block to place the distal edge of the proton-beam within the slide. gamma-H2AX foci along the slide in the beam axis is imaged with a microscope at different positions in order to correlate number of gamma-H2AX foci with dose and LET, where dose is obtained from a strip of gafchromic film placed on the side of the slide. Each slide is fixed at different time points. Results: We will present the correlation between an increase of LET and the increase of the gamma-H2AX along the depth within the proton beam, at different post-irradiation times and doses. Different fractions of unrepaired damage at 24h after irradiation will be presented at each depth of the proton beam, with larger fractions at the distal edge of the beam, where normal tissue exist. Larger values of NTCP are therefore observed at the distal edge. Conclusion: Slower repair kinetics is observed at the distal edge of a proton beam, and this study shows a method to obtain such information and the correlation between increased LET and increased NTCP. This research is supported by the Department of Radiation Oncology at the Hospital of the University of Pennsylvania as a pilot project.

  20. Local potential evolutions during proton exchange membrane fuel cell operation with dead-ended anode - Part II: Aging mitigation strategies based on water management and nitrogen crossover (United States)

    Abbou, S.; Dillet, J.; Maranzana, G.; Didierjean, S.; Lottin, O.


    Proton exchange membrane (PEM) fuel cells operate with dead-ended anode in order to reduce system cost and complexity when compared with hydrogen re-circulation systems. In the first part of this work, we showed that localized fuel starvation events may occur, because of water and nitrogen accumulation in the anode side, which could be particularly damaging to the cell performance. To prevent these degradations, the anode compartment must be purged which may lead to an overall system efficiency decrease because of significant hydrogen waste. In the second part, we present several purge strategies in order to minimize both hydrogen waste and membrane-electrode assembly degradations during dead-ended anode operation. A linear segmented cell with reference electrodes was used to monitor simultaneously the current density distribution along the gas channel and the time evolution of local anode and cathode potentials. To asses MEA damages, Platinum ElectroChemical Surface Area (ECSA) and cell performance were periodically measured. The results showed that dead-end mode operation with an anode plate maintained at a temperature 5 °C hotter than the cathode plate limits water accumulation in the anode side, reducing significantly purge frequency (and thus hydrogen losses) as well as MEA damages. As nitrogen contribution to hydrogen starvation is predominant in this thermal configuration, we also tested a microleakage solution to discharge continuously most the nitrogen accumulating in the anode side while ensuring low hydrogen losses and minimum ECSA losses provided the right microleakage flow rate is chosen.

  1. DIFFUSIVE-Magnetoresistance(DMR) Proton(PMR)/Hydrogen-ion WATER: PRE-``Fert''/``Grunberg'' GMR[and CMR]: Quo-Vadis ``Honesty''???: PLAGIARISM!!! (United States)

    Fart, Albart; Gruntbug, Peter; Siegel, Edward


    Proton/Hydrogen-ion Diffusive-Magnetoresistance(DMR) of Siegel[APS March-Mtgs.(70s)] based upon Siegel[Int'l. Conf. Mag.-Alloys and Oxides("ICMAO"), The Technion(77); J. Mag. Mag. Mtls. 7, 312(78)] FIRST experimental-discovery of GMR and FIRST theoretical prediction of CMR[ibid. 7, 338 (78)], facilitates NEW water production in global-warming exacerbated dry arid/semi-arid regions: Only HYDROGEN is/can be "FLYING-WATER"!!! (aka "chemical-rain-in-pipelines"). EMET/TRUTH-in-the-``SEANCES'', would-be "Sciences": C. Perelman-Corredoira [Against the Tide(07)] featuring Martin-Bradshaw ["Healing the SHAME That BINDS You"(80s)] systemic sociological-dysfunctionality(S-D), and Grigory Perelman's HEROIC ETHICS (refusal of both pure-maths Poincare-conjecture proof 2007 Fields-medal and 2010 Clay-Institute so-called/media-hyped/P.Red/spin-doctored millennium-prize million-dollar would-be award, militates as well in the current "SEANCE" of physics/maths politics/media-hype/P.R /spin-doctoring VS. Siegel FIRST experimental GMR a never-acknowledged full decade PRE-"Fert"(88) /"Grunberg(89)" ``Phales-GroPE''/Thompson-CSF/ KFZ-JEWlich 2007 physics Wolf/Japan/Nobel-prizes!!!

  2. Experimental study on the influence of clamping pressure on proton exchange membrane water electrolyzer (PEMWE) cell’s characteristics

    DEFF Research Database (Denmark)

    Al Shakhshir, Saher; Cui, Xiaoti; Kær, Søren Knudsen

    at lower clamping pressure values at the same temperature and current density. Furthermore, early results have not shown any significant change in the amount of hydrogen crossing-over from cathode to anode and water from anode to cathode. This might be attributed to the membrane properties which might....... PEMWE cell splits water into hydrogen and oxygen when an electric current is passed through it. Electrical current forces the positively charged ions to migrate to negatively charged cathode, where hydrogen is reduced. Meanwhile, oxygen is produced at the anode side electrode and escapes as a gas...... with the circulating water. In the recent few years, PEMWE’s R&D has inched towards; operating conditions; such as increased operating temperature and cathode-anode high differential pressure operation, flow field design, stack development, and numerical modelling [2,3]. In this work the effect of clamping pressure...

  3. Proton scaling

    Energy Technology Data Exchange (ETDEWEB)

    Canavan, Gregory H [Los Alamos National Laboratory


    This note presents analytic estimates of the performance of proton beams in remote surveillance for nuclear materials. The analysis partitions the analysis into the eight steps used by a companion note: (1) Air scattering, (2) Neutron production in the ship and cargo, (3) Target detection probability, (4) Signal produced by target, (5) Attenuation of signal by ship and cargo, (6) Attenuation of signal by air, (7) Geometric dilution, and (8) Detector Efficiency. The above analyses indicate that the dominant air scattering and loss mechanisms for particle remote sensing are calculable with reliable and accepted tools. They make it clear that the conversion of proton beams into neutron sources rapidly goes to completion in all but thinnest targets, which means that proton interrogation is for all purposes executed by neutrons. Diffusion models and limiting approximations to them are simple and credible - apart from uncertainty over the cross sections to be used in them - and uncertainty over the structure of the vessels investigated. Multiplication is essentially unknown, in part because it depends on the details of the target and its shielding, which are unlikely to be known in advance. Attenuation of neutron fluxes on the way out are more complicated due to geometry, the spectrum of fission neutrons, and the details of their slowing down during egress. The attenuation by air is large but less uncertain. Detectors and technology are better known. The overall convolution of these effects lead to large but arguably tolerable levels of attenuation of input beams and output signals. That is particularly the case for small, mobile sensors, which can more than compensate for size with proximity to operate reliably while remaining below flux limits. Overall, the estimates used here appear to be of adequate accuracy for decisions. That assessment is strengthened by their agreement with companion calculations.

  4. Biodegradation of hydrocarbon mixtures in surface waters at environmentally relevant levels - Effect of inoculum origin on kinetics and sequence of degradation. (United States)

    Birch, Heidi; Hammershøj, Rikke; Comber, Mike; Mayer, Philipp


    Biodegradation is a dominant removal process for many organic pollutants, and biodegradation tests serve as tools for assessing their environmental fate within regulatory risk assessment. In simulation tests, the inoculum is not standardized, varying in microbial quantity and quality, thereby potentially impacting the observed biodegradation kinetics. In this study we investigated the effect of inoculum origin on the biodegradation kinetics of hydrocarbons for five inocula from surface waters varying in urbanization and thus expected pre-exposure to petroleum hydrocarbons. A new biodegradation method for testing mixtures of hydrophobic chemicals at trace concentrations was demonstrated: Aqueous solutions containing 9 hydrocarbons were generated by passive dosing and diluted with surface water resulting in test systems containing native microorganisms exposed to test substances at ng-μg/L levels. Automated Headspace Solid Phase Microextraction coupled to GC-MS was applied directly to these test systems to determine substrate depletion relative to abiotic controls. Lag phases were generally less than 8 days. First order rate constants were within one order of magnitude for each hydrocarbon in four of the five waters but lower in water from a rural lake. The sequence of degradation between the 9 hydrocarbons showed similar patterns in the five waters indicating the potential for using selected hydrocarbons for benchmarking between biodegradation tests. Degradation half-times were shorter than or within one order of magnitude of BioHCwin predictions for 8 of 9 hydrocarbons. These results showed that location choice is important for biodegradation kinetics and can provide a relevant input to aquatic exposure and fate models. Copyright © 2017 Elsevier Ltd. All rights reserved.

  5. Concerted O atom—proton transfer in the O—O bond forming step in water oxidation

    National Research Council Canada - National Science Library

    Zuofeng Chen; Javier J. Concepcion; Xiangqian Hu; Weitao Yang; Paul G. Hoertz; Thomas J. Meyer


    ...⁻/4H⁺ loss and O—O bond formation. Significant progress in water oxidation catalysis has been achieved recently by use of single-site Ru metal complex catalysts such as [Ru(Mebimpy)(bpy)(OH₂)]²⁺ [Mebimpy = 2,6-bis...

  6. High Temperature, Low Relative Humidity, Polymer-type Membranes Based on Disulfonated Poly(arylene ether) Block and Random Copolymers Optionally Incorporating Protonic Conducting Layered Water insoluble Zirconium Fillers

    Energy Technology Data Exchange (ETDEWEB)

    McGrath, James E.; Baird, Donald G.


    Our research group has been engaged in the past few years in the synthesis of biphenol based partially disulfonated poly(arylene ether sulfone) random copolymers as potential PEMs. This series of polymers are named as BPSH-xx, where BP stands for biphenol, S stands for sulfonated, H stands for acidified and xx represents the degree of disulfonation. All of these sulfonated copolymers phase separate to form nano scale hydrophilic and hydrophobic morphological domains. The hydrophilic phase containing the sulfonic acid moieties causes the copolymer to absorb water. Water confined in hydrophilic pores in concert with the sulfonic acid groups serve the critical function of proton (ion) conduction and water transport in these systems. Both Nafion and BPSH show high proton conductivity at fully hydrated conditions. However proton transport is especially limited at low hydration level for the BPSH random copolymer. It has been observed that the diffusion coefficients of both water and protons change with the water content of the pore. This change in proton and water transport mechanisms with hydration level has been attributed to the solvation of the acid groups and the amount of bound and bulk-like water within a pore. At low hydration levels most of the water is tightly associated with sulfonic groups and has a low diffusion coefficient. This tends to encourage isolated domain morphology. Thus, although there may be significant concentrations of protons, the transport is limited by the discontinuous morphological structure. Hence the challenge lies in how to modify the chemistry of the polymers to obtain significant protonic conductivity at low hydration levels. This may be possible if one can alter the chemical structure to synthesize nanophase separated ion containing block copolymers. Unlike the BPSH copolymers, where the sulfonic acid groups are randomly distributed along the chain, the multiblock copolymers will feature an ordered sequence of hydrophilic and

  7. Exploring water radiolysis in proton cancer therapy: Time-dependent, non-adiabatic simulations of H+ + (H2O1-6.

    Directory of Open Access Journals (Sweden)

    Austin J Privett

    Full Text Available To elucidate microscopic details of proton cancer therapy (PCT, we apply the simplest-level electron nuclear dynamics (SLEND method to H+ + (H2O1-6 at ELab = 100 keV. These systems are computationally tractable prototypes to simulate water radiolysis reactions-i.e. the PCT processes that generate the DNA-damaging species against cancerous cells. To capture incipient bulk-water effects, ten (H2O1-6 isomers are considered, ranging from quasi-planar/multiplanar (H2O1-6 to "smallest-drop" prism and cage (H2O6 structures. SLEND is a time-dependent, variational, non-adiabatic and direct method that adopts a nuclear classical-mechanics description and an electronic single-determinantal wavefunction in the Thouless representation. Short-time SLEND/6-31G* (n = 1-6 and /6-31G** (n = 1-5 simulations render cluster-to-projectile 1-electron-transfer (1-ET total integral cross sections (ICSs and 1-ET probabilities. In absolute quantitative terms, SLEND/6-31G* 1-ET ICS compares satisfactorily with alternative experimental and theoretical results only available for n = 1 and exhibits almost the same accuracy of the best alternative theoretical result. SLEND/6-31G** overestimates 1-ET ICS for n = 1, but a comparable overestimation is also observed with another theoretical method. An investigation on H+ + H indicates that electron direct ionization (DI becomes significant with the large virtual-space quasi-continuum in large basis sets; thus, SLEND/6-31G** 1-ET ICS is overestimated by DI contributions. The solution to this problem is discussed. In relative quantitative terms, both SLEND/6-31* and /6-31G** 1-ET ICSs precisely fit into physically justified scaling formulae as a function of the cluster size; this indicates SLEND's suitability for predicting properties of water clusters with varying size. Long-time SLEND/6-31G* (n = 1-4 simulations predict the formation of the DNA-damaging radicals H, OH, O and H3O. While "smallest-drop" isomers are included, no

  8. Effect of water on the transport properties of protic and aprotic imidazolium ionic liquids - an analysis of self-diffusivity, conductivity, and proton exchange mechanism. (United States)

    Yaghini, N; Nordstierna, L; Martinelli, A


    In this paper we report on the transport properties of protic and aprotic ionic liquids of the imidazolium cation (C2C1Im(+) or C2HIm(+)) and the TFSI(-) or TfO(-) anion as a function of added water. We observe that the self-diffusion coefficient of the ionic species increases upon addition of water, and that the cation diffuses faster than the anion in the entire water concentration range investigated. We also observe that the overall increase of anionic and cationic diffusion coefficients is significant for C2HImTfO while it is rather weak for C2C1ImTFSI, the former being more hydrophilic. Moreover, the difference between cationic and anionic self-diffusivity specifically depends on the structure of the ionic liquid's ions. The degree of ion-ion association has been investigated by comparing the molar conductivity obtained by impedance measurements with the molar conductivity calculated from NMR data using the Nernst-Einstein equation. Our data indicate that the ions are partly dissociated (Λimp/ΛNMR in the range 0.45-0.75) but also that the degree of association decreases in the order C2HImTfO > C2HImTFSI ≈ C2C1ImTfO > C2C1ImTFSI. From these results, it seems that water finds different sites of interaction in the protic and aprotic ionic liquids, with a strong preference for hydrogen bonding to the -NH group (when available) and a stronger affinity to the TfO anion as compared to the TFSI. For the protic ionic liquids, the analysis of (1)H NMR chemical shifts (upon addition of H2O and D2O, respectively) indicates a water-cation interaction of hydrogen bonding nature. In addition, we could probe proton exchange between the -NH group and deuterated water for the protic cation, which occurs at a significantly faster rate if associated with the TfO anion as compared to the TFSI.

  9. Angle-averaged effective proton-carbon analyzing powers at intermediate energies

    NARCIS (Netherlands)

    Amir Ahmadi, H.R.; van den Berg, A.M.; Hunyadi, M.D.; Kalantar-Nayestanaki, N.; Kis, M.; Shafiei, M.; Messchendorp, J.G.; Wörtche, H.J.


    The angle-averaged effective analyzing powers, (A) over barc, for proton-carbon inclusive scattering were measured as a function of the kinetic energy of protons in a double scattering experiment. The measurements were performed in the kinetic energy range of 44.8-136.5 MeV at the center of 1-5 cm

  10. Water and tissue equivalence properties of biological materials for photons, electrons, protons and alpha particles in the energy region 10 keV-1 GeV: a comparative study. (United States)

    Kurudirek, Murat


    To compare some biological materials in respect to the water and tissue equivalence properties for photon, electron, proton and alpha particle interactions as means of the effective atomic number (Zeff) and electron density (Ne). A Z-wise interpolation procedure has been adopted for calculation of Zeff using the mass attenuation coefficients for photons and the mass stopping powers for charged particles. At relatively low energies (100 keV-3 MeV), Zeff and Ne for photons and electrons were found to be constant while they vary much more for protons and alpha particles. In contrast, Zeff and Ne for protons and alpha particles were found to be constant after 3 MeV whereas for photons and electrons they were found to increase with the increasing energy. Also, muscle eq. liquid (with sucrose) have Zeff and Ne values close to the Muscle Skeletal (ICRP) and Muscle Striated (ICRU) within low relative differences below 9%. Muscle eq. liquid (without sucrose) have Zeff and Ne values close to the Muscle Skeletal (ICRP) and Muscle Striated (ICRU) with difference below 10%. The reported data should be useful in determining best water as well as tissue equivalent materials for photon, electron, proton and alpha particle interactions.

  11. APEX (Aqueous Photochemistry of Environmentally occurring Xenobiotics): a free software tool to predict the kinetics of photochemical processes in surface waters. (United States)

    Bodrato, Marco; Vione, Davide


    The APEX software predicts the photochemical transformation kinetics of xenobiotics in surface waters as a function of: photoreactivity parameters (direct photolysis quantum yield and second-order reaction rate constants with transient species, namely ˙OH, CO₃(-)˙, (1)O₂ and the triplet states of chromophoric dissolved organic matter, (3)CDOM*), water chemistry (nitrate, nitrite, bicarbonate, carbonate, bromide and dissolved organic carbon, DOC), and water depth (more specifically, the optical path length of sunlight in water). It applies to well-mixed surface water layers, including the epilimnion of stratified lakes, and the output data are average values over the considered water column. Based on intermediate formation yields from the parent compound via the different photochemical pathways, the software can also predict intermediate formation kinetics and overall yield. APEX is based on a photochemical model that has been validated against available field data of pollutant phototransformation, with good agreement between model predictions and field results. The APEX software makes allowance for different levels of knowledge of a photochemical system. For instance, the absorption spectrum of surface water can be used if known, or otherwise it can be modelled from the values of DOC. Also the direct photolysis quantum yield can be entered as a detailed wavelength trend, as a single value (constant or average), or it can be defined as a variable if unknown. APEX is based on the free software Octave. Additional applications are provided within APEX to assess the σ-level uncertainty of the results and the seasonal trend of photochemical processes.

  12. Zirconium phosphate as the proton conducting material in direct hydrocarbon polymer electrolyte membrane fuel cells operating above the boiling point of water

    Energy Technology Data Exchange (ETDEWEB)

    Al-Othman, Amani [Chemical and Biological Engineering, University of Ottawa, 161 Louis Pasteur, Ottawa, ON K1N 6N5 (Canada); Catalysis Centre for Research and Innovation, University of Ottawa, 161 Louis Pasteur, Ottawa, ON K1N 6N5 (Canada); Tremblay, Andre Y. [Chemical and Biological Engineering, University of Ottawa, 161 Louis Pasteur, Ottawa, ON K1N 6N5 (Canada); Pell, Wendy; Letaief, Sadok [Catalysis Centre for Research and Innovation, University of Ottawa, 161 Louis Pasteur, Ottawa, ON K1N 6N5 (Canada); Burchell, Tara J. [Department of Physics, University of Ottawa, 161 Louis Pasteur, Ottawa, ON K1N 6N5 (Canada); Peppley, Brant A. [Chemical Engineering, Queens University, Dupuis Hall, Kingston, ON K7L 3N6 (Canada); Ternan, Marten [EnPross Inc., 147 Banning Road, Ottawa, ON K2L 1C5 (Canada)


    Zirconium phosphate (ZrP) was investigated as a possible proton conductor material in direct hydrocarbon polymer electrolyte membrane (PEM) fuel cells that operate at greater temperatures than conventional PEM fuel cells. Amorphous zirconium phosphate was synthesized in this work by precipitation at room temperature via reaction of ZrOCl{sub 2} with H{sub 3}PO{sub 4} aqueous solutions. The conductivity of the synthesized ZrP materials were 7.04 x 10{sup -5} S cm{sup -1} for ZrP oven dried in laboratory air at 70 C and 3.57 x 10{sup -4} S cm{sup -1} for ZrP powder dried first at 70 C in laboratory air and then processed at 200 C with continuous H{sub 2}O injection at an H{sub 2}O/N{sub 2} molar ratio of 6. This work showed that by maintaining appropriate water content in the vapour phase at processing conditions, it was possible to alter the composition of zirconium phosphate to a sufficiently hydrated state, and thereby avoid the normal decrease in conductivity with increasing temperature. (author)

  13. Kinetic Typography

    DEFF Research Database (Denmark)

    van Leeuwen, Theo; Djonov, Emilia


    After discussing broad cultural drivers behind the development of kinetic typography, the chapter outlines an approach to analysing kinetic typography which is based on Halliday's theory of transitivity, as applied by Kress and Van Leeuwen to visual images....

  14. Kinetic modeling of levulinic acid hydrogenation to gamma-valerolactone in water using a carbon supported Ru catalyst

    NARCIS (Netherlands)

    Piskun, A.S.; van de Bovenkamp, H.H.; Rasrendra, C.B.; Winkelman, J.G.M.; Heeres, H.J.


    gamma-Valerolactone (GVL) is considered a very interesting green, bio-based platform chemical with highapplication potential for the production of both biofuels and biobased chemicals. In this contribution, wereport a kinetic study on the hydrogenation of levulinic acid (LA) to 4-hydroxypentanoic

  15. Thermodynamic evaluation and modeling of proton and water exchange associated with benzamidine and berenil binding to ß-trypsin

    Directory of Open Access Journals (Sweden)

    M.T. Pereira


    Full Text Available Serine-proteases are involved in vital processes in virtually all species. They are important targets for researchers studying the relationships between protein structure and activity, for the rational design of new pharmaceuticals. Trypsin was used as a model to assess a possible differential contribution of hydration water to the binding of two synthetic inhibitors. Thermodynamic parameters for the association of bovine ß-trypsin (homogeneous material, observed 23,294.4 ± 0.2 Da, theoretical 23,292.5 Da with the inhibitors benzamidine and berenil at pH 8.0, 25ºC and with 25 mM CaCl2, were determined using isothermal titration calorimetry and the osmotic stress method. The association constant for berenil was about 12 times higher compared to the one for benzamidine (binding constants are K = 596,599 ± 25,057 and 49,513 ± 2,732 M-1, respectively; the number of binding sites is the same for both ligands, N = 0.99 ± 0.05. Apparently the driving force responsible for this large difference of affinity is not due to hydrophobic interactions because the variation in heat capacity (DCp, a characteristic signature of these interactions, was similar in both systems tested (-464.7 ± 23.9 and -477.1 ± 86.8 J K-1 mol-1 for berenil and benzamidine, respectively. The results also indicated that the enzyme has a net gain of about 21 water molecules regardless of the inhibitor tested. It was shown that the difference in affinity could be due to a larger number of interactions between berenil and the enzyme based on computational modeling. The data support the view that pharmaceuticals derived from benzamidine that enable hydrogen bond formation outside the catalytic binding pocket of ß-trypsin may result in more effective inhibitors.

  16. The kinetics of activation and deactivation in the process of water ozonising used for advanced oxidation of the dust waste from moulding sands

    Directory of Open Access Journals (Sweden)

    A. Baliński


    Full Text Available Adding coal dust and organic carriers of the lustrous carbon to bentonite-bonded moulding sands in amounts justified by thetechnological regime and the use of cores and protective coatings based on organic compounds create serious threats to the environment.During thermal destruction of the individual components of moulding and core sands, some toxic organic compounds are emitted. They formthe majority of the Hazardous Air Pollutants (HAPs, and include mainly compounds like benzene, toluene, xylene, naphtalene, hexane,acetaldehyde, acrolein, aniline, cresol and cumene, their polycyclic derivatives, phenol, formaldehyde, and other similar matters. In thusformed dust waste, the amount of which constitutes about 20% of all the waste from foundries using traditional moulding and core sands, there are still full-value materials which can undergo total recycling, providing the HAPs are partially or totally removed from them. The article discusses some problems of the advanced oxidation of selected toxic chemical compounds present in bentonite-bonded moulding sands due to the effect of high temperature. The results of the investigations of the kinetics of the process of maximum water saturation with ozone (acting as an oxidiser and of the kinetics of the natural process of ozone decomposition to diatomic oxygen were presented. It has been stated that the maximum time of water saturation with ozone using an OZOMATIC OSC-MODULAR 4HC ozone generator and a 1m3 capacity tank with water is 60 minutes. After 30 minute break in the ozonising process, the ozone concentration in water decreases by 40 to 50%. To obtain maximum ozone concentration in water during the next ozonising cycle, it is necessary to have the ozone-generating device running for the next 30 minutes. The stabilisation of ozone concentration in water takes place only after the third ozonising cycle, when it reaches nearly 80%of the maximum value obtained after the first process cycle

  17. Water-soluble Mo3S4 clusters bearing hydroxypropyl diphosphine ligands: synthesis, crystal structure, aqueous speciation, and kinetics of substitution reactions. (United States)

    Basallote, Manuel G; Fernández-Trujillo, M Jesús; Pino-Chamorro, Jose Ángel; Beltrán, Tomás F; Corao, Carolina; Llusar, Rosa; Sokolov, Maxim; Vicent, Cristian


    The [Mo(3)S(4)Cl(3)(dhprpe)(3)](+) (1(+)) cluster cation has been prepared by reaction between Mo(3)S(4)Cl(4)(PPh(3))(3) (solvent)(2) and the water-soluble 1,2-bis(bis(hydroxypropyl)phosphino)ethane (dhprpe, L) ligand. The crystal structure of [1](2)[Mo(6)Cl(14)] has been determined by X-ray diffraction methods and shows the typical incomplete cuboidal structure with a capping and three bridging sulfides. The octahedral coordination around each metal center is completed with a chlorine and two phosphorus atoms of the diphosphine ligand. Depending on the pH, the hydroxo group of the functionalized diphosphine can substitute the chloride ligands and coordinate to the cluster core to give new clusters with tridentate deprotonated dhprpe ligands of formula [Mo(3)S(4)(dhprpe-H)(3)](+) (2(+)). A detailed study based on stopped-flow, (31)P{(1)H} NMR, and electrospray ionization mass spectrometry techniques has been carried out to understand the behavior of acid-base equilibria and the kinetics of interconversion between the 1(+) and the 2(+) forms. Both conversion of 1(+) to 2(+) and its reverse process occur in a single kinetic step, so that reactions proceed at the three metal centers with statistically controlled kinetics. The values of the rate constants under different conditions are used to discuss on the mechanisms of opening and closing of the chelate rings with coordination or dissociation of chloride.

  18. Novel quantum mechanical/molecular mechanical method combined with the theory of energy representation: Free energy calculation for the Beckmann rearrangement promoted by proton transfers in the supercritical water (United States)

    Takahashi, Hideaki; Tanabe, Kohsuke; Aketa, Masataka; Kishi, Ryohei; Furukawa, Shin-ichi; Nakano, Masayoshi


    The Beckmann rearrangement of acetone oxime promoted by proton transfers in the supercritical water has been investigated by means of the hybrid quantum mechanical/molecular mechanical approach combined with the theory of energy representation (QM/MM-ER) recently developed. The transition state (TS) structures have been explored by ab initio calculations for the reaction of hydrated acetone oxime on the assumption that the reaction is catalyzed by proton transfers along the hydrogen bonds connecting the solute and the solvent water molecules. Up to two water molecules have been considered as reactants that take part in the proton transfers. As a result of the density functional theory calculations with B3LYP functional and aug-cc-pVDZ basis set, it has been found that participation of two water molecules in the reaction reduces the activation free energy by -12.3kcal/mol. Furthermore, the QM/MM-ER simulations have revealed that the TS is more stabilized than the reactant state in the supercritical water by 2.7kcal/mol when two water molecules are involved in the reaction. Solvation free energies of the reactant and the TS have been decomposed into terms due to the electronic polarization of the solute, electron density fluctuation, and others to elucidate the origin of the stabilization of the TS as compared with the reactant. It has been revealed that the promotion of the chemical reaction due to the hydration mainly originates from the interaction between the nonpolarized solute and the solvent water molecules at the supercritical state.

  19. Novel quantum mechanical/molecular mechanical method combined with the theory of energy representation: free energy calculation for the Beckmann rearrangement promoted by proton transfers in the supercritical water. (United States)

    Takahashi, Hideaki; Tanabe, Kohsuke; Aketa, Masataka; Kishi, Ryohei; Furukawa, Shin-ichi; Nakano, Masayoshi


    The Beckmann rearrangement of acetone oxime promoted by proton transfers in the supercritical water has been investigated by means of the hybrid quantum mechanical/molecular mechanical approach combined with the theory of energy representation (QM/MM-ER) recently developed. The transition state (TS) structures have been explored by ab initio calculations for the reaction of hydrated acetone oxime on the assumption that the reaction is catalyzed by proton transfers along the hydrogen bonds connecting the solute and the solvent water molecules. Up to two water molecules have been considered as reactants that take part in the proton transfers. As a result of the density functional theory calculations with B3LYP functional and aug-cc-pVDZ basis set, it has been found that participation of two water molecules in the reaction reduces the activation free energy by -12.3 kcal/mol. Furthermore, the QM/MM-ER simulations have revealed that the TS is more stabilized than the reactant state in the supercritical water by 2.7 kcal/mol when two water molecules are involved in the reaction. Solvation free energies of the reactant and the TS have been decomposed into terms due to the electronic polarization of the solute, electron density fluctuation, and others to elucidate the origin of the stabilization of the TS as compared with the reactant. It has been revealed that the promotion of the chemical reaction due to the hydration mainly originates from the interaction between the nonpolarized solute and the solvent water molecules at the supercritical state.

  20. Mechanisms of proton conductance in polymer electrolyte membranes

    DEFF Research Database (Denmark)

    Eikerling, M.; Kornyshev, A. A.; Kuznetsov, A. M.


    We provide a phenomenological description of proton conductance in polymer electrolyte membranes, based on contemporary views of proton transfer processes in condensed media and a model for heterogeneous polymer electrolyte membrane structure. The description combines the proton transfer events...... in a single pore with the total pore-network performance and, thereby, relates structural and kinetic characteristics of the membrane. The theory addresses specific experimentally studied issues such as the effect of the density of proton localization sites (equivalent weight) of the membrane material...

  1. Kinetic and equilibrium study for the sorption of Pb(II ions from aqueous phase by water hyacinth (Eichhornia crassipes

    Directory of Open Access Journals (Sweden)

    Gerald. K. Muthakia


    Full Text Available This paper reports the kinetic and equilibrium studies of Eichhornia crassipes root biomass as a biosorbent for Pb(II ions from aqueous system. Batch adsorption studies were carried out to examine the influence of various parameters such as the pH, contact time, adsorbent dose, initial metal ion concentration, temperature and agitation speed on the metal ion uptake. Uptake of Pb(II ions on the E. crassipes roots showed a pH-dependent profile. The maximum metal uptake values were 164 μg/mL. Langmuir model fitted the experimental sorption equilibrium data with a good fit (R2 › 0.99. The biosorption kinetics was described by the pseudo-second-order model (R2 › 0.99.DOI:

  2. Kinetic proofreading at single molecular level: aminoacylation of tRNA(Ile and the role of water as an editor.

    Directory of Open Access Journals (Sweden)

    Mantu Santra

    Full Text Available Proofreading/editing in protein synthesis is essential for accurate translation of information from the genetic code. In this article we present a theoretical investigation of efficiency of a kinetic proofreading mechanism that employs hydrolysis of the wrong substrate as the discriminatory step in enzyme catalytic reactions. We consider aminoacylation of tRNA(Ile which is a crucial step in protein synthesis and for which experimental results are now available. We present an augmented kinetic scheme and then employ methods of stochastic simulation algorithm to obtain time dependent concentrations of different substances involved in the reaction and their rates of formation. We obtain the rates of product formation and ATP hydrolysis for both correct and wrong substrates (isoleucine and valine in our case, respectively, in single molecular enzyme as well as ensemble enzyme kinetics. The present theoretical scheme correctly reproduces (i the amplitude of the discrimination factor in the overall rates between isoleucine and valine which is obtained as (1.8×10(2.(4.33×10(2 = 7.8×10(4, (ii the rates of ATP hydrolysis for both Ile and Val at different substrate concentrations in the aminoacylation of tRNA(Ile. The present study shows a non-michaelis type dependence of rate of reaction on tRNA(Ile concentration in case of valine. The overall editing in steady state is found to be independent of amino acid concentration. Interestingly, the computed ATP hydrolysis rate for valine at high substrate concentration is same as the rate of formation of Ile-tRNA(Ile whereas at intermediate substrate concentration the ATP hydrolysis rate is relatively low. We find that the presence of additional editing domain in class I editing enzyme makes the kinetic proofreading more efficient through enhanced hydrolysis of wrong product at the editing CP1 domain.

  3. Proton movies

    CERN Multimedia


    A humorous short film made by three secondary school students received an award at a Geneva film festival. Even without millions of dollars or Hollywood stars at your disposal, it is still possible to make a good science fiction film about CERN. That is what three students from the Collège Madame de Staël in Carouge, near Geneva, demonstrated. For their amateur short film on the LHC, they were commended by the jury of the video and multimedia festival for schools organised by the "Media in education" service of the Canton of Geneva’s Public Education Department. The film is a spoof of a television news report on the LHC start-up. In sequences full of humour and imagination, the reporter conducts interviews with a very serious "Professor Sairne", some protons preparing for their voyage and even the neutrons that were rejected by the LHC. "We got the idea of making a film about CERN at the end of the summer," explains Lucinda Päsche, one of the three students. "We did o...

  4. What Really Prevents Proton Transport through Aquaporin? Charge Self-Energy versus Proton Wire Proposals


    Burykin, Anton; Warshel, Arieh


    The nature of the control of water/proton selectivity in biological channels is a problem of a fundamental importance. Most studies of this issue have proposed that an interference with the orientational requirements of the so-called proton wire is the source of selectivity. The elucidation of the structures of aquaporins, which have evolved to prevent proton transfer (PT), provided a clear benchmark for exploring the selectivity problem. Previous simulations of this system have not examined,...

  5. Water

    Directory of Open Access Journals (Sweden)

    E. Sanmuga Priya


    Full Text Available Phytoremediation through aquatic macrophytes treatment system (AMATS for the removal of pollutants and contaminants from various natural sources is a well established environmental protection technique. Water hyacinth (Eichhornia crassipes, a worst invasive aquatic weed has been utilised for various research activities over the last few decades. The biosorption capacity of the water hyacinth in minimising various contaminants present in the industrial wastewater is well studied. The present review quotes the literatures related to the biosorption capacity of the water hyacinth in reducing the concentration of dyestuffs, heavy metals and minimising certain other physiochemical parameters like TSS (total suspended solids, TDS (total dissolved solids, COD (chemical oxygen demand and BOD (biological oxygen demand in textile wastewater. Sorption kinetics through various models, factors influencing the biosorption capacity, and role of physical and chemical modifications in the water hyacinth are also discussed.

  6. Water equivalent thickness of immobilization devices in proton therapy planning - Modelling at treatment planning and validation by measurements with a multi-layer ionization chamber. (United States)

    Fellin, Francesco; Righetto, Roberto; Fava, Giovanni; Trevisan, Diego; Amelio, Dante; Farace, Paolo


    To investigate the range errors made in treatment planning due to the presence of the immobilization devices along the proton beam path. The measured water equivalent thickness (WET) of selected devices was measured by a high-energy spot and a multi-layer ionization chamber and compared with that predicted by treatment planning system (TPS). Two treatment couches, two thermoplastic masks (both un-stretched and stretched) and one headrest were selected. At TPS, every immobilization device was modelled as being part of the patient. The following parameters were assessed: CT acquisition protocol, dose-calculation grid-sizes (1.5 and 3.0mm) and beam-entrance with respect to the devices (coplanar and non-coplanar). Finally, the potential errors produced by a wrong manual separation between treatment couch and the CT table (not present during treatment) were investigated. In the thermoplastic mask, there was a clear effect due to beam entrance, a moderate effect due to the CT protocols and almost no effect due to TPS grid-size, with 1mm errors observed only when thick un-stretched portions were crossed by non-coplanar beams. In the treatment couches the WET errors were negligible (0.5mm with a 3.0mm grid-size. In the headrest, WET errors were negligible (0.2mm). With only one exception (un-stretched mask, non-coplanar beams), the WET of all the immobilization devices was properly modelled by the TPS. Copyright © 2017 Associazione Italiana di Fisica Medica. Published by Elsevier Ltd. All rights reserved.

  7. Characterization, non-isothermal decomposition kinetics and photocatalytic water splitting of green chemically synthesized polyoxoanions of molybdenum containing phosphorus as hetero atom

    Energy Technology Data Exchange (ETDEWEB)

    D’Cruz, Bessy [Department of Chemistry, Mar Ivanios College, Thiruvananthapuram 695015 (India); Samuel, Jadu, E-mail: [Department of Chemistry, Mar Ivanios College, Thiruvananthapuram 695015 (India); George, Leena [Catalysis and Inorganic Chemistry Division, National Chemical Laboratory, Pune 411008 (India)


    Highlights: • CPM nanorods were synthesized by applying the principles of green chemistry. • The isoconversional method was used to analyze the effective activation energy. • The appropriate reaction models of the two decomposition stages were determined. • Photocatalytic water splitting was investigated in the presence of platinum co-catalyst. - Abstract: In here, the green synthesis and thermal characterization of a novel polyoxoanions of molybdenum containing phosphorus as hetero atom are reported. The composition and morphology of the nanorods were established by fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA) and inductively coupled plasma atomic emission spectroscopic (ICP-AES) techniques. Thermal properties of the nanoparticles were investigated by non-isothermal analysis under nitrogen atmosphere. The values activation energy of each stage of thermal decomposition for all heating rates was calculated by Flynn–Wall–Ozawa (FWO) and Kissinger–Akahira–Sunnose (KAS) methods. Invariant kinetic parameter (IKP) method and master plot method were also used to evaluate the kinetic parameters and mechanism for the thermal decomposition of cetylpyridinium phosphomolybdate (CPM). Photocatalytic water oxidation mechanism using CPM catalyst in the presence of platinum (Pt) co-catalyst enhances the H{sub 2} evolution and was found to be 1.514 mmol/g/h.

  8. Enzymatic synthesis of farnesyl laurate in organic solvent: initial water activity, kinetics mechanism, optimization of continuous operation using packed bed reactor and mass transfer studies. (United States)

    Rahman, N K; Kamaruddin, A H; Uzir, M H


    The influence of water activity and water content was investigated with farnesyl laurate synthesis catalyzed by Lipozyme RM IM. Lipozyme RM IM activity depended strongly on initial water activity value. The best results were achieved for a reaction medium with an initial water activity of 0.11 since it gives the best conversion value of 96.80%. The rate constants obtained in the kinetics study using Ping-Pong-Bi-Bi and Ordered-Bi-Bi mechanisms with dead-end complex inhibition of lauric acid were compared. The corresponding parameters were found to obey the Ordered-Bi-Bi mechanism with dead-end complex inhibition of lauric acid. Kinetic parameters were calculated based on this model as follows: V (max) = 5.80 mmol l(-1) min(-1) g enzyme(-1), K (m,A) = 0.70 mmol l(-1) g enzyme(-1), K (m,B) = 115.48 mmol l(-1) g enzyme(-1), K (i) = 11.25 mmol l(-1) g enzyme(-1). The optimum conditions for the esterification of farnesol with lauric acid in a continuous packed bed reactor were found as the following: 18.18 cm packed bed height and 0.9 ml/min substrate flow rate. The optimum molar conversion of lauric acid to farnesyl laurate was 98.07 ± 0.82%. The effect of mass transfer in the packed bed reactor has also been studied using two models for cases of reaction limited and mass transfer limited. A very good agreement between the mass transfer limited model and the experimental data obtained indicating that the esterification in a packed bed reactor was mass transfer limited.

  9. Biodegradation and kinetics of organic compounds and heavy metals in an artificial wetland system (AWS) by using water hyacinths as a biological filter. (United States)

    Rodríguez-Espinosa, P F; Mendoza-Pérez, J A; Tabla-Hernandez, J; Martínez-Tavera, E; Monroy-Mendieta, M M


    The objective of the present study was to investigate the ability of water hyacinth (Eichhornia crassipes) to absorb organic compounds (potassium hydrogen phthalate, sodium tartrate, malathion, 2,4-dichlorophenoxy acetic acid (2,4-D), and piroxicam). For the aforementioned purpose, an artificial wetland system (AWS) was constructed and filled with water hyacinth collected from the Valsequillo Reservoir, Puebla, Mexico. Potassium hydrogen phthalate and sodium tartrate were measured in terms of chemical oxygen demand (COD) and biological oxygen demand (BOD). The present study indicated that the water hyacinths absorbed nearly 1.8-16.6 g of COD kg -1 dm (dry mass of water hyacinth), while the absorbance efficiency of BOD was observed to be 45.8%. The results also indicated that the maximum absorbance efficiency of malathion, 2,4-D, and piroxicam was observed to be 67.6%, 58.3%, and 99.1%, respectively. The kinetics of organic compounds fitted different orders as malathion followed a zeroth-order reaction, while 2,4-D and piroxicam followed the first-order reactions. Preliminary assessment of absorption of heavy metals by the water hyacinth in the AWS was observed to be (all values in mg g -1 ) 7 (Ni), 13.4 (Cd), 16.3 (Pb), and 17.5 (Zn) of dry biomass, thus proving its feasibility to depurate wastewater.

  10. Proton emission from a laser ion sourcea) (United States)

    Torrisi, L.; Cavallaro, S.; Cutroneo, M.; Margarone, D.; Gammino, S.


    At intensities of the order of 1010 W/cm2, ns pulsed lasers can be employed to ablate solid bulk targets in order to produce high emission of ions at different charge state and kinetic energy. A special interest is devoted to the production of protons with controllable energy and current from a roto-translating target irradiated in repetition rate at 1-10 Hz by a Nd:Yag pulsed laser beam. Different hydrogenated targets based on polymers and hydrates were irradiated in high vacuum. Special nanostrucutres can be embedded in the polymers in order to modify the laser absorption properties and the amount of protons to be accelerated in the plasma. For example, carbon nanotubes may increase the laser absorption and the hydrogen absorption to generate high proton yields from the plasma. Metallic nanostrucutres may increase the electron density of the plasma and the kinetic energy of the accelerated protons. Ion collectors, ion energy analyzer, and mass spectrometers, used in time-of-flight configuration, were employed to characterize the ion beam properties. A comparison with traditional proton ion source is presented and discussed.

  11. Proton emission from a laser ion source

    Energy Technology Data Exchange (ETDEWEB)

    Torrisi, L. [INFN-LNS Via S. Sofia 44, 95123 Catania (Italy); di Fisica, Universita di Messina, V.le F.S. D' Alcontres 31, 98166 S. Agata, Messina (Italy); Cavallaro, S.; Gammino, S. [INFN-LNS Via S. Sofia 44, 95123 Catania (Italy); Cutroneo, M. [ di Fisica, Universita di Messina, V.le F.S. D' Alcontres 31, 98166 S. Agata, Messina (Italy); Margarone, D. [Institute of Physics, ASCR, v.v.i., 182 21 Prague 8 (Czech Republic)


    At intensities of the order of 10{sup 10} W/cm{sup 2}, ns pulsed lasers can be employed to ablate solid bulk targets in order to produce high emission of ions at different charge state and kinetic energy. A special interest is devoted to the production of protons with controllable energy and current from a roto-translating target irradiated in repetition rate at 1-10 Hz by a Nd:Yag pulsed laser beam. Different hydrogenated targets based on polymers and hydrates were irradiated in high vacuum. Special nanostrucutres can be embedded in the polymers in order to modify the laser absorption properties and the amount of protons to be accelerated in the plasma. For example, carbon nanotubes may increase the laser absorption and the hydrogen absorption to generate high proton yields from the plasma. Metallic nanostrucutres may increase the electron density of the plasma and the kinetic energy of the accelerated protons. Ion collectors, ion energy analyzer, and mass spectrometers, used in time-of-flight configuration, were employed to characterize the ion beam properties. A comparison with traditional proton ion source is presented and discussed.

  12. Proton emission from a laser ion source. (United States)

    Torrisi, L; Cavallaro, S; Cutroneo, M; Margarone, D; Gammino, S


    At intensities of the order of 10(10) W∕cm(2), ns pulsed lasers can be employed to ablate solid bulk targets in order to produce high emission of ions at different charge state and kinetic energy. A special interest is devoted to the production of protons with controllable energy and current from a roto-translating target irradiated in repetition rate at 1-10 Hz by a Nd:Yag pulsed laser beam. Different hydrogenated targets based on polymers and hydrates were irradiated in high vacuum. Special nanostrucutres can be embedded in the polymers in order to modify the laser absorption properties and the amount of protons to be accelerated in the plasma. For example, carbon nanotubes may increase the laser absorption and the hydrogen absorption to generate high proton yields from the plasma. Metallic nanostrucutres may increase the electron density of the plasma and the kinetic energy of the accelerated protons. Ion collectors, ion energy analyzer, and mass spectrometers, used in time-of-flight configuration, were employed to characterize the ion beam properties. A comparison with traditional proton ion source is presented and discussed.

  13. Modeling the Proton Radiation Belt With Van Allen Probes Relativistic Electron-Proton Telescope Data (United States)

    Selesnick, R. S.; Baker, D. N.; Kanekal, S. G.; Hoxie, V. C.; Li, X.


    An empirical model of the proton radiation belt is constructed from data taken during 2013-2017 by the Relativistic Electron-Proton Telescopes on the Van Allen Probes satellites. The model intensity is a function of time, kinetic energy in the range 18-600 MeV, equatorial pitch angle, and L shell of proton guiding centers. Data are selected, on the basis of energy deposits in each of the nine silicon detectors, to reduce background caused by hard proton energy spectra at low L. Instrument response functions are computed by Monte Carlo integration, using simulated proton paths through a simplified structural model, to account for energy loss in shielding material for protons outside the nominal field of view. Overlap of energy channels, their wide angular response, and changing satellite orientation require the model dependencies on all three independent variables be determined simultaneously. This is done by least squares minimization with a customized steepest descent algorithm. Model uncertainty accounts for statistical data error and systema