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Sample records for water proton kinetic

  1. Kinetics of proton migration in liquid water.

    Science.gov (United States)

    Chen, Hanning; Voth, Gregory A; Agmon, Noam

    2010-01-14

    We have utilized multistate empirical valence bond (MS-EVB3) simulations of protonated liquid water to calculate the relative mean-square displacement (MSD) and the history-independent time correlation function, c(t), of the hydrated proton center of excess charge (CEC) with respect to the water molecule on which it has initially resided. The MSD is nonlinear for the first 15 ps, suggesting that the relative diffusion coefficient increases from a small value, D(0), at short separations to its larger bulk value, D(infinity), at large separations. With the ensuing distance-dependent diffusion coefficient, D(r), the time dependence of both the MSD and c(t) agrees quantitatively with the solution of a diffusion equation for reversible geminate recombination. This suggests that the relative motion of the CEC is not independent from the nearby water molecules, in agreement with theoretical and experimental observations that large water clusters participate in the mechanism of proton mobility.

  2. Kinetics of proton transport in water

    DEFF Research Database (Denmark)

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

    2003-01-01

    for rationalizing the excess proton mobility, based on computer simulations, theory of proton transfer (PT) in condensed media, and analysis of classical proton conductivity experiments over broad temperature ranges. The mechanistic options involved are (i) classical hydrodynamic motion of the hydronium ion (H3O...... 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...

  3. Kinetics of water-mediated proton transfer in our atmosphere

    International Nuclear Information System (INIS)

    Loerting, T.

    2000-07-01

    Variational transition state theory and multidimensional tunneling methods on hybrid density functional theory generated hypersurfaces have been used to investigate the temperature dependence of the reaction rate constants of water-mediated proton transfer reactions relevant to the chemistry of our atmosphere, namely the hydration of sulfur dioxide and sulfur trioxide and the decomposition of chlorine nitrate. Highly accurate reaction barriers were calculated using ab initio methods taking into account most of the electron correlation, namely CCSD(T)/aug-cc-pVDZ//MP2/aug-cc-pVDZ and G2(MP2). On comparing the determined rate constants with laboratory and atmospheric data, the following points could be established: All of the investigated reactions are highly sensitive to changes in humidity, as water acts as efficient catalyst, i.e., the barrier to the reaction is reduced drastically. Present-day atmospheric chemistry can only be explained when a limited number of water molecules is available for the formation of molecular clusters. Both in the troposphere and in the stratosphere SO 3 is hydrated rather than SO 2 . SO 2 emissions have to be oxidized, therefore, before being subject to hydration. A mechanism involving two or three water molecules is relevant for the production of sulfate aerosols, which play a decisive role in the context of global climate change and acid rain. A third water molecule has the function of assisting double-proton transfer rather than acting as active participant in triple-proton transfer in the case of the hydration of sulfur oxides. The observed ozone depletion above Arctica and Antarctica can be explained either by decomposition of chlorine nitrate in the presence of three water molecules (triple proton transfer) or by decomposition of chlorine nitrate in the presence of one molecule of HCl and one molecule of water (double proton transfer). The preassociation reaction required for homogeneous gas-phase conversion of chlorine

  4. DINS measurements on VESUVIO in the Resonance Detector configuration: proton mean kinetic energy in water

    Science.gov (United States)

    Pietropaolo, Antonino; Andreani, Carla; Filabozzi, Alessandra; Senesi, Roberto; Gorini, Giuseppe; Perelli-Cippo, Enrico; Tardocchi, Marco; Rhodes, Nigel J.; Schooneveld, Erik M.

    2006-04-01

    Deep Inelastic Neutron Scattering (DINS) measurements have been performed on a liquid water sample at two different temperatures and pressures. The experiments were carried out using the VESUVIO spectrometer at the ISIS spallation neutron source. This experiment represents the first DINS measurement from water using the Resonance Detector configuration, employing yttrium-aluminum-perovskite scintillator and a 238U analyzer foil. The maximum energy of the scattered neutrons was about 70 eV, allowing to access an extended kinematic space with energy and wave vector transfers at the proton recoil peak in the range 1 eV <= hbarω <= 20 eV and 25 Å-1 <= q <= 90 Å-1, respectively. Comparison with DINS measurements on water performed in the standard Resonance Filter configuration indicates the potential advantages offered by the use of Resonance Detector approach for DINS measurements at forward scattering angles.

  5. Relaxation dynamics and transformation kinetics of deeply supercooled water: Temperature, pressure, doping, and proton/deuteron isotope effects.

    Science.gov (United States)

    Lemke, Sonja; Handle, Philip H; Plaga, Lucie J; Stern, Josef N; Seidl, Markus; Fuentes-Landete, Violeta; Amann-Winkel, Katrin; Köster, Karsten W; Gainaru, Catalin; Loerting, Thomas; Böhmer, Roland

    2017-07-21

    Above its glass transition, the equilibrated high-density amorphous ice (HDA) transforms to the low-density pendant (LDA). The temperature dependence of the transformation is monitored at ambient pressure using dielectric spectroscopy and at elevated pressures using dilatometry. It is found that near the glass transition temperature of deuterated samples, the transformation kinetics is 300 times slower than the structural relaxation, while for protonated samples, the time scale separation is at least 30 000 and insensitive to doping. The kinetics of the HDA to LDA transformation lacks a proton/deuteron isotope effect, revealing that this process is dominated by the restructuring of the oxygen network. The x-ray diffraction experiments performed on samples at intermediate transition stages reflect a linear combination of the LDA and HDA patterns implying a macroscopic phase separation, instead of a local intermixing of the two amorphous states.

  6. Relaxation dynamics and transformation kinetics of deeply supercooled water: Temperature, pressure, doping, and proton/deuteron isotope effects

    Science.gov (United States)

    Lemke, Sonja; Handle, Philip H.; Plaga, Lucie J.; Stern, Josef N.; Seidl, Markus; Fuentes-Landete, Violeta; Amann-Winkel, Katrin; Köster, Karsten W.; Gainaru, Catalin; Loerting, Thomas; Böhmer, Roland

    2017-07-01

    Above its glass transition, the equilibrated high-density amorphous ice (HDA) transforms to the low-density pendant (LDA). The temperature dependence of the transformation is monitored at ambient pressure using dielectric spectroscopy and at elevated pressures using dilatometry. It is found that near the glass transition temperature of deuterated samples, the transformation kinetics is 300 times slower than the structural relaxation, while for protonated samples, the time scale separation is at least 30 000 and insensitive to doping. The kinetics of the HDA to LDA transformation lacks a proton/deuteron isotope effect, revealing that this process is dominated by the restructuring of the oxygen network. The x-ray diffraction experiments performed on samples at intermediate transition stages reflect a linear combination of the LDA and HDA patterns implying a macroscopic phase separation, instead of a local intermixing of the two amorphous states.

  7. Vlasov simulations of Kinetic Alfven Waves at proton kinetic scales

    NARCIS (Netherlands)

    C.L. Vasconez; F. Valentini (Francesco); E. Camporeale (Enrico); P. Veltri

    2014-01-01

    htmlabstractKinetic Alfv ́en 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 inertial length d p and beyond). A

  8. Proton exchange membrane water electrolysers

    International Nuclear Information System (INIS)

    Millet, P.

    2007-01-01

    This work deals with the PEM water electrolysis process. Are successively described: the thermodynamical, kinetic and energetic aspects, the different possible used electrolysis cells, the preparation of the membrane-electrode assembling, the used electrolysers, the annex production equipment, the uses fields and the limits of the process. (O.M.)

  9. 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)

    2014-11-15

    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.

  10. Kinetic Study on Channelling of Protons in Metallic Carbon Nanotubes

    International Nuclear Information System (INIS)

    Dan, Zhao; Yuan-Hong, Song; You-Nian, Wang

    2008-01-01

    Based on the kinetic model and the dielectric response theory, a theoretical model is put forward to describe the transport of protons along nanotube axes. With the introduction of electron band structure for different nanotubes like zigzag and armchair nanotubes of metallic properties, the collective excitation of electrons on the cylinders induced by the incident ions is studied, showing several distinct peaks in the curves of the energy loss function. Furthermore, the stopping power and the self-energy are calculated as functions of ion velocities, especially taking into account the influence of damping coefficients. It is conceivable from the results that, in the kinetic formulation, plasmon excitation plays a major role in the stopping. And as the damping increases, the peaks of the stopping power shift to the lower velocities, with the broadening of the plasmon resonance. (condensed matter: structure, mechanical and thermal properties)

  11. Kinetic Effects Of Increased Proton Transfer Distance On Proton-Coupled Oxidations Of Phenol-Amines

    Science.gov (United States)

    Rhile, Ian J.

    2011-01-01

    To test the effect of varying the proton donor-acceptor distance in proton-coupled electron transfer (PCET) reactions, the oxidation of a bicyclic amino-indanol (2) is compared with that of a closely related phenol with an ortho CPh2NH2 substituent (1). Spectroscopic, structural, thermochemical and computational studies show that the two amino-phenols are very similar, except that the O⋯N distance (dON) is >0.1 Å longer in 2 than in 1. The difference in dON is 0.13 ± 0.03 Å from X-ray crystallography and 0.165 Å from DFT calculations. Oxidations of these phenols by outer-sphere oxidants yield distonic radical cations •OAr–NH3+ by concerted proton-electron transfer (CPET). Simple tunneling and classical kinetic models both predict that the longer donor-acceptor distance in 2 should lead to slower reactions, by ca. two orders of magnitude, as well as larger H/D kinetic isotope effects (KIEs). However, kinetic studies show that the compound with the longer proton-transfer distance, 2, exhibits smaller KIEs and has rate constants that are quite close to those of 1. For example, the oxidation of 2 by the triarylamminium radical cation N(C6H4OMe)3•+ (3a+) occurs at (1.4 ± 0.1) × 104 M-1 s-1, only a factor of two slower than the closely related reaction of 1 with N(C6H4OMe)2(C6H4Br)•+ (3b+). This difference in rate constants is well accounted for by the slightly different free energies of reaction: ΔG°(2 + 3a+) = +0.078 V vs. ΔG°(1 + 3b+) = +0.04 V. The two phenol-amines do display some subtle kinetic differences: for instance, compound 2 has a shallower dependence of CPET rate constants on driving force (Brønsted α, Δln(k)/Δln(Keq)). These results show that the simple tunneling model is not a good predictor of the effect of proton donor-acceptor distance on concerted-electron transfer reactions involving strongly hydrogen-bonded systems. Computational analysis of the observed similarity of the two phenols emphasizes the importance of the highly

  12. NMR studies of proton exchange kinetics in aqueous formaldehyde solutions.

    Science.gov (United States)

    Rivlin, Michal; Eliav, Uzi; Navon, Gil

    2014-05-01

    Aqueous solutions of formaldehyde, formalin, are commonly used for tissue fixation and preservation. Treatment with formalin is known to shorten the tissue transverse relaxation time T2. Part of this shortening is due to the effect of formalin on the water T2. In the present work we show that the shortening of water T2 is a result of proton exchange between water and the major constituent of aqueous solutions of formaldehyde, methylene glycol. We report the observation of the signal of the hydroxyl protons of methylene glycol at 2ppm to high frequency of the water signal that can be seen at low temperatures and at pH range of 6.0±1.5 and, at conditions where it cannot be observed by the single pulse experiment, it can be detected indirectly through the water signal by the chemical exchange saturation transfer (CEST) experiment. The above finding made it possible to obtain the exchange rate between the hydroxyl protons of the methylene glycol and water in aqueous formaldehyde solutions, either using the dispersion of the spin-lattice relaxation rate in the rotating frame (1/T1ρ) or, at the slow exchange regime, from the line width hydroxyl protons of methylene glycol. The exchange rate was ∼10(4)s(-1) at pH 7.4 and 37°C, the activation energy, 50.2kJ/mol and its pH dependence at 1.1°C was fitted to: k (s(-1))=520+6.5×10(7)[H(+)]+3.0×10(9)[OH(-)]. Copyright © 2014. Published by Elsevier Inc.

  13. Influence of Proton Acceptors on the Proton-Coupled Electron Transfer Reaction Kinetics of a Ruthenium-Tyrosine Complex.

    Science.gov (United States)

    Lennox, J Christian; Dempsey, Jillian L

    2017-11-22

    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.

  14. Hydrogen peroxide kinetics in water radiolysis

    Science.gov (United States)

    Iwamatsu, Kazuhiro; Sundin, Sara; LaVerne, Jay A.

    2018-04-01

    The kinetics of the formation and reaction of hydrogen peroxide in the long time γ- radiolysis of water is examined using a combination of experiment with model calculations. Escape yields of hydrogen peroxide on the microsecond time scale are easily measured with added radical scavengers even with substantial amounts of initial added hydrogen peroxide. The γ-radiolysis of aqueous hydrogen peroxide solutions without added radical scavengers reach a steady state limiting concentration of hydrogen peroxide with increasing dose, and that limit is directly proportional to the initial concentration of added hydrogen peroxide. The dose necessary to reach that limiting hydrogen peroxide concentration is also proportional to the initial concentration, but dose rate has a very small effect. The addition of molecular hydrogen to aqueous solutions of hydrogen peroxide leads to a decrease in the high dose limiting hydrogen peroxide concentration that is linear with the initial hydrogen concentration, but the amount of decrease is not stoichiometric. Proton irradiations of solutions with added hydrogen peroxide and hydrogen are more difficult to predict because of the decreased yields of radicals; however, with a substantial increase in dose rate there is a sufficient decrease in radical yields that hydrogen addition has little effect on hydrogen peroxide decay.

  15. Determination of kinetic coefficients for proton-nucleus collisions at high energy

    International Nuclear Information System (INIS)

    Rizzato, C.M.

    1987-01-01

    From the effective proton dynamics, the approximations in the context of high energy collisions which lead to the Boltzmann equation, are established. From this equation, general expressions for the kinetic coefficients are deduced. Using a simple model, analytical expressions for kinetic coefficients are obtained. The importance of the effect of Pauli blocking is also shown. (author) [pt

  16. Stabilities of protonated water-ammonia clusters

    Science.gov (United States)

    Sundén, A. E. K.; Støchkel, K.; Hvelplund, P.; Brøndsted Nielsen, S.; Dynefors, B.; Hansen, K.

    2018-05-01

    Branching ratios of water and ammonia evaporation have been measured for spontaneous evaporation from protonated mixed clusters H+(H2O)n(NH3)m in the size range 0 ≤ n ≤ 11 and 0 ≤ m ≤ 7. Mixed clusters evaporate water except for clusters containing six or more ammonia molecules, indicating the formation of a stable core of one ammonium ion surrounded by four ammonia molecules and a second shell consisting predominantly of water. We relate evaporative branching ratios to free energy differences between the products of competing channels and determine the free energy differences for clusters with up to seven ammonia molecules. Clusters containing up to five ammonia molecules show a very strong scaling of these free energy differences.

  17. A KINETIC ALFVEN WAVE AND THE PROTON DISTRIBUTION FUNCTION IN THE FAST SOLAR WIND

    International Nuclear Information System (INIS)

    Li Xing; Lu Quanming; Chen Yao; Li Bo; Xia Lidong

    2010-01-01

    Using one-dimensional test particle simulations, the effect of a kinetic Alfven wave on the velocity distribution function (VDF) of protons in the collisionless solar wind is investigated. We first use linear Vlasov theory to numerically obtain the property of a kinetic Alfven wave (the wave propagates in the direction almost perpendicular to the background magnetic field). We then numerically simulate how the wave will shape the proton VDF. It is found that Landau resonance may be able to generate two components in the initially Maxwellian proton VDF: a tenuous beam component along the direction of the background magnetic field and a core component. The streaming speed of the beam relative to the core proton component is about 1.2-1.3 Alfven speed.

  18. A quasilinear kinetic model for solar wind electrons and protons instabilities

    Science.gov (United States)

    Sarfraz, M.; Yoon, P. H.

    2017-12-01

    In situ measurements confirm the anisotropic behavior in temperatures of solar wind species. These anisotropies associated with charge particles are observed to be relaxed. In collionless limit, kinetic instabilities play a significant role to reshape particles distribution. The linear analysis results are encapsulated in inverse relationship between anisotropy and plasma beta based observations fittings techniques, simulations methods, or solution of linearized Vlasov equation. Here amacroscopic quasilinear technique is adopted to confirm inverse relationship through solutions of set of self-consistent kinetic equations. Firstly, for a homogeneous and non-collisional medium, quasilinear kinetic model is employed to display asymptotic variations of core and halo electrons temperatures and saturations of wave energy densities for electromagnetic electron cyclotron (EMEC) instability sourced by, T⊥}>T{∥ . It is shown that, in (β ∥ , T⊥}/T{∥ ) phase space, the saturations stages of anisotropies associated with core and halo electrons lined up on their respective marginal stability curves. Secondly, for case of electrons firehose instability ignited by excessive parallel temperature i.e T⊥}>T{∥ , both electrons and protons are allowed to dynamically evolve in time. It is also observed that, the trajectories of protons and electrons at saturation stages in phase space of anisotropy and plasma beta correspond to proton cyclotron and firehose marginal stability curves, respectively. Next, the outstanding issue that most of observed proton data resides in nearly isotropic state in phase space is interpreted. Here, in quasilinear frame-work of inhomogeneous solar wind system, a set of self-consistent quasilinear equations is formulated to show a dynamical variations of temperatures with spatial distributions. On choice of different initial parameters, it is shown that, interplay of electron and proton instabilities provides an counter-balancing force to slow

  19. Probing water structure and transport in proton exchange membranes

    NARCIS (Netherlands)

    Ling, X.

    2018-01-01

    Proton exchange membrane fuel cells (PEMFCs) have attracted tremendous attention as alternative energy sources because of their high energy density and practically zero greenhouse gas emission - water is their only direct by-product. Critical to the function of PEMFCs is fast proton and water

  20. 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

    2013-08-08

    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.

  1. Electron and proton kinetics and dynamics in flaring atmospheres

    CERN Document Server

    Zharkova, Valentina

    2012-01-01

    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. Hydrogen peroxide decomposition kinetics in aquaculture water

    DEFF Research Database (Denmark)

    Arvin, Erik; Pedersen, Lars-Flemming

    2015-01-01

    during the HP decomposition. The model assumes that the enzyme decay is controlled by an inactivation stoichiometry related to the HP decomposition. In order to make the model easily applicable, it is furthermore assumed that the COD is a proxy of the active biomass concentration of the water and thereby......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...

  3. The protonation state around TyrD/TyrD• in photosystem II is reflected in its biphasic oxidation kinetics.

    Science.gov (United States)

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

    2017-02-01

    The tyrosine residue D2-Tyr160 (Tyr D ) in photosystem II (PSII) can be oxidized through charge equilibrium with the oxygen evolving complex in PSII. The kinetics of the electron transfer from Tyr D has been followed using time-resolved EPR spectroscopy after triggering the oxidation of pre-reduced Tyr D by a short laser flash. After its oxidation Tyr D is observed as a neutral radical (Tyr D • ) indicating that the oxidation is coupled to a deprotonation event. The redox state of Tyr D 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 Tyr D the oxidation kinetics has been followed in the presence of deuterated buffers, thereby resolving the kinetic isotope effect (KIE) of Tyr D oxidation at different H/D concentrations. Two kinetic phases of Tyr D 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 Tyr D . Copyright © 2016 Elsevier B.V. All rights reserved.

  4. Water versus DNA: new insights into proton track-structure modelling in radiobiology and radiotherapy.

    Science.gov (United States)

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

    2015-10-21

    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.

  5. Kinetics of steel corrosion in water

    International Nuclear Information System (INIS)

    Vettegren', V.I.; Bashkarev, A.Ya.; Danchukov, K.G.; Morozov, G.I.

    2003-01-01

    Kinetics of corrosion damage accumulation in steels of different composition (Cr-Ni-Mo-Ti, Cr-Ni-Mn-N-V, Cr-Ni-N-Mn-Mo, Cr-Ni-Nb, Cr-Ni-Ti, Cr-Mn-Ni, Mn-Al-Nb-Si, Mn-Cr-Al-Si and Mn-Al-Si) in NaCl solution and in sea water was studied. It is shown that degree of corrosion damage relates to time according to the first order reaction expression. The values of corrosion activation energy and of parameter characterizing protection properties of corrosion film are determined [ru

  6. Proton production, neutralisation and reduction in a floating water bridge

    Science.gov (United States)

    Sammer, Martina; Wexler, Adam D.; Kuntke, Philipp; Wiltsche, Helmar; Stanulewicz, Natalia; Lankmayr, Ernst; Woisetschläger, Jakob; Fuchs, Elmar C.

    2015-10-01

    This work reports on proton production, transport, reduction and neutralization in floating aqueous bridges under the application of a high dc voltage (‘floating water bridge’). Recently possible mechanisms for proton transfer through the bridge were suggested. In this work we visualize and describe the production of protons in the anolyte and their neutralization in the catholyte. Apart from that, protons are reduced to hydrogen due to electrolysis. Microbubbles are detached instantly, due to the electrohydrodynamic flow at the electrode surface. No larger, visible bubbles are formed and the system degasses through the bridge due to its higher local temperature. A detailed analysis of trace elements originating from beaker material, anode or the atmosphere is presented, showing that their influence on the overall conduction compared to the contribution of protons is negligible. Finally, an electrochemical rationale of high voltage electrolysis of low ionic strength solutions is presented.

  7. Proton production, neutralisation and reduction in a floating water bridge

    International Nuclear Information System (INIS)

    Sammer, Martina; Wexler, Adam D; Kuntke, Philipp; Stanulewicz, Natalia; Lankmayr, Ernst; Woisetschläger, Jakob; Fuchs, Elmar C; Wiltsche, Helmar

    2015-01-01

    This work reports on proton production, transport, reduction and neutralization in floating aqueous bridges under the application of a high dc voltage (‘floating water bridge’). Recently possible mechanisms for proton transfer through the bridge were suggested. In this work we visualize and describe the production of protons in the anolyte and their neutralization in the catholyte. Apart from that, protons are reduced to hydrogen due to electrolysis. Microbubbles are detached instantly, due to the electrohydrodynamic flow at the electrode surface. No larger, visible bubbles are formed and the system degasses through the bridge due to its higher local temperature. A detailed analysis of trace elements originating from beaker material, anode or the atmosphere is presented, showing that their influence on the overall conduction compared to the contribution of protons is negligible. Finally, an electrochemical rationale of high voltage electrolysis of low ionic strength solutions is presented. (paper)

  8. Muonium kinetics in sub- and supercritical water

    Energy Technology Data Exchange (ETDEWEB)

    Ghandi, K.; Addison-Jones, B.; Brodovitch, J.C.; Kecman, S.; McKenzie, I.; Percival, P.W

    2003-02-01

    Muonium is long-lived in pure water and has been studied over a very wide range of temperatures and pressures, from 5 deg. C to over 400 deg. C and from 1 to 400 bar. We have determined rate constants for representative reactions of muonium in aqueous solution; equivalent data on H atom kinetics is sparse and stops well short of the maximum temperature and pressure attained in our experiments. The results show remarkable deviations from the predictions of standard reaction theories. In particular, rate constants pass through a maximum with temperature well below the critical point. This seems to be a general phenomenon, since we have observed it for spin-exchange and chemical reactions that are diffusion limited at low temperatures, as well as for activated reactions. We believe that a key factor in the drop of rate constants at high temperature is the cage effect, in particular the number of collisions between a pair of reactants over the duration of their encounter. Whatever the reason, the implications are profound for both the efficiency of supercritical water oxidation reactors and for the modelling of radiation chemistry in pressurized water nuclear reactors.

  9. Muonium kinetics in sub- and supercritical water

    International Nuclear Information System (INIS)

    Ghandi, K.; Addison-Jones, B.; Brodovitch, J.C.; Kecman, S.; McKenzie, I.; Percival, P.W.

    2003-01-01

    Muonium is long-lived in pure water and has been studied over a very wide range of temperatures and pressures, from 5 deg. C to over 400 deg. C and from 1 to 400 bar. We have determined rate constants for representative reactions of muonium in aqueous solution; equivalent data on H atom kinetics is sparse and stops well short of the maximum temperature and pressure attained in our experiments. The results show remarkable deviations from the predictions of standard reaction theories. In particular, rate constants pass through a maximum with temperature well below the critical point. This seems to be a general phenomenon, since we have observed it for spin-exchange and chemical reactions that are diffusion limited at low temperatures, as well as for activated reactions. We believe that a key factor in the drop of rate constants at high temperature is the cage effect, in particular the number of collisions between a pair of reactants over the duration of their encounter. Whatever the reason, the implications are profound for both the efficiency of supercritical water oxidation reactors and for the modelling of radiation chemistry in pressurized water nuclear reactors

  10. The State of Water in Proton Conducting Membranes

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-08-27

    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.

  11. Proton non-Rutherford backscattering study of oxidation kinetics in Cu and Fe sulphides

    International Nuclear Information System (INIS)

    Chiari, M.; Giuntini, L.; Pratesi, G.; Santo, A.P.

    1998-01-01

    Non-Rutherford backscattering spectrometry (NBS) with 2.4 MeV protons was performed for depth profiling of oxygen in three species of copper and iron sulphides - pyrite, chalcopyrite and bornite - on both altered and fresh surfaces. The tarnished surfaces were obtained by bathing samples in H 2 O 2 (35% vol.) for 100 and 1000 s. The spectra collected were compared to simulations to extract quantitative data on oxygen depth distributions for the different bathing times. The measurements have shown that the kinetics of oxidation has completely different patterns in the three investigated minerals. (orig.)

  12. Kinetics and mechanism of the dissociation of chlorophyll and its metalloanalogues in proton-donating media

    International Nuclear Information System (INIS)

    Berezin, B.D.; Drobysheva, A.N.; Karmanova, L.P.

    1976-01-01

    The kinetics of the dissociation of chlorophyll a and its metalloanalogues (Zn 2+ and Cd 2+ complexes of chlorophyllic acid) have been investigated in t-butyl alcohol-trichloracetic acid mixtures. The dissociation reaction is kinetically firts-order with respect to the complex. The rate constants and the activation energies and entropies for the dissociation reaction have been calculated. In order to determine the order of the reaction with respect to the protogenic species, a study was made of the ionisation of m-nitroaniline in t-butyl alcohol at 25 0 C in the trichloroacetic acid concentration range from 0.15 to 4.75 M. The dissociation reaction of chlorophyll and its zinc-containing metalloanalogue has been shown to be of second order with respect to the solvated proton. The cadmium complex dissociates by a second-order reaction with respect to trichloroacetic acid

  13. Parity Nonconservation in Proton-Proton and Proton-Water Scattering at 1.5 GeV/c

    Science.gov (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.

    1984-07-01

    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}.

  14. Changes in the Zero-Point Energy of the Protons as the Source of the Binding Energy of Water to A-Phase DNA

    International Nuclear Information System (INIS)

    Reiter, G. F.; Senesi, R.; Mayers, J.

    2010-01-01

    The measured changes in the zero-point kinetic energy of the protons are entirely responsible for the binding energy of water molecules to A phase DNA at the concentration of 6 water molecules/base pair. The changes in kinetic energy can be expected to be a significant contribution to the energy balance in intracellular biological processes and the properties of nano-confined water. The shape of the momentum distribution in the dehydrated A phase is consistent with coherent delocalization of some of the protons in a double well potential, with a separation of the wells of 0.2 Angst .

  15. Changes in the zero-point energy of the protons as the source of the binding energy of water to A-phase DNA.

    Science.gov (United States)

    Reiter, G F; Senesi, R; Mayers, J

    2010-10-01

    The measured changes in the zero-point kinetic energy of the protons are entirely responsible for the binding energy of water molecules to A phase DNA at the concentration of 6  water molecules/base pair. The changes in kinetic energy can be expected to be a significant contribution to the energy balance in intracellular biological processes and the properties of nano-confined water. The shape of the momentum distribution in the dehydrated A phase is consistent with coherent delocalization of some of the protons in a double well potential, with a separation of the wells of 0.2 Å.

  16. Correlated proton-electron hole dynamics in protonated water clusters upon extreme ultraviolet photoionization

    Directory of Open Access Journals (Sweden)

    Zheng Li

    2016-07-01

    Full Text Available The ultrafast nuclear and electronic dynamics of protonated water clusters H+(H2On after extreme ultraviolet photoionization is investigated. In particular, we focus on cluster cations with n = 3, 6, and 21. Upon ionization, two positive charges are present in the cluster related to the excess proton and the missing electron, respectively. A correlation is found between the cluster's geometrical conformation and initial electronic energy with the size of the final fragments produced. For situations in which the electron hole and proton are initially spatially close, the two entities become correlated and separate in a time-scale of 20 to 40 fs driven by strong non-adiabatic effects.

  17. Correlated proton-electron hole dynamics in protonated water clusters upon extreme ultraviolet photoionization

    Science.gov (United States)

    Li, Zheng; Vendrell, Oriol

    2016-01-01

    The ultrafast nuclear and electronic dynamics of protonated water clusters H+(H2O)n after extreme ultraviolet photoionization is investigated. In particular, we focus on cluster cations with n = 3, 6, and 21. Upon ionization, two positive charges are present in the cluster related to the excess proton and the missing electron, respectively. A correlation is found between the cluster's geometrical conformation and initial electronic energy with the size of the final fragments produced. For situations in which the electron hole and proton are initially spatially close, the two entities become correlated and separate in a time-scale of 20 to 40 fs driven by strong non-adiabatic effects. PMID:26798842

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

    NARCIS (Netherlands)

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

    2010-01-01

    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

  19. What's new in the proton transfer reaction from pyranine to water? A femtosecond study of the proton transfer dynamics

    International Nuclear Information System (INIS)

    Prayer, C.; Gustavsson, T.; Tran-Thi, T.-H.

    1996-01-01

    The proton transfer from excited pyranine to water is studied by the femtosecond fluorescence upconversion technique. It is shown for the first time that the proton transfer reaction in water proceeds by three successive steps: the solvent cage relaxation, the specific solute-solvent hydrogen-bond formation and finally the ion pair dissociation/diffusion

  20. 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

    2004-01-01

    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...... of two closest water molecules to and from the reaction complex as crucial steps. The water molecules induce a "gated" shift of the proton from the donor to the acceptor in the double-well potential with simultaneous breaking/formation of hydrogen bonds between these molecules and the proton donor...... and acceptor. The short-range and long-range proton transfer as "structural diffusion" of Zundel complexes is also considered. The theoretical formalism is illustrated with the use of Morse, exponential, and harmonic molecular potentials. This approach is extended to proton transfer in strongly hydrogen...

  1. Proton Resonance Lines of Water in Heulandite, Mordenite and Clinoptilolite

    International Nuclear Information System (INIS)

    Cruz Inclan, C.; Diaz Quintanilla, D.; Diaz Ruano, A.

    1986-01-01

    It is reported for the first time the proton magnetic resonance spectra of the clinoptilolite and mordenite between 220 K and 440 K. In mordenite it was observed that all water molecules have so an intensive diffusive movement, that they are completely delocalized. In clinoptilolite below 390 K, only a part of the water molecules are completely delocalized. Over 390 K all water molecules become delocalized. This particular behavior of the water molecules in clinoptilolite and mordenite is confronted with those structural models proposed by D.W. Breck. The concept of non-localized quantum state is introduced in order to explain the difference observed with the structural models. (author)

  2. Environment-sensitive quinolone demonstrating long-lived fluorescence and unusually slow excited-state intramolecular proton transfer kinetics

    Czech Academy of Sciences Publication Activity Database

    Zamotaiev, O. M.; Shvadchak, Volodymyr; Sych, T. P.; Melnychuk, N. A.; Yushchenko, Dmytro A.; Mely, Y.; Pivovarenko, V. G.

    2016-01-01

    Roč. 4, č. 3 (2016), č. článku 034004. ISSN 2050-6120 Institutional support: RVO:61388963 Keywords : quinolone * fluorescent probes * local polarity * hydration * excited-state intramolecular proton transfer * kinetics Subject RIV: CC - Organic Chemistry Impact factor: 2.656, year: 2016

  3. Superconductivity and fast proton transport in nanoconfined water

    Science.gov (United States)

    Johnson, K. H.

    2018-04-01

    A real-space molecular-orbital density-wave 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 K (-43 °C).

  4. Proton exchange in systems: Glucose-water and uric acid-water

    International Nuclear Information System (INIS)

    Maarof, S.

    2007-01-01

    It is clear that formation of glucose-water and uric acid-water solutions is related in principle to interaction accepter - donor between hydrogen atom in water and oxygen atom in glucose or uric acid. The proton exchange in hydrogen bond system is an integral process and it goes by tunnel mechanism (transfer of proton within the hydrogen bridge in these structures). Proton exchange process goes very quickly at low concentrations for glucose and uric acid solutions, because these compounds are able to form more than one hydrogen bond, which helps the proton transfer within obtained structure. However, at its high concentrations, the process becomes very slow due to higher viscosity of its solutions, which result in break down of the structures, and more hydrogen bonds. (author)

  5. Proton Transfers at the Air-Water Interface

    Science.gov (United States)

    Mishra, Himanshu

    Proton transfer reactions at the interface of water with hydrophobic media, such as air or lipids, are ubiquitous on our planet. These reactions orchestrate a host of vital phenomena in the environment including, for example, acidification of clouds, enzymatic catalysis, chemistries of aerosol and atmospheric gases, and bioenergetic transduction. Despite their importance, however, quantitative details underlying these interactions have remained unclear. Deeper insight into these interfacial reactions is also required in addressing challenges in green chemistry, improved water quality, self-assembly of materials, the next generation of micro-nanofluidics, adhesives, coatings, catalysts, and electrodes. This thesis describes experimental and theoretical investigation of proton transfer reactions at the air-water interface as a function of hydration gradients, electrochemical potential, and electrostatics. Since emerging insights hold at the lipid-water interface as well, this work is also expected to aid understanding of complex biological phenomena associated with proton migration across membranes. Based on our current understanding, it is known that the physicochemical properties of the gas-phase water are drastically different from those of bulk water. For example, the gas-phase hydronium ion, H3O +(g), can protonate most (non-alkane) organic species, whereas H 3O+(aq) can neutralize only relatively strong bases. Thus, to be able to understand and engineer water-hydrophobe interfaces, it is imperative to investigate this fluctuating region of molecular thickness wherein the 'function' of chemical species transitions from one phase to another via steep gradients in hydration, dielectric constant, and density. Aqueous interfaces are difficult to approach by current experimental techniques because designing experiments to specifically sample interfacial layers (applied quantum mechanics and molecular dynamics to simulate our experiments toward gaining insight at the

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

    KAUST Repository

    Hisatomi, Takashi

    2014-10-16

    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.

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

    Directory of Open Access Journals (Sweden)

    Maurizio Cocucci

    2011-02-01

    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.

  8. Water equivalence of some plastic-water phantom materials for clinical proton beam dosimetry

    International Nuclear Information System (INIS)

    Al-Sulaiti, L.; Shipley, D.; Thomas, R.; Owen, P.; Kacperek, A.; Regan, P.H.; Palmans, H.

    2012-01-01

    Plastic-water phantom materials are not exactly water equivalent since they have a different elemental composition and different interaction cross sections for protons than water. Several studies of the water equivalence of plastic-water phantom materials have been reported for photon and electron beams, but none for clinical proton beams. In proton beams, the difference between non-elastic nuclear interactions in plastic-water phantom materials compared to those in water should be considered. In this work, the water equivalence of Plastic Water ® (PW) 1 , Plastic Water ® Diagnostic Therapy (PWDT) 1 and solid water (WT1) 2 phantoms was studied for clinical proton energies of 60 MeV and 200 MeV. This was done by evaluating the fluence correction factor at equivalent depths; first with respect to water and then with respect to graphite by experiment and Monte Carlo (MC) simulations using FLUKA. MC simulations showed that the fluence correction with respect to water was less than 0.5% up to the entire penetration depth of the protons at 60 MeV and less than 1% at 200 MeV up to 20 cm depth for PWDT, PW and WT1. With respect to graphite the fluence correction was about 0.5% for 60 MeV and about 4% for 200 MeV. The experimental results for modulated and un-modulated 60 MeV proton beams showed good agreement with the MC simulated fluence correction factors with respect to graphite deviating less than 1% from unity for the three plastic-water phantoms. - Highlights: ► We study plastic-water in clinical proton beams by experiment and Monte Carlo. ► We obtain fluence correction factors for water and graphite. ► The correction factor for water was close to 1 at 60 MeV and <0.990 at 200 MeV. ► The correction factor for graphite was ∼0.5% at 60 MeV and up to 4% at 200 MeV.

  9. Water-Free Proton-Conducting Membranes for Fuel Cells

    Science.gov (United States)

    Narayanan, Sekharipuram; Yen, Shiao-Pin

    2007-01-01

    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

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

    Directory of Open Access Journals (Sweden)

    Bing-Joe Hwang

    2012-03-01

    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.

  11. Automated processing for proton spectroscopic imaging using water reference deconvolution.

    Science.gov (United States)

    Maudsley, A A; Wu, Z; Meyerhoff, D J; Weiner, M W

    1994-06-01

    Automated formation of MR spectroscopic images (MRSI) is necessary before routine application of these methods is possible for in vivo studies; however, this task is complicated by the presence of spatially dependent instrumental distortions and the complex nature of the MR spectrum. A data processing method is presented for completely automated formation of in vivo proton spectroscopic images, and applied for analysis of human brain metabolites. This procedure uses the water reference deconvolution method (G. A. Morris, J. Magn. Reson. 80, 547(1988)) to correct for line shape distortions caused by instrumental and sample characteristics, followed by parametric spectral analysis. Results for automated image formation were found to compare favorably with operator dependent spectral integration methods. While the water reference deconvolution processing was found to provide good correction of spatially dependent resonance frequency shifts, it was found to be susceptible to errors for correction of line shape distortions. These occur due to differences between the water reference and the metabolite distributions.

  12. 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)

    2016-02-07

    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.

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

    International Nuclear Information System (INIS)

    Finkelstein, Y.; Moreh, R.; Shang, S. L.; Wang, Y.; Liu, Z. K.; Shchur, Ya.

    2016-01-01

    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 2 PO 4 , X = K, Cs, Rb, Tl), the DKDP (XD 2 PO 4 , X = K, Cs, Rb) type, and the X 3 H(SO 4 ) 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 3 H(SO 4 ) 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 OO , being a measure of the HB strength

  14. Kinetics of pyrophosphate-driven proton uptake by acidocalcisomes of Leptomonas wallacei

    International Nuclear Information System (INIS)

    Moraes Moreira, Bernardo Luiz; Soares Medeiros, Lia Carolina A.; Miranda, Kildare; Souza, Wanderley de; Hentschel, Joachim; Plattner, Helmut; Barrabin, Hector

    2005-01-01

    In this work, we show the kinetics of pyrophosphate-driven H + uptake by acidocalcisomes in digitonin-permeabilized promastigotes of Leptomonas wallacei. The vacuolar proton pyrophosphatase activity was optimal in the pH range of 7.5-8.0, was inhibited by imidiodiphosphate, and was completely dependent on K + and PPi. H + was released with the addition of Ca 2+ , suggesting the presence of a Ca 2+ /H + antiport. In addition, X-ray elemental mapping associated with energy-filtering transmission electron microscopy showed that most of the Ca, Na, Mg, P, K, Fe, and Zn were located in acidocalcisomes. L. wallacei immunolabeled with antibodies against Trypanosoma cruzi pyrophosphatase show intense fluorescence in cytoplasmatic organelles of size and distribution similar to the acidocalcisomes. Altogether, the results show that L. wallacei acidocalcisomes possess a H + -pyrophosphatase with characteristics of type I V-H + -PPase. However, we did not find any evidence, either for the presence of H + -ATPases or for Na + /H + exchangers in these acidocalcisomes

  15. NDMA formation kinetics from three pharmaceuticals in four water matrices.

    Science.gov (United States)

    Shen, Ruqiao; Andrews, Susan A

    2011-11-01

    N, N-nitrosodimethylamine (NDMA) is an emerging disinfection by-product (DBP) that has been widely detected in many drinking water systems and commonly associated with the chloramine disinfection process. Some amine-based pharmaceuticals have been demonstrated to form NDMA during chloramination, but studies regarding the reaction kinetics are largely lacking. This study investigates the NDMA formation kinetics from ranitidine, chlorphenamine, and doxylamine under practical chloramine disinfection conditions. The formation profile was monitored in both lab-grade water and real water matrices, and a statistical model is proposed to describe and predict the NDMA formation from selected pharmaceuticals in various water matrices. The results indicate the significant impact of water matrix components and reaction time on the NDMA formation from selected pharmaceuticals, and provide fresh insights on the estimation of ultimate NDMA formation potential from pharmaceutical precursors. Copyright © 2011 Elsevier Ltd. All rights reserved.

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

    African Journals Online (AJOL)

    The water proton resonance initially shifts to higher frequencies (low fields) as the cosolvent is added to water, and the shift to higher frequency is strongly temperature dependent, the effect being greatly enhanced at lower temperatures. As the proportion of cosolvent increases the hydroxyl proton signals in the water + ...

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

    Indian Academy of Sciences (India)

    Unknown

    therefore implicates bulk solvent-controlled protein dynamics in the protonation process. ... recently to protein–protein interactions in the bacterial response regulator SpoOF. NMR ..... molecular mechanism for redox-driven proton transfer to a buried iron–sulphur cluster ... Dynamic simulations of proton transfer from bulk.

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

    Energy Technology Data Exchange (ETDEWEB)

    Yamamoto, Seiichi, E-mail: s-yama@met.nagoya-u.ac.jp; 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)

    2015-11-15

    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.

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

    International Nuclear Information System (INIS)

    Yamamoto, Seiichi; Okumura, Satoshi; Komori, Masataka; Toshito, Toshiyuki

    2015-01-01

    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

  20. Interfacial Water-Transport Effects in Proton-Exchange Membranes

    Energy Technology Data Exchange (ETDEWEB)

    Kienitz, Brian; Yamada, Haruhiko; Nonoyama, Nobuaki; Weber, Adam

    2009-11-19

    It is well known that the proton-exchange membrane is perhaps the most critical component of a polymer-electrolyte fuel cell. Typical membranes, such as Nafion(R), require hydration to conduct efficiently and are instrumental in cell water management. Recently, evidence has been shown that these membranes might have different interfacial morphology and transport properties than in the bulk. In this paper, experimental data combined with theoretical simulations will be presented that explore the existence and impact of interfacial resistance on water transport for Nafion(R) 21x membranes. A mass-transfer coefficient for the interfacial resistance is calculated from experimental data using different permeation cells. This coefficient is shown to depend exponentially on relative humidity or water activity. The interfacial resistance does not seem to exist for liquid/membrane or membrane/membrane interfaces. The effect of the interfacial resistance is to flatten the water-content profiles within the membrane during operation. Under typical operating conditions, the resistance is on par with the water-transport resistance of the bulk membrane. Thus, the interfacial resistance can be dominant especially in thin, dry membranes and can affect overall fuel-cell performance.

  1. A multi water bag model of drift kinetic electron plasma

    International Nuclear Information System (INIS)

    Morel, P.; Dreydemy Ghiro, F.; Berionni, V.; Gurcan, O.D.; Coulette, D.; Besse, N.

    2014-01-01

    A Multi Water Bag model is proposed for describing drift kinetic plasmas in a magnetized cylindrical geometry, relevant for various experimental devices, solar wind modeling... The Multi Water Bag (MWB) model is adapted to the description of a plasma with kinetic electrons as well as an arbitrary number of kinetic ions. This allows to describe the kinetic dynamics of the electrons, making possible the study of electron temperature gradient (ETG) modes, in addition to the effects of non adiabatic electrons on the ion temperature gradient (ITG) modes, that are of prime importance in the magnetized plasmas micro-turbulence [X. Garbet, Y. Idomura, L. Villard, T.H. Watanabe, Nucl. Fusion 50, 043002 (2010); J.A. Krommes, Ann. Rev. Fluid Mech. 44, 175 (2012)]. The MWB model is shown to link kinetic and fluid descriptions, depending on the number of bags considered. Linear stability of the ETG modes is presented and compared to the existing results regarding cylindrical ITG modes [P. Morel, E. Gravier, N. Besse, R. Klein, A. Ghizzo, P. Bertrand, W. Garbet, Ph. Ghendrih, V. Grandgirard, Y. Sarazin, Phys. Plasmas 14, 112109 (2007)]. (authors)

  2. Protein folding kinetics by combined use of rapid mixing techniques and NMR observation of individual amide protons

    International Nuclear Information System (INIS)

    Roder, H.; Wuethrich, K.

    1986-01-01

    A method to be used for experimental studies of protein folding introduced by Schmid and Baldwin, which is based on the competition between amide hydrogen exchange and protein refolding, was extended by using rapid mixing techniques and 1 H NMR to provide site-resolved kinetic information on the early phases of protein structure acquisition. In this method, a protonated solution of the unfolded protein is rapidly mixed with a deuterated buffer solution at conditions assuring protein refolding in the mixture. This simultaneously initiates the exchange of unprotected amide protons with solvent deuterium and the refolding of protein segments which can protect amide groups from further exchange. After variable reaction times the amide proton exchange is quenched while folding to the native form continues to completion. By using 1 H NMR, the extent of exchange at individual amide sites is then measured in the refolded protein. Competition experiments at variable reaction times or variable pH indicate the time at which each amide group is protected in the refolding process. This technique was applied to the basic pancreatic trypsin inhibitor, for which sequence-specific assignments of the amide proton NMR lines had previously been obtained. For eight individual amide protons located in the beta-sheet and the C-terminal alpha-helix of this protein, apparent refolding rates in the range from 15 s-1 to 60 s-1 were observed. These rates are on the time scale of the fast folding phase observed with optical probes

  3. Track etch parameters and annealing kinetics assessment of protons of low energy in CR-39 detector

    International Nuclear Information System (INIS)

    Jain, R.K.; Kumar, Ashok; Singh, B.K.

    2012-01-01

    Highlights: ► We calibrate CR-39 detector with very low energy protons. ► We establish linear relationship between track diameter and time/energy up to 200 keV. ► We determine activation energy of annealing using different models. ► We justify concept of single annealing activation energy in CR-39. - Abstract: In this paper threshold of the registration sensitivity of very low energy proton in CR-39 is investigated. Irradiation of CR-39 (poly-allyl-diglycol carbonate) was carried out with very low energy mono energetic protons of 20–60 keV from a mini proton accelerator. Nearly 10 4 /cm 2 fluence of protons was used. The variation of track diameter with etching time as well as proton energy response curve was carefully calibrated. The bulk and track etch rates were measured by using proton track diameters. Bulk etch rate was also measured by the thickness of removed surface layer. The thermal annealing of proton track at temperatures ranging from 100 to 200 °C in CR-39 was studied by several models. Activation energy of annealed CR-39 detectors was calculated by slope of track etch rate and temperature plot. The data of proton tracks of 200, 250 and 300 keV from 400 kV Van-de-Graaff accelerator was also used and compared with the track diameters of different energies of proton.

  4. Umbrella sampling of proton transfer in a creatine-water system

    Science.gov (United States)

    Ivchenko, Olga; Bachert, Peter; Imhof, Petra

    2014-04-01

    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. 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.

  6. Reaction kinetics of cellulose hydrolysis in subcritical and supercritical water

    Science.gov (United States)

    Olanrewaju, Kazeem Bode

    The uncertainties in the continuous supply of fossil fuels from the crisis-ridden oil-rich region of the world is fast shifting focus on the need to utilize cellulosic biomass and develop more efficient technologies for its conversion to fuels and chemicals. One such technology is the rapid degradation of cellulose in supercritical water without the need for an enzyme or inorganic catalyst such as acid. This project focused on the study of reaction kinetics of cellulose hydrolysis in subcritical and supercritical water. Cellulose reactions at hydrothermal conditions can proceed via the homogeneous route involving dissolution and hydrolysis or the heterogeneous path of surface hydrolysis. The work is divided into three main parts. First, the detailed kinetic analysis of cellulose reactions in micro- and tubular reactors was conducted. Reaction kinetics models were applied, and kinetics parameters at both subcritical and supercritical conditions were evaluated. The second major task was the evaluation of yields of water soluble hydrolysates obtained from the hydrolysis of cellulose and starch in hydrothermal reactors. Lastly, changes in molecular weight distribution due to hydrothermolytic degradation of cellulose were investigated. These changes were also simulated based on different modes of scission, and the pattern generated from simulation was compared with the distribution pattern from experiments. For a better understanding of the reaction kinetics of cellulose in subcritical and supercritical water, a series of reactions was conducted in the microreactor. Hydrolysis of cellulose was performed at subcritical temperatures ranging from 270 to 340 °C (tau = 0.40--0.88 s). For the dissolution of cellulose, the reaction was conducted at supercritical temperatures ranging from 375 to 395 °C (tau = 0.27--0.44 s). The operating pressure for the reactions at both subcritical and supercritical conditions was 5000 psig. The results show that the rate-limiting step in

  7. Kinetic Theory and Simulation of Single-Channel Water Transport

    Science.gov (United States)

    Tajkhorshid, Emad; Zhu, Fangqiang; Schulten, Klaus

    Water translocation between various compartments of a system is a fundamental process in biology of all living cells and in a wide variety of technological problems. The process is of interest in different fields of physiology, physical chemistry, and physics, and many scientists have tried to describe the process through physical models. Owing to advances in computer simulation of molecular processes at an atomic level, water transport has been studied in a variety of molecular systems ranging from biological water channels to artificial nanotubes. While simulations have successfully described various kinetic aspects of water transport, offering a simple, unified model to describe trans-channel translocation of water turned out to be a nontrivial task.

  8. Kinetics and mechanism of methane oxidation in supercritical water

    International Nuclear Information System (INIS)

    Rofer, C.K.; Streit, G.E.

    1988-10-01

    This project, is a Hazardous Waste Remedial Actions Program (HAZWRAP) Research and Development task being carried out by the Los Alamos National Laboratory. Its objective is to achieve an understanding of the technology for use in scaling up and applying oxidation in supercritical water as a viable process for treating a variety of Department of Energy Defense Programs (DOE-DP) waste streams. This report presents experimental results for the kinetics of the oxidation of methane and methanol in supercritical water and computer modeling results for the oxidation of carbonmonoxide and methane in supercritical water. The experimental and modeling results obtained to date on these one-carbon model compounds indicate that the mechanism of oxidation in supercritical water can be represented by free-radical reactions with appropriate modifications for high pressure and the high water concentration. If these current trends are sustained, a large body of existing literature data on the kinetics of elementary reactions can be utilized to predict the behavior of other compounds and their mixtures. 7 refs., 4 figs., 3 tabs

  9. Proton transport facilitating water-oxidation: the role of second sphere ligands surrounding the catalytic metal cluster.

    Science.gov (United States)

    Bao, Han; Dilbeck, Preston L; Burnap, Robert L

    2013-10-01

    The ability of PSII to extract electrons from water, with molecular oxygen as a by-product, is a remarkable biochemical and evolutionary innovation. From an evolutionary perspective, the invention of PSII approximately 2.7 Ga led to the accelerated accumulation of biomass in the biosphere and the accumulation of oxygen in the atmosphere, a combination that allowed for the evolution of a much more complex and extensive biosphere than would otherwise have been possible. From the biochemical and enzymatic perspective, PSII is remarkable because of the thermodynamic and kinetic obstacles that needed to have been overcome to oxidize water as the ultimate photosynthetic electron donor. This article focuses on how proton release is an integral part of how these kinetic and thermodynamic obstacles have been overcome: the sequential removal of protons from the active site of H2O-oxidation facilitates the multistep oxidation of the substrate water at the Mn4CaOx, the catalytic heart of the H2O-oxidation reaction. As noted previously, the facilitated deprotonation of the Mn4CaOx cluster exerts a redox-leveling function preventing the accumulation of excess positive charge on the cluster, which might otherwise hinder the already energetically difficult oxidation of water. Using recent results, including the characteristics of site-directed mutants, the role of the second sphere of amino acid ligands and the associated network of water molecules surrounding the Mn4CaOx is discussed in relation to proton transport in other systems. In addition to the redox-leveling function, a trapping function is assigned to the proton release step occurring immediately prior to the dioxygen chemistry. This trapping appears to involve a yet-to-be clarified gating mechanism that facilitates to coordinated release of a proton from the neighborhood of the active site thereby insuring that the backward charge-recombination reaction does not out-compete the forward reaction of dioxygen chemistry

  10. 13N species formed by proton irradiation of water

    International Nuclear Information System (INIS)

    Tilbury, R.S.; Dahl, J.R.

    1979-01-01

    We have shown that the irradiation of aerated water with 14.5-MeV protons produces as principal radioactive products nitrogen-13-labeled nitrate, nitrite, and ammonium ions. The yield of 13 NH 4 + varied from approximately 40% at low integrated dose (0.01 μAh) to 0.4% at high integrated dose (25 μAh), 13 NO 3 - varied from 50% at low dose to 85% at high dose. 13 N 2 - varied from 10% at low dose to 5% at high dose and 40% at intermediate doses. The results varied with recent use of target chamber. Induced radioactivity in the window foil was shown to have an effect on product composition. The effect of dissolved oxygen and certain additives (ethanol, ascorbic acid, formic acid, and ammonia) were investigated. In the absence of dissolved oxygen, or in the presence of ethanol, formic acid or ascorbic acid, almost pure 13 NH 3 could be produced at doses up to 2μAh. The data are explained by postulating the initial production of 13 NH 3 by successive abstraction of H atoms by the 13 NH 3 to HNO 2 and HNO 3

  11. Water versus DNA A new deal for proton transport modeling in biological matter

    International Nuclear Information System (INIS)

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

    2015-01-01

    Water vapor is a common surrogate of DNA for modeling the proton-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, self-consistent quantum mechanical modeling 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. (paper)

  12. Study of water vapour adsorption kinetics on aluminium oxide materials

    Science.gov (United States)

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

    2017-11-01

    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.

  13. Unstirred Water Layers and the Kinetics of Organic Cation Transport

    Science.gov (United States)

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

    2015-01-01

    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

  14. The water equivalence of solid materials used for dosimetry with small proton beams

    International Nuclear Information System (INIS)

    Schneider, Uwe; Pemler, Peter; Besserer, Juergen; Dellert, Matthias; Moosburger, Martin; Boer, Jorrit de; Pedroni, Eros; Boehringer, Terence

    2002-01-01

    Various solid materials are used instead of water for absolute dosimetry with small proton beams. This may result in a dose measurement different to that in water, even when the range of protons in the phantom material is considered correctly. This dose difference is caused by the diverse cross sections for inelastic nuclear scattering in water and in the phantom materials respectively. To estimate the magnitude of this effect, flux and dose measurements with a 177 MeV proton pencil beam having a width of 0.6 cm (FWHM) were performed. The proton flux and the deposited dose in the beam path were determined behind water, lucite, polyethylene, teflon, and aluminum of diverse thicknesses. The number of out-scattered protons due to inelastic nuclear scattering was determined for water and the different materials. The ratios of the number of scattered protons in the materials relative to that in water were found to be 1.20 for lucite, 1.16 for polyethylene, 1.22 for teflon, and 1.03 for aluminum. The difference between the deposited dose in water and in the phantom materials taken in the center of the proton pencil beam, was estimated from the flux measurements, always taking the different ranges of protons in the materials into account. The estimated dose difference relative to water in 15 cm water equivalent thickness was -2.3% for lucite, -1.7% for polyethylene, -2.5% for teflon, and -0.4% for aluminum. The dose deviation was verified by a measurement using an ionization chamber. It should be noted that the dose error is larger when the effective point of measurement in the material is deeper or when the energy is higher

  15. Kinetic isotope effects and tunnelling in the proton-transfer reaction between 4-nitrophenylnitromethane and tetramethylguanidine in various aprotic solvents

    International Nuclear Information System (INIS)

    Caldin, E.F.; Mateo, S.

    1975-01-01

    Rates and equilibrium constants have been determined for the proton-transfer reaction of 4-nitrophenylnitromethane, NO 2 C 6 H 4 CH 2 NO 2 , and its αα-deuterated analogue NO 2 C 6 H 4 CD 2 NO 2 , with the strong base tetramethylguanidine [HN=C(NMe 2 ) 2 ), at temperatures between -60 0 C and +65 0 in a range of aprotic solvents. Spectrophotometry and the stopped-flow technique were used. The reaction is a simple proton-transfer process leading to an ion-pair. The kinetic isotope effects are correlated with the polarity of the solvents, as measured by the dielectric constant or by the empirical parameter Esub(T). In the less polar solvents they are exceptionally large. In toluene, for example, at 25 0 C the rate ratio ksup(H)/ksup(D) = 45 +- 2, the activation energy difference Esub(a)sup(D) - Esub(a)sup(H) =4.3 +- 0.3 kcal molsup(-1) (16 kJ molsup(-1), and the ratio of the pre-exponential factors logsub(10) (Asup(D)/Asup(H)) = 1.5 +- 0.2+ and even larger values of logsub(10)(Asup(D)/Asup(H)) are found for mesitylene (1.94 +- 0.06) and cyclohexane (2.4 +- 0.2). Positive deviations from linear Arrhenius plots are found for these solvents. Tunnelling is the only interpretation that cannot account for these results. For the more polar solvents (dielectric constant 7 to 37), the isotope effects are closer to the range predicted by semi-classical theory. The isotope effects in all solvents have been fitted to Bell's equation for a parabolic barrier, and the barrier dimensions calculated for each solvent. The suggested interpretation of the results is that the solvent-solute interactions affect the height of the barrier and that motions of solvent molecules are coupled with the motion of the proton in the more polar solvents but not in the less polar ones; reorganization of solvent molecules accompanies the proton-transfer in the more polar solvents, but only electron-polarization in the less polar. Tunnelling has large effects in the less polar solvents, where the

  16. Hydroxide diffuses slower than hydronium in water because its solvated structure inhibits correlated proton transfer

    Science.gov (United States)

    Chen, Mohan; Zheng, Lixin; Santra, Biswajit; Ko, Hsin-Yu; DiStasio, Robert A., Jr.; Klein, Michael L.; Car, Roberto; Wu, Xifan

    2018-03-01

    Proton transfer via hydronium and hydroxide ions in water is ubiquitous. It underlies acid-base chemistry, certain enzyme reactions, and even infection by the flu. Despite two centuries of investigation, the mechanism underlying why hydroxide diffuses slower than hydronium in water is still not well understood. Herein, we employ state-of-the-art density-functional-theory-based molecular dynamics—with corrections for non-local van der Waals interactions, and self-interaction in the electronic ground state—to model water and hydrated water ions. At this level of theory, we show that structural diffusion of hydronium preserves the previously recognized concerted behaviour. However, by contrast, proton transfer via hydroxide is less temporally correlated, due to a stabilized hypercoordination solvation structure that discourages proton transfer. Specifically, the latter exhibits non-planar geometry, which agrees with neutron-scattering results. Asymmetry in the temporal correlation of proton transfer leads to hydroxide diffusing slower than hydronium.

  17. Correlation between morphology, water uptake, and proton conductivity in radiation-grafted proton-exchange membranes

    DEFF Research Database (Denmark)

    Balog, Sandor; Gasser, Urs; Mortensen, Kell

    2010-01-01

    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...

  18. Kinetic enantioselectivity of a protonated bis(diamido)-bridged basket resorcin[4]arene towards alanine peptides.

    Science.gov (United States)

    Fraschetti, C; Montagna, M; Crestoni, M E; Calcaterra, A; Aiello, F; Santi, L; Filippi, A

    2017-02-01

    Efficient enantiodiscrimination of some alanine-containing di- and tri-peptides by using chiral protonated bis(diamido)-bridged basket resorcin[4]arenes depends on several factors, including the basicity of the amino acid residues at the C- and N-termini of the peptide.

  19. Mathematical modeling of water mass balance for proton exchange membrane fuel cell

    International Nuclear Information System (INIS)

    Wan Ramli Wan Daud; Kamaruzzaman Sopian; Jaafar Sahari; Nik Suhaimi Mat Hassan

    2006-01-01

    Gas and water management are key to achieving good performance from a proton exchange membrane fuel cell (PEMFC) stack. Water plays a critical role in PEMFC. The proton conductivity is increase with the water content. In order to achieve enough hydration, water is normally introduced into the cell externally by a variety of methods such as liquid injection, steam introduction, and humidification of reactants by passing them through humidifiers before entering the cell. In this paper, mathematical modeling of water mass balance for PEMFC at anode and cathode side are proposed by using external humidification and assume that steady state, constant pressure, constant temperature and gases distribution are uniform

  20. Thermodynamic stability and kinetic dissolution of perovskite in natural waters

    International Nuclear Information System (INIS)

    Nesbitt, H.W.; Bancroft, G.M.; Fyfe, W.S.; Karkhanis, S.; Melling, P.; Nishijima, A.

    1981-01-01

    Ringwood and coworkers have recently proposed using titanates and zirconates as hosts for nuclear waste in the Synroc B process. Three minerals are used as hosts: perovskite (CaTiO 3 ), Ba-hollandite (BaAl 2 Ti 6 O 16 ), and zirconolite (CaZrTi 2 O 7 ). The Synroc philosophy relies heavily on geological and geochemical observations in selecting stable host minerals. Although it has been recognized that the Synroc minerals are not thermodynamically compatible with siliceous rocks, the minerals are considered to be thermodynamically stable in the presence of water, and it has been reported that these minerals are kinetically stable under high-temperature (up to 900 0 C) hydrothermal conditions. Detailed thermodynamic calculations and leach tests have been performed which demonstrate: first, that perovskite is thermodynamically unstable in all known natural waters; and second, that pervoskite leaches at a significant rate even at 100 0 C. Hydrothermal leach tests have been made on natural and synthetic perovskite and perovskite analogues between 100 0 C and 300 0 C. Weight losses and solution concentrations were monitored. The results reported previously in the literature also show that perovskite is kinetically unstable in the presence of common silicates. Our results show that perovskite may be no more stable than siliceous glasses, such as rhyolite, which have been studied previously. Geologic evidence from common alkaline rocks also indicates that hollandite and zirconolite probably will not survive in common rock matrices

  1. A proton wire and water channel revealed in the crystal structure of isatin hydrolase

    DEFF Research Database (Denmark)

    Bjerregaard-Andersen, Kaare; Sommer, Theis; Jensen, Jan Kristian

    2014-01-01

    to a novel family of metalloenzymes that include the bacterial kynurenine formamidase. The product state, mimicked by bound thioisatinate, reveals a water molecule that bridges the thioisatinate to a proton wire in an adjacent water channel and thus allows the proton released by the reaction to escape only...... when the product is formed. The functional proton wire present in IH-b represents a unique catalytic feature common to all hydrolases is here trapped and visualized for the first time. The local molecular environment required to coordinate thioisatinate allows stronger and more confident identification...

  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)

    2010-09-30

    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. 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.

    2016-08-09

    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.

  4. Experimental test of a four-level kinetic model for excited-state intramolecular proton transfer dye lasers

    Energy Technology Data Exchange (ETDEWEB)

    Costela, A; Munnoz, J M; Douhal, A; Figuera, J M; Acuna, A U [Inst. de Quimica Fisica ' ' Rocasolano' ' , C.S.I.C., Madrid (Spain)

    1989-11-01

    The nanosecond pulses of a dye laser oscillator based on the excited-state intramolecular proton-transfer reaction (IPT) of salicylamide and 2'-hydroxylphenyl benzimidazole dyes have been studied as a function of several experimental parameters. To explain the operation of this laser a numerical four-level kinetic model was developed until the lasing properties of these dyes, in the presence of a variable oxygen concentration and pumped with a double pulse technique, could be reproduced. This was possible only by assuming that the efficiency of the laser is controlled by the absorption cross-section of a transient state with a lifetime in the nanosecond-picosecond range, which was tentatively identified as a ground state tautomeric species. (orig.).

  5. Acoustic time-of-flight for proton range verification in water

    Energy Technology Data Exchange (ETDEWEB)

    Jones, Kevin C.; Avery, Stephen, E-mail: Stephen.Avery@uphs.upenn.edu [Department of Radiation Oncology, University of Pennsylvania, Philadelphia, Pennsylvania 19104 (United States); Vander Stappen, François [Ion Beam Applications SA, Louvain-la-Neuve 1348 (Belgium); Sehgal, Chandra M. [Department of Radiology, University of Pennsylvania, Philadelphia, Pennsylvania 19104 (United States)

    2016-09-15

    Purpose: Measurement of the arrival times of thermoacoustic waves induced by pulsed proton dose depositions (protoacoustics) may provide a proton range verification method. The goal of this study is to characterize the required dose and protoacoustic proton range (distance) verification accuracy in a homogeneous water medium at a hospital-based clinical cyclotron. Methods: Gaussian-like proton pulses with 17 μs widths and instantaneous currents of 480 nA (5.6 × 10{sup 7} protons/pulse, 3.4 cGy/pulse at the Bragg peak) were generated by modulating the cyclotron proton source with a function generator. After energy degradation, the 190 MeV proton pulses irradiated a water phantom, and the generated protoacoustic emissions were measured by a hydrophone. The detector position and proton pulse characteristics were varied. The experimental results were compared to simulations. Different arrival time metrics derived from acoustic waveforms were compared, and the accuracy of protoacoustic time-of-flight distance calculations was assessed. Results: A 27 mPa noise level was observed in the treatment room during irradiation. At 5 cm from the proton beam, an average maximum pressure of 5.2 mPa/1 × 10{sup 7} protons (6.1 mGy at the Bragg peak) was measured after irradiation with a proton pulse with 10%–90% rise time of 11 μs. Simulation and experiment arrival times agreed well, and the observed 2.4 μs delay between simulation and experiment is attributed to the difference between the hydrophone’s acoustic and geometric centers. Based on protoacoustic arrival times, the beam axis position was measured to within (x, y) = (−2.0,  0.5) ± 1 mm. After deconvolution of the exciting proton pulse, the protoacoustic compression peak provided the most consistent measure of the distance to the Bragg peak, with an error distribution with mean = − 4.5 mm and standard deviation = 2.0 mm. Conclusions: Based on water tank measurements at a clinical hospital-based cyclotron

  6. Kinetics and Mechanisms of Calcite Reactions with Saline Waters

    Energy Technology Data Exchange (ETDEWEB)

    Gorman, Brian P [Colorado School of Mines, Golden, CO (United States)

    2015-09-02

    Project Description: The general objective of the proposed research is to determine the kinetics and mechanisms of calcite reactions with saline waters over a wide range of saline water composition, pCO2, and modest ranges in T and P. This will be accomplished by studying both reaction rates and solubility from changes in solution chemistry, and making nanoscale observations of calcite precipitate surface morphology and composition at the micro-to-nano-scale to provide an understanding of controlling reaction mechanisms and pathways. The specific objectives necessary to reach the general objective are: a) determination of how pCO2, Ca2+, ionic strength and “foreign” ions influence reaction rates; and b) investigate the influence of these parameters on apparent kinetic solubility from dissolution and precipitation reactions. This information will clearly be central to the construction of reliable reaction-transport models to predict reservoir and formation response to increased CO2 in saline waters. This program was initially collaborative with John Morse at Texas A&M, however his passing shortly after the beginning of this program resulted in abbreviated research time and effort. Summary of Results: Early studies using electron microscopy and spectroscopy indicated that carbonate precipitation from natural seawater (NSW) conditions onto aragonite substrates was mediated by a surface amorphous calcium carbonate layer. It was hypothesized that this ACC layer (observed after < 5days reaction time) was responsible for the abnormal reaction kinetics and also served as a metastable seed layer for growth of epitaxial aragonite. Further studies of the ACC formation mechanism indicated a strong dependence on the Mg concentration in solution. Subsequent studies at shorter times (10 hrs) on calcite substrates and in a wide range of supersaturation conditions did not indicate any ACC layer. Instead, an epitaxial layer by layer

  7. Hydrolysis kinetics of tulip tree xylan in hot compressed water.

    Science.gov (United States)

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

    2016-08-01

    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.

  8. Kinetics of the water formation in the propene epoxidation over gold-titania catalysts

    NARCIS (Netherlands)

    Nijhuis, T.A.; Weckhuysen, B.M.

    2007-01-01

    The kinetics of the hydrogen oxidation were determined for a number of different gold catalysts supported on titania, silica, and silicalite-1. A dual site Langmuir-Hinshelwood kinetic model was able to describe the reaction well. The kinetic parameters are independent of the support. Water was

  9. Electron transfer activation of a second water channel for proton transport in [FeFe]-hydrogenase

    Energy Technology Data Exchange (ETDEWEB)

    Sode, Olaseni; Voth, Gregory A., E-mail: gavoth@uchicago.edu [Department of Chemistry, James Franck Institute, Institute for Biophysical Dynamics, Computation Institute, The University of Chicago, Chicago, Illinois 60637, USA and Computing, Environment and Life Sciences, Argonne National Laboratory, Argonne, Illinois 60439 (United States)

    2014-12-14

    Hydrogenase enzymes are important because they can reversibly catalyze the production of molecular hydrogen. Proton transport mechanisms have been previously studied in residue pathways that lead to the active site of the enzyme via residues Cys299 and Ser319. The importance of this pathway and these residues has been previously exhibited through site-specific mutations, which were shown to interrupt the enzyme activity. It has been shown recently that a separate water channel (WC2) is coupled with electron transport to the active site of the [FeFe]-hydrogenase. The water-mediated proton transport mechanisms of the enzyme in different electronic states have been studied using the multistate empirical valence bond reactive molecular dynamics method, in order to understand any role WC2 may have in facilitating the residue pathway in bringing an additional proton to the enzyme active site. In a single electronic state A{sup 2−}, a water wire was formed through which protons can be transported with a low free energy barrier. The remaining electronic states were shown, however, to be highly unfavorable to proton transport in WC2. A double amino acid substitution is predicted to obstruct proton transport in electronic state A{sup 2-} by closing a cavity that could otherwise fill with water near the proximal Fe of the active site.

  10. Electron transfer activation of a second water channel for proton transport in [FeFe]-hydrogenase

    International Nuclear Information System (INIS)

    Sode, Olaseni; Voth, Gregory A.

    2014-01-01

    Hydrogenase enzymes are important because they can reversibly catalyze the production of molecular hydrogen. Proton transport mechanisms have been previously studied in residue pathways that lead to the active site of the enzyme via residues Cys299 and Ser319. The importance of this pathway and these residues has been previously exhibited through site-specific mutations, which were shown to interrupt the enzyme activity. It has been shown recently that a separate water channel (WC2) is coupled with electron transport to the active site of the [FeFe]-hydrogenase. The water-mediated proton transport mechanisms of the enzyme in different electronic states have been studied using the multistate empirical valence bond reactive molecular dynamics method, in order to understand any role WC2 may have in facilitating the residue pathway in bringing an additional proton to the enzyme active site. In a single electronic state A 2− , a water wire was formed through which protons can be transported with a low free energy barrier. The remaining electronic states were shown, however, to be highly unfavorable to proton transport in WC2. A double amino acid substitution is predicted to obstruct proton transport in electronic state A 2- by closing a cavity that could otherwise fill with water near the proximal Fe of the active site

  11. Kinetic theory of oxygen isotopic exchange between minerals and water

    Science.gov (United States)

    Criss, R.E.; Gregory, R.T.; Taylor, H.P.

    1987-01-01

    Kinetic and mass conservation equations are used to describe oxygen isotopic exchange between minerals and water in "closed" and open hydrothermal systems. In cases where n coexisting mineral phases having different reaction rates are present, the exchange process is described by a system of n + 1 simultaneous differential equations consisting of n pseudo first-order rate equations and a conservation of mass equation. The simultaneous solutions to these equations generate curved exchange trajectories on ??-?? plots. Families of such trajectories generated under conditions allowing for different fluid mole fractions, different fluid isotopic compositions, or different fluid flow rates are connected by positive-sloped isochronous lines. These isochrons reproduce the effects observed in hydrothermally exchanged mineral pairs including 1) steep positive slopes, 2) common reversals in the measured fractionation factors (??), and 3) measured fractionations that are highly variable over short distances where no thermal gradient can be geologically demonstrated. ?? 1987.

  12. Zirconium metal-water oxidation kinetics. I. Thermometry

    International Nuclear Information System (INIS)

    Cathcart, J.V.; McElroy, D.L.; Pawel, R.E.; Perkins, R.A.; Williams, R.K.; Yurek, G.J.

    1976-02-01

    A description is given of the thermometry techniques used in the Zirconium Metal--Water Oxidation Kinetics Program. Temperature measurements in the range 900 to 1500 0 C are made in three experimental systems: two oxidation apparatuses and the annealing furnace used in a corollary study of the diffusion of oxygen in β-Zircaloy. Carefully calibrated Pt vs Pt--10 percent Rh thermocouples are employed in all three apparatuses, while a Pt--6 percent Rh vs Pt-- 30 percent Rh thermocouple and an optical pyrometer are used in addition in the annealing furnace. Features of the experimental systems pertaining to thermocouple installation, temperature control, emf measurements, etc. are described, and potential temperature-measurement error sources are discussed in detail. The accuracy of the temperature measurements is analyzed

  13. Protonic charge defect structures in floating water bridges observed as Zundel and Eigen solvation arrangements

    Science.gov (United States)

    Teschke, Omar; de Castro, Jose Roberto; Valente Filho, Juracyr Ferraz; Soares, David Mendez

    2017-10-01

    Protonic arrangements were detected in water bridge structures using confocal Raman microscopy, and the spectra show two formed structures. The measured Raman spectra were modified using the voltage applied to the bridge structure, which changed the proportion of these two species. Initially, for a 6.3 kV applied voltage, there was a measurable increase in the bridge current above the Ohmic contribution and the observed Raman spectrum of this new injected specie corresponded to the computed spectrum for the Zundel protonic arrangement. As the voltage further increases a contribution from the Eigen proton solvation specie is added to the measured spectrum.

  14. 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)

    1997-09-01

    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.)

  15. Cooling-water chlorination: the kinetics of chlorine, bromine, and ammonia in sea water

    International Nuclear Information System (INIS)

    Johnson, J.D.; Inman, G.W. Jr.; Trofe, T.W.

    1982-11-01

    The major inorganic reaction pathways for the chlorination of saline waters were measured by a variety of techniques including: (1) amperometric titration, (2) amperometric membrane covered electrode, (3) uv spectrophotometry, (4) conventional kinetics methods for slow reactions, and (5) stopped-flow kinetics measurements with a microcomputer data acquisition system. The major reactions studied were: (1) the competitive reactions of ammonia and bromide ion with hypochlorous acid, (2) bromide oxidation by hypochlorous acid, (3) monochloramine formation in sea water, (4) monobromamine formation and subsequent disproportionation to form dibromamine, and (5) monochloramine oxidation of bromide to form bromochloramine. Reaction rates were determined in sodium chloride and sea water as a function of reactant concentration, pH, salinity, and ammonia concentration. Rate constants and corresponding rate laws and mechanisms were developed for each reaction

  16. Kinetics of Pressurized Water Reactors with Hot or Cold Moderators

    Energy Technology Data Exchange (ETDEWEB)

    Norinder, O

    1960-11-15

    The set of neutron kinetic equations developed in this report permits the use of long integration steps during stepwise integration. Thermal relations which describe the transfer of heat from fuel to coolant are derived. The influence upon the kinetic behavior of the reactor of a number of parameters is studied. A comparison of the kinetic properties of the hot and cold moderators is given.

  17. Proton-induced fission cross sections on "2"0"8Pb at high kinetic energies

    International Nuclear Information System (INIS)

    Rodriguez-Sanchez, J.L.; Benlliure, J.; Paradela, C.; Ayyad, Y.; Alvarez-Pol, H.; Cortina-Gil, D.; Pietras, B.; Ramos, D.; Vargas, J.; Taieb, J.; Chatillon, A.; Belier, G.; Boutoux, G.; Gorbinet, T.; Laurent, B.; Martin, J.F.; Pellereau, E.; Casarejos, E.; Rodriguez-Tajes, C.

    2014-01-01

    Total fission cross sections of "2"0"8Pb induced by protons have been determined at 370 A, 500 A, and 650 A MeV. The experiment was performed at GSI Darmstadt where the combined use of the inverse kinematics technique with an efficient detection setup allowed us to determine these cross sections with an uncertainty below 6%. This result was achieved by an accurate beam selection and registration of both fission fragments in coincidence which were also clearly distinguished from other reaction channels. These data solve existing discrepancies between previous measurements, providing new values for the Prokofiev systematics. The data also allow us to investigate the fission process at high excitation energies and small deformations. In particular, some fundamental questions about fission dynamics have been addressed, which are related to dissipative and transient time effects. (authors)

  18. Evaporation kinetics of sessile water droplets on micropillared superhydrophobic surfaces.

    Science.gov (United States)

    Xu, Wei; Leeladhar, Rajesh; Kang, Yong Tae; Choi, Chang-Hwan

    2013-05-21

    Evaporation modes and kinetics of sessile droplets of water on micropillared superhydrophobic surfaces are experimentally investigated. The results show that a constant contact radius (CCR) mode and a constant contact angle (CCA) mode are two dominating evaporation modes during droplet evaporation on the superhydrophobic surfaces. With the decrease in the solid fraction of the superhydrophobic surfaces, the duration of a CCR mode is reduced and that of a CCA mode is increased. Compared to Rowan's kinetic model, which is based on the vapor diffusion across the droplet boundary, the change in a contact angle in a CCR (pinned) mode shows a remarkable deviation, decreasing at a slower rate on the superhydrophobic surfaces with less-solid fractions. In a CCA (receding) mode, the change in a contact radius agrees well with the theoretical expectation, and the receding speed is slower on the superhydrophobic surfaces with lower solid fractions. The discrepancy between experimental results and Rowan's model is attributed to the initial large contact angle of a droplet on superhydrophobic surfaces. The droplet geometry with a large contact angle results in a narrow wedge region of air along the contact boundary, where the liquid-vapor diffusion is significantly restricted. Such an effect becomes minor as the evaporation proceeds with the decrease in a contact angle. In both the CCR and CCA modes, the evaporative mass transfer shows the linear relationship between mass(2/3) and evaporation time. However, the evaporation rate is slower on the superhydrophobic surfaces, which is more significant on the surfaces with lower solid fractions. As a result, the superhydrophobic surfaces slow down the drying process of a sessile droplet on them.

  19. MO-FG-CAMPUS-JeP1-03: Luminescence Imaging of Water During Proton Beam Irradiation for Range Estimation

    International Nuclear Information System (INIS)

    Yamamoto, S; Komori, M; Toshito, T; Watabe, H

    2016-01-01

    Purpose: Since proton therapy has the ability to selectively deliver a dose to a target tumor, the dose distribution should be accurately measured. A precise and efficient method to evaluate the dose distribution is desired. We found that luminescence was emitted from water during proton irradiation and thought this phenomenon could be used for estimating the dose distribution. Methods: For this purpose, we placed water phantoms set on a table with a spot-scanning proton-therapy system, and luminescence images of these phantoms were measured with a high-sensitivity cooled charge coupled device (CCD) camera during proton-beam irradiation. We also conducted the imaging of phantoms of pure-water, fluorescein solution and acrylic block. We made three dimensional images from the projection data. Results: The luminescence images of water phantoms during the proton-beam irradiations showed clear Bragg peaks, and the measured proton ranges from the images were almost the same as those obtained with an ionization chamber. The image of the pure-water phantom also 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 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 14.5% shorter proton range than that of water; the proton range in the acrylic phantom was relatively matched with the calculated value. The luminescence images of the tap-water phantom during proton irradiation could be obtained in less than 2 sec. Three dimensional images were successfully obtained which have more quantitative information. Conclusion: Luminescence imaging during proton-beam irradiation has the potential to be a new method for range estimations in proton therapy.

  20. MO-FG-CAMPUS-JeP1-03: Luminescence Imaging of Water During Proton Beam Irradiation for Range Estimation

    Energy Technology Data Exchange (ETDEWEB)

    Yamamoto, S; Komori, M [Nagoya University, Nagoya, Aichi (Japan); Toshito, T [Nagoya Proton Therapy Center, Nagoya, Aichi (Japan); Watabe, H [Tohoku University, Sendai, Miyagi (Japan)

    2016-06-15

    Purpose: Since proton therapy has the ability to selectively deliver a dose to a target tumor, the dose distribution should be accurately measured. A precise and efficient method to evaluate the dose distribution is desired. We found that luminescence was emitted from water during proton irradiation and thought this phenomenon could be used for estimating the dose distribution. Methods: For this purpose, we placed water phantoms set on a table with a spot-scanning proton-therapy system, and luminescence images of these phantoms were measured with a high-sensitivity cooled charge coupled device (CCD) camera during proton-beam irradiation. We also conducted the imaging of phantoms of pure-water, fluorescein solution and acrylic block. We made three dimensional images from the projection data. Results: The luminescence images of water phantoms during the proton-beam irradiations showed clear Bragg peaks, and the measured proton ranges from the images were almost the same as those obtained with an ionization chamber. The image of the pure-water phantom also 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 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 14.5% shorter proton range than that of water; the proton range in the acrylic phantom was relatively matched with the calculated value. The luminescence images of the tap-water phantom during proton irradiation could be obtained in less than 2 sec. Three dimensional images were successfully obtained which have more quantitative information. Conclusion: Luminescence imaging during proton-beam irradiation has the potential to be a new method for range estimations in proton therapy.

  1. Hydrated proton and hydroxide charge transfer at the liquid/vapor interface of water

    Energy Technology Data Exchange (ETDEWEB)

    Soniat, Marielle; Rick, Steven W., E-mail: srick@uno.edu [Department of Chemistry, University of New Orleans, New Orleans, Louisiana 70148 (United States); Kumar, Revati [Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70808 (United States)

    2015-07-28

    The role of the solvated excess proton and hydroxide ions in interfacial properties is an interesting scientific question with applications in a variety of aqueous behaviors. The role that charge transfer (CT) plays in interfacial behavior is also an unsettled question. Quantum calculations are carried out on clusters of water with an excess proton or a missing proton (hydroxide) to determine their CT. The quantum results are applied to analysis of multi-state empirical valence bond trajectories. The polyatomic nature of the solvated excess proton and hydroxide ion results in directionally dependent CT, depending on whether a water molecule is a hydrogen bond donor or acceptor in relation to the ion. With polyatomic molecules, CT also depends on the intramolecular bond distances in addition to intermolecular distances. The hydrated proton and hydroxide affect water’s liquid/vapor interface in a manner similar to monatomic ions, in that they induce a hydrogen-bonding imbalance at the surface, which results in charged surface waters. This hydrogen bond imbalance, and thus the charged waters at the surface, persists until the ion is at least 10 Å away from the interface.

  2. Hydrated proton and hydroxide charge transfer at the liquid/vapor interface of water

    International Nuclear Information System (INIS)

    Soniat, Marielle; Rick, Steven W.; Kumar, Revati

    2015-01-01

    The role of the solvated excess proton and hydroxide ions in interfacial properties is an interesting scientific question with applications in a variety of aqueous behaviors. The role that charge transfer (CT) plays in interfacial behavior is also an unsettled question. Quantum calculations are carried out on clusters of water with an excess proton or a missing proton (hydroxide) to determine their CT. The quantum results are applied to analysis of multi-state empirical valence bond trajectories. The polyatomic nature of the solvated excess proton and hydroxide ion results in directionally dependent CT, depending on whether a water molecule is a hydrogen bond donor or acceptor in relation to the ion. With polyatomic molecules, CT also depends on the intramolecular bond distances in addition to intermolecular distances. The hydrated proton and hydroxide affect water’s liquid/vapor interface in a manner similar to monatomic ions, in that they induce a hydrogen-bonding imbalance at the surface, which results in charged surface waters. This hydrogen bond imbalance, and thus the charged waters at the surface, persists until the ion is at least 10 Å away from the interface

  3. The reaction kinetics of lithium salt with water vapor

    International Nuclear Information System (INIS)

    Balooch, M.; Dinh, L.N.; Calef, D.F.

    2002-01-01

    The interaction of lithium salt (LiH and/or LiD) with water vapor in the partial pressure range of 10 -5 -2657 Pa has been investigated. The reaction probability of water with LiH cleaved in an ultra high vacuum environment was obtained using the modulated molecular beam technique. This probability was 0.11 and independent of LiH surface temperature, suggesting a negligible activation energy for the reaction in agreement with quantum chemical calculations. The value gradually reduced, however, to 0.007 as the surface concentration of oxygen containing product approached full coverage. As the film grew beyond a monolayer, the phase lag of hydrogen product increased from 0 deg. C to 20 deg. C and the reaction probability reduced further until it approached our detection limit (∼10 -4 ). This phase lag was attributed to a diffusion-limited process in this regime. For micrometer thick hydroxide films grown in high moisture concentration environment on LiD and LiH, the reaction probability reduced to ∼4x10 -7 and was independent of exposure time. In this regime of thick hydroxide films (LiOH and/or LiOD), microcracks generated in the films to release stress provided easier pathways for moisture to reach the interface. A modified microscope, capable of both atomic force microscopy and nanoindentation, was also employed to investigate the surface morphology of hydroxide monohydrate (LiOH · H 2 O and/or LiOD · H 2 O) grown on hydroxide at high water vapor partial pressures and the kinetics of this growth

  4. Effect of glycidyl methacrylate (GMA) incorporation on water uptake and conductivity of proton exchange membranes

    Science.gov (United States)

    Sproll, Véronique; Schmidt, Thomas J.; Gubler, Lorenz

    2018-03-01

    The aim of this work was to investigate how hygroscopic moieties like hydrolyzed glycidyl methacrylate (GMA) influence the properties of sulfonated polysytrene based proton exchange membranes (PEM). Therefore, several membranes were synthesized by electron beam treatment of the ETFE (ethylene-alt-tetrafluoroethylene) base film with a subsequent co-grafting of styrene and GMA at different ratios. The obtained membranes were sulfonated to introduce proton conducting groups and the epoxide moiety of the GMA unit was hydrolyzed for a better water absorption. The PEM was investigated regarding its structural composition, water uptake and through-plane conductivity. It could be shown that the density of sulfonic acid groups has a higher influence on the proton conductivity of the PEM than an increased water uptake.

  5. Highly Water-Stable Lanthanide-Oxalate MOFs with Remarkable Proton Conductivity and Tunable Luminescence.

    Science.gov (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

    2017-09-01

    Although proton conductors derived from metal-organic frameworks (MOFs) are highly anticipated for various applications including solid-state electrolytes, H 2 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.

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

    Science.gov (United States)

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

    2010-09-28

    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 calorimetry and ionization chamber dosimetry in an 85-MeV clinical proton beam.

    Science.gov (United States)

    Palmans, H; Seuntjens, J; Verhaegen, F; Denis, J M; Vynckier, S; Thierens, H

    1996-05-01

    In recent years, the increased use of proton beams for clinical purposes has enhanced the demand for accurate absolute dosimetry for protons. As calorimetry is the most direct way to establish the absorbed dose and because water has recently been accepted as standard material for this type of beam, the importance of water calorimetry is obvious. In this work we report water calorimeter operation in an 85-MeV proton beam and a comparison of the absorbed dose to water measured by ionometry with the dose resulting from water calorimetric measurements. To ensure a proper understanding of the heat defect for defined impurities in water for this type of radiation, a relative response study was first done in comparison with theoretical calculations of the heat defect. The results showed that pure hypoxic water and hydrogen-saturated water yielded the same response with practically zero heat defect, in agreement with the model calculations. The absorbed dose inferred from these measurements was then compared with the dose derived from ionometry by applying the European Charged Heavy Particle Dosimetry (ECHED) protocol. Restricting the comparison to chambers recommended in the protocol, the calorimeter dose was found to be 2.6% +/- 0.9% lower than the average ionometry dose. In order to estimate the significance of chamber-dependent effects in this deviation, measurements were performed using a set of ten ionization chambers of five different types. The maximum internal deviation in the ionometry results amounted to 1.1%. We detected no systematic chamber volume dependence, but observed a small but systematic effect of the chamber wall thickness. The observed deviation between calorimetry and ionometry can be attributed to a combination of the value of (Wair/e)p for protons, adopted in the ECHED protocol, the mass stopping power ratios of water to air for protons, and possibly small ionization chamber wall effects.

  8. Electronic stopping power calculation for water under the Lindhard formalism for application in proton computed tomography

    Energy Technology Data Exchange (ETDEWEB)

    Guerrero, A. F., E-mail: afguerreror@uqvirtual.edu.co [Departamento de Física, Universidad Del Quindío Cra 15 # 12N Armenia, Quindío (Colombia); Mesa, J., E-mail: jmesa@ibb.unesp.br [Instituto de Biociências de Botucatu da UNESP Distrito de Rubião Jr. s/n°, 18618-000, Botucatu, SP (Brazil)

    2016-07-07

    Because of the behavior that charged particles have when they interact with biological material, proton therapy is shaping the future of radiation therapy in cancer treatment. The planning of radiation therapy is made up of several stages. The first one is the diagnostic image, in which you have an idea of the density, size and type of tumor being treated; to understand this it is important to know how the particles beam interacts with the tissue. In this work, by using de Lindhard formalism and the Y.R. Waghmare model for the charge distribution of the proton, the electronic stopping power (SP) for a proton beam interacting with a liquid water target in the range of proton energies 10{sup 1} eV - 10{sup 10} eV taking into account all the charge states is calculated.

  9. The water proton spin-lattice relaxation times in virus-infected cells

    International Nuclear Information System (INIS)

    Valensin, G.; Gaggelli, E.; Tiezzi, E.; Valensin, P.E.; Bianchi Bandinelli, M.L.

    1979-01-01

    The water proton spin-lattice relaxation times in HEp-2 cell cultures were determined immediately after 1 h of polio-virus adsorption. The shortening of the water T 1 was closely related to the multiplicity of infection, allowing direct inspections of the virus-cell interaction since the first steps of the infectious cycle. Virus-induced structural and conformational changes of cell constituents were suggested to be detectable by NMR investigation of cell water. (Auth.)

  10. Water sorption kinetics of damaged beans: GAB model

    Directory of Open Access Journals (Sweden)

    Fernanda M. Baptestini

    Full Text Available ABSTRACT The objective of this study was to model the water sorption kinetics of damaged beans. Grains with initial moisture content of 53.85%, dry basis (d.b., were used. One portion of the grains was used to obtain desorption isotherms, while the other was subjected to drying until the moisture content of 5.26% (d.b., so that it was subjected to the adsorption. For the induction of damage, a Stein Breakage Tester was used. To obtain the equilibrium moisture content, grains were placed in a climatic chamber at 20, 30, 40 and 50 ± 1 °C combined with relative humidity of 30, 40, 50, 70 and 90 ± 3%. The GAB model fitted well to the equilibrium moisture experimental data of damaged grains and control. With increasing temperature, the monolayer moisture contents decreased in adsorption and desorption processes, ranging from 9.84 to 5.10% d.b. The lower moisture content in the monolayer in damaged grains indicates that lower moisture content is necessary to ensure their conservation.

  11. SU-C-207A-04: Accuracy of Acoustic-Based Proton Range Verification in Water

    International Nuclear Information System (INIS)

    Jones, KC; Sehgal, CM; Avery, S; Vander Stappen, F

    2016-01-01

    Purpose: To determine the accuracy and dose required for acoustic-based proton range verification (protoacoustics) in water. Methods: Proton pulses with 17 µs FWHM and instantaneous currents of 480 nA (5.6 × 10 7 protons/pulse, 8.9 cGy/pulse) were generated by a clinical, hospital-based cyclotron at the University of Pennsylvania. The protoacoustic signal generated in a water phantom by the 190 MeV proton pulses was measured with a hydrophone placed at multiple known positions surrounding the dose deposition. The background random noise was measured. The protoacoustic signal was simulated to compare to the experiments. Results: The maximum protoacoustic signal amplitude at 5 cm distance was 5.2 mPa per 1 × 10 7 protons (1.6 cGy at the Bragg peak). The background random noise of the measurement was 27 mPa. Comparison between simulation and experiment indicates that the hydrophone introduced a delay of 2.4 µs. For acoustic data collected with a signal-to-noise ratio (SNR) of 21, deconvolution of the protoacoustic signal with the proton pulse provided the most precise time-of-flight range measurement (standard deviation of 2.0 mm), but a systematic error (−4.5 mm) was observed. Conclusion: Based on water phantom measurements at a clinical hospital-based cyclotron, protoacoustics is a potential technique for measuring the proton Bragg peak range with 2.0 mm standard deviation. Simultaneous use of multiple detectors is expected to reduce the standard deviation, but calibration is required to remove systematic error. Based on the measured background noise and protoacoustic amplitude, a SNR of 5.3 is projected for a deposited dose of 2 Gy.

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

    Directory of Open Access Journals (Sweden)

    E. Kallio

    2012-11-01

    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.

  13. Energetic protons at Mars. Interpretation of SLED/Phobos-2 observations by a kinetic model

    International Nuclear Information System (INIS)

    Kallio, E.; Alho, M.; Jarvinen, R.; Dyadechkin, S.; McKenna-Lawlor, S.; Afonin, V.V.

    2012-01-01

    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 2.8RM). 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. (orig.)

  14. Energetic protons at Mars. Interpretation of SLED/Phobos-2 observations by a kinetic model

    Energy Technology Data Exchange (ETDEWEB)

    Kallio, E.; Alho, M.; Jarvinen, R.; Dyadechkin, S. [Finnish Meteorological Institute, Helsinki (Finland); McKenna-Lawlor, S. [Space Technology Ireland, Maynooth, Co. Kildare (Ireland); Afonin, V.V. [Space Research Institute, Moscow (Russian Federation)

    2012-07-01

    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 2.8RM). 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. (orig.)

  15. Proton NMR investigation of heme pocket mobility in hemoglobin via hydrogen isotope exchange kinetics

    International Nuclear Information System (INIS)

    Han, K.

    1985-01-01

    Dynamic mobility of heme cavity, the active site of Hb, was investigated by analyzing the hydrogen isotope exchange kinetics of the proximal histidyl ring NH of various kinds of Hbs with the aid of the high field Fourier Transform 1 H NMR spectroscopy. The exchange reaction occurs faster in oxy or R-state Hb than in deoxy or T-state Hb and there exists a good correlation between the oxygen affinity of Hb and the heme pocket mobility reflected in the hydrogen exchange rate. The effect of pH on the exchange is dramatically different for the two subunits of Hb A. Studying the exchange characteristics of mutant Hbs and chemically modified Hbs not only showed the existence of three well-defined localized paths for transmission of conformational changes between different heme pockets through a 1 b 2 subunit interface, but also indicated that the heme pocket mobility is regulated by the quaternary state of Hb as well as by the ligation state of Hb. Finally, the effect of the quaternary state on the heme pocket mobility is separated from that of the ligation by following the exchange reactions in Hbs where only their quaternary structure transition can be achieved without changing their ligation states by adjusting experimental conditions such as adding inositol hexaphosphate

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

    Directory of Open Access Journals (Sweden)

    M. Nishihara

    2018-03-01

    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.

  17. Proton dynamics and the phase diagram of dense water ice.

    Science.gov (United States)

    Hernandez, J-A; Caracas, R

    2018-06-07

    All the different phases of water ice between 2 GPa and several megabars are based on a single body-centered cubic sub-lattice of oxygen atoms. They differ only by the behavior of the hydrogen atoms. In this study, we investigate the dynamics of the H atoms at high pressures and temperatures in water ice from first-principles molecular dynamics simulations. We provide a detailed analysis of the O-H⋯O bonding dynamics over the entire stability domain of the body-centered cubic (bcc) water ices and compute transport properties and vibrational density-of-states. We report the first ab initio evidence for a plastic phase of water and we propose a coherent phase diagram for bcc water ices compatible with the two groups of melting curves and with the multiple anomalies reported in ice VII around 15 GPa.

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

    NARCIS (Netherlands)

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

    2007-01-01

    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

  19. Hyperthyroidism stimulates mitochondrial proton leak and ATP turnover in rat hepatocytes but does not change the overall kinetics of substrate oxidation reactions.

    Science.gov (United States)

    Harper, M E; Brand, M D

    1994-08-01

    Thyroid hormones have well-known effects on oxidative phosphorylation, but there is little quantitative information on their important sites of action. We have used top-down elasticity analysis, an extension of metabolic control analysis, to identify the sites of action of thyroid hormones on oxidative phosphorylation in rat hepatocytes. We divided the oxidative phosphorylation system into three blocks of reactions: the substrate oxidation subsystem, the phosphorylating subsystem, and the mitochondrial proton leak subsystem and have identified those blocks of reactions whose kinetics are significantly changed by hyperthyroidism. Our results show significant effects on the kinetics of the proton leak and the phosphorylating subsystems. Quantitative analyses revealed that 43% of the increase in resting respiration rate in hyperthyroid hepatocytes compared with euthyroid hepatocytes was due to differences in the proton leak and 59% was due to differences in the activity of the phosphorylating subsystem. There were no significant effects on the substrate oxidation subsystem. Changes in nonmitochondrial oxygen consumption accounted for -2% of the change in respiration rate. Top-down control analysis revealed that the distribution of control over the rates of mitochondrial oxygen consumption, ATP synthesis and consumption, and proton leak and over mitochondrial membrane potential (delta psi m) was similar in hepatocytes from hyperthyroid and littermate-paired euthyroid controls. The results of this study include the first complete top-down elasticity and control analyses of oxidative phosphorylation in hepatocytes from hyperthyroid rats.

  20. Investigation of water distribution in proton exchange membrane fuel cells via Terahertz imaging

    International Nuclear Information System (INIS)

    Thamboon, P.; Buaphad, P.; Thongbai, C.; Saisud, J.; Kusoljariyakul, K.; Rhodes, M.W.; Vilaithong, T.

    2011-01-01

    Coherent transition radiation in a THz regime generated from a femtosecond electron bunch is explored for its potential use in imaging applications. Due to water sensitivity, the THz imaging experiment is performed on a proton exchange membrane fuel cell (PEMFC) to assess the ability to quantify water in the flow field of the cell. In this investigation, the PEMFC design and the experimental setup for the THz imaging is described. The results of the THz images in the flow field are also discussed.

  1. Kinetics of reactions of aquacobalamin with aspartic and glutamic acids and their amides in water solutions

    Science.gov (United States)

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

    2017-04-01

    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.

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

    Science.gov (United States)

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

    2011-02-07

    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. Comparison of the secondary electrons produced by proton and electron beams in water

    Energy Technology Data Exchange (ETDEWEB)

    Kia, Mohammad Reza, E-mail: m-r-kia@aut.ac.ir; Noshad, Houshyar [Department of Energy Engineering and Physics, Amirkabir University of Technology (Tehran Polytechnic), P.O. Box 15875-4413, Hafez Avenue, Tehran (Iran, Islamic Republic of)

    2016-05-15

    The secondary electrons produced in water by electron and proton beams are compared with each other. The total ionization cross section (TICS) for an electron impact in water is obtained by using the binary-encounter-Bethe model. Hence, an empirical equation based on two adjustable fitting parameters is presented to determine the TICS for proton impact in media. In order to calculate the projectile trajectory, a set of stochastic differential equations based on the inelastic collision, elastic scattering, and bremsstrahlung emission are used. In accordance with the projectile trajectory, the depth dose deposition, electron energy loss distribution in a certain depth, and secondary electrons produced in water are calculated. The obtained results for the depth dose deposition and energy loss distribution in certain depth for electron and proton beams with various incident energies in media are in excellent agreement with the reported experimental data. The difference between the profiles for the depth dose deposition and production of secondary electrons for a proton beam can be ignored approximately. But, these profiles for an electron beam are completely different due to the effect of elastic scattering on electron trajectory.

  4. Water equivalence of various materials for clinical proton dosimetry by experiment and Monte Carlo simulation

    International Nuclear Information System (INIS)

    Al-Sulaiti, Leena; Shipley, David; Thomas, Russell; Kacperek, Andrzej; Regan, Patrick; Palmans, Hugo

    2010-01-01

    The accurate conversion of dose to various materials used in clinical proton dosimetry to dose-to-water is based on fluence correction factors, accounting for attenuation of primary protons and production of secondary particles due to non-elastic nuclear interactions. This work aims to investigate the depth dose distribution and the fluence correction with respect to water or graphite at water equivalent depths (WED) in different target materials relevant for dosimetry such as polymethyl methacrylate (PMMA), graphite, A-150, aluminium and copper at 60 and 200 MeV. This was done through a comparison between Monte Carlo simulation using MCNPX 2.5.0, analytical model calculations and experimental measurements at Clatterbridge Centre of Oncology (CCO) in a 60 MeV modulated and un-modulated proton beam. MCNPX simulations indicated small fluence corrections for all materials with respect to graphite and water in 60 and 200 MeV except for aluminium. The analytical calculations showed an increase in the fluence correction factor to a few percent for all materials with respect to water at 200 MeV. The experimental measurements for 60 MeV un-modulated beam indicated a good agreement with MCNPX. For the modulated beam the fluence correction factor was found to be decreasing below unity by up to few percent with depth for aluminium and copper but almost constant and unity for A-150.

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

    NARCIS (Netherlands)

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

    2012-01-01

    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

  6. 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

    1999-05-01

    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

  7. 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 ...

  8. Celerity, pulse and wavelength of De broglie for a nucleon (proton or neutron), according to its kinetic energy. - Formulas and curves; Vitesse, impulsion et longueur d'onde de de broglie d'un nucleon (proton ou neutron), en fonction de son energie cinetique. - Formules et courbes

    Energy Technology Data Exchange (ETDEWEB)

    Rogozmski, A [Commissariat a l' Energie Atomique, Saclay (France). Centre d' Etudes Nucleaires

    1952-07-01

    The celerity curves, pulse and wavelength of De Broglie for a nucleon (proton or neutron) have been calculated and traced accordingly to its kinetic energy. (M.B.) [French] Les courbes de vitesses, d mpulsion et de longueur d nde de Broglie d n nucleon (proton ou neutron) ont ete calcule et trace en fonction de son energie cinetique. (M.B.)

  9. 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

    2016-01-01

    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. Precise determination of the Bragg peak position of proton beams in liquid water

    International Nuclear Information System (INIS)

    Marouane, Abdelhak; Ouaskit, Said; Inchaouh, Jamal

    2011-01-01

    The influence of water molecules on the surrounding biological molecules during irradiation with protons is currently a major subject in radiation science. Proton collisions with the water molecules are estimated around the Bragg peak region, taking into account ionization, excitation, charge-changing processes, and energetic secondary electron behavior. The Bragg peak profile and position was determined by adopting a new approach involving discretization, incrementation, and dividing the target into layers, the thickness of each layer being selected randomly from a distribution weighted by the values of the total interaction cross section, from excitation up to ionization of the target and the incident projectile charge exchange. The calculation was carried out by a Monte-Carlo simulation in the energy range 20 ≤ E ≤ 10 8 eV, including the relativistic corrections.

  11. Thermodynamics of proton binding at the alumina-water interface revisited

    International Nuclear Information System (INIS)

    Morel, J.P.; Morel-Desrosiers, N.; Guillaud, A.; Marmier, N.

    2005-01-01

    Full text of publication follows: Since sorption on natural or synthetic materials can attenuate the migration of the radionuclides, sorption reactions have to be taken into account in repository performance assessment models. In order to check these models at different temperatures, experimental data such as the enthalpies of sorption are thus required. Highly sensitive micro-calorimeters can now be used to determine the heat effects accompanying the sorption of radionuclides on oxide-water interfaces, but enthalpies of sorption cannot be extracted from microcalorimetric data without a clear knowledge of the thermodynamics of protonation and deprotonation of the oxide surface. However, the values reported in the literature show large discrepancies and one must conclude that, amazingly, this fundamental problem of proton binding is not yet resolved. We have thus undertaken to measure by titration micro-calorimetry the heat effects accompanying proton exchange at the alumina-water interface at 25 deg. C. Based on (i) the surface sites speciation provided by a surface complexation model (built from acid-base titrations at 25 deg. C), and (ii) results of the microcalorimetric experiments, calculations have been made to extract the enthalpy variations associated respectively to protonation and deprotonation of the alumina surface. In a second step, the protonation and deprotonation enthalpy values have been used to calculate the alumina surface acidity constants at 60 deg. C via the Van't Hoff equation. Then, a theoretical titration curve at 60 deg. C has been calculated and compared to the experimental alumina surface titration curve. A good agreement between the predicted acid-base titration curve and the experimental one was observed. (authors)

  12. Thermodynamics of proton binding at the alumina-water interface revisited

    Energy Technology Data Exchange (ETDEWEB)

    Morel, J.P.; Morel-Desrosiers, N. [Laboratoire de Thermodynamique des Solutions et des Polymeres, UMR CNRS 6003, Universite Blaise Pascal, 24 avenue des Landais, 63177 Aubiere cedex (France); Guillaud, A.; Marmier, N. [Laboratoire de Radiochimie, Sciences Analytiques et Environnement, EA 1175, Universite de Nice, 28 avenue de Valrose, 06108 Nice cedex 2 (France)

    2005-07-01

    Full text of publication follows: Since sorption on natural or synthetic materials can attenuate the migration of the radionuclides, sorption reactions have to be taken into account in repository performance assessment models. In order to check these models at different temperatures, experimental data such as the enthalpies of sorption are thus required. Highly sensitive micro-calorimeters can now be used to determine the heat effects accompanying the sorption of radionuclides on oxide-water interfaces, but enthalpies of sorption cannot be extracted from microcalorimetric data without a clear knowledge of the thermodynamics of protonation and deprotonation of the oxide surface. However, the values reported in the literature show large discrepancies and one must conclude that, amazingly, this fundamental problem of proton binding is not yet resolved. We have thus undertaken to measure by titration micro-calorimetry the heat effects accompanying proton exchange at the alumina-water interface at 25 deg. C. Based on (i) the surface sites speciation provided by a surface complexation model (built from acid-base titrations at 25 deg. C), and (ii) results of the microcalorimetric experiments, calculations have been made to extract the enthalpy variations associated respectively to protonation and deprotonation of the alumina surface. In a second step, the protonation and deprotonation enthalpy values have been used to calculate the alumina surface acidity constants at 60 deg. C via the Van't Hoff equation. Then, a theoretical titration curve at 60 deg. C has been calculated and compared to the experimental alumina surface titration curve. A good agreement between the predicted acid-base titration curve and the experimental one was observed. (authors)

  13. DEFLUORIDATION OF DRINKING WATER BY ELECTROCOAGULATION/ELECTROFLOTATION - KINETIC STUDY

    Directory of Open Access Journals (Sweden)

    Bennajah Mounir

    2010-06-01

    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.

  14. PMR spectra and proton magnetic relaxation in uranyl nitrate-hexamethylenetetramine-urea-water gel forming system

    International Nuclear Information System (INIS)

    Vashman, A.A.; Pronin, I.S.; Brylkina, T.V.; Makarov, V.M.

    1979-01-01

    PMR spectra and proton relaxation in the nitrate-hexamethylenetetramine (HMTA)-urea-water gelling system are studied. According to PMR spectra products of HMTA chemical decomposition, which are supposed to be formed in the gelling process, have not been detected. Effect of hydrogen exchange upon PMR spectra of urea and water in the presence of HMTA and uranyl nitrate is studied. Periods of spin-lattice and spin-spin relaxations of water and HMTA protons in gels on the base of uranyl nitrate are found. Data on relaxation permitted to make qualitative conclusions upon the gel structure and HMTA molecule distribution over ''phases''. Nonproducibility of the results of period measurements in gels is the result of nonproducibility of the gel structure in the course of transformation of liquid solution into gel. Temperature dependences of proton relaxation in the gels are impossible yet to interpret on the basis of temperature behaviour of one correlation period, controlling dipole-dipole nuclear magnetic relaxation, and obeying Arrhenius dependence on the temperature

  15. Which Density Functional Should Be Used to Describe Protonated Water Clusters?

    Science.gov (United States)

    Shi, Ruili; Huang, Xiaoming; Su, Yan; Lu, Hai-Gang; Li, Si-Dian; Tang, Lingli; Zhao, Jijun

    2017-04-27

    Protonated water cluster is one of the most important hydrogen-bond network systems. Finding an appropriate DFT method to study the properties of protonated water clusters can substantially improve the economy in computational resources without sacrificing the accuracy compared to high-level methods. Using high-level MP2 and CCSD(T) methods as well as experimental results as benchmark, we systematically examined the effect of seven exchange-correlation GGA functionals (with BLYP, B3LYP, X3LYP, PBE0, PBE1W, M05-2X, and B97-D parametrizations) in describing the geometric parameters, interaction energies, dipole moments, and vibrational properties of protonated water clusters H + (H 2 O) 2-9,12 . The overall performance of all these functionals is acceptable, and each of them has its advantage in certain aspects. X3LYP is the best to describe the interaction energies, and PBE0 and M05-2X are also recommended to investigate interaction energies. PBE0 gives the best anharmonic frequencies, followed by PBE1W, B97-D and BLYP methods. PBE1W, B3LYP, B97-D, and X3LYP can yield better geometries. The capability of B97-D to distinguish the relative energies between isomers is the best among all the seven methods, followed by M05-2X and PBE0.

  16. Radiation damage to uracil and water by proton and electron impact

    International Nuclear Information System (INIS)

    Scheier, P.; Hanel, G.; Denifl, S; Gstir, B.; Maerk, T.D.; Farizon, B.; Farizon, M.; Coupier, B.

    2002-01-01

    Full text: The inelastic interaction of protons (in the energy range from 20 keV to 150 keV) and electrons (from thermal energies up to 20 eV) with water and uracil, the latter a building block of the RNA has been studied in two laboratories with specially designed experimental setups. These measurements are motivated from a present lack of understanding how on a molecular level damage to living cells and organisms is caused. A unique way of simultaneous detection of the product ions after swift proton (or hydrogen) impact and the analysis of the charge state of the projectile after the collision allows to distinguish between direct ionization (e.g., projectile remains a proton) and electron capture events (e.g., proton becomes neutralized). The latter process turns out to be more destructive, i.e. leads to a higher yield of fragmentation. For electrons both the formation of positively and negatively charged ions has been investigated. We discovered that already thermal electrons lead with a rather large cross section to a dissociation of the uracil molecule producing an anion and a fast hydrogen radical. (author)

  17. 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

  18. Parity Nonconservation in Proton-water Scattering at 800 MeV

    Science.gov (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.

    1982-01-01

    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}.

  19. Hydrogen-exchange kinetics of the indole NH proton of the buried tryptophan in the constant fragment of the immunoglobulin light chain

    International Nuclear Information System (INIS)

    Kawata, Y.; Goto, Y.; Hamaguchi, K.; Hayashi, F.; Kobayashi, Y.; Kyogoku, Y.

    1988-01-01

    The constant fragment of the immunoglobulin light chain (type λ) has two trytophyl residues at positions 150 and 187. Trp-150 is buried in the interior, and Trp-187 lies on the surface of the molecule. The hydrogen-deuterium exchange kinetics of the indole NH proton Trp-150 were studied at various pH values at 25 0 C by 1 H nuclear magnetic resonance. Exchange rates were approximately first order in hydroxyl ion dependence above pH 8, were relatively independent of pH between pH 7 and 8, and decreased below pH 7. On the assumption that the exchange above pH 8 proceeds through local fluctuations of the protein molecule, the exchange rates between pH 7 and 8 through global unfolding were estimated. The exchange rate constant within this pH range at 25 0 C thus estimated was consistent with that of the global unfolding of the constant fragment under the same conditions as those reported previously. The activation energy for the exchange process at pH 7.8 was the same as that for the unfolding process by 2 M guanidine hydrochloride. The exchange rates of backbone NH protons were almost the same as that of the indole NH proton of Trp-150 at pH 7.l. These observations also indicated that the exchange between pH 7 and 8 occurs through global unfolding of the protein molecule and is rate-limited by the unfolding. At around pH 9, on the other hand, the activation energy for the exchange process of the indole NH proton of Trp-150 was smaller than that for the unfolding process, and the exchange rates differed according to the different signals of backbone NH protons. These findings together with the pH dependence of the rate constant indicated that exchange due to local fluctuations is predominant above pH 8

  20. Kinetics of Chemical Agents Destruction in Supercritical Water

    National Research Council Canada - National Science Library

    Tester, Jefferson

    2003-01-01

    .... An experimental study of methylphosphonic acid (MPA) oxidation has been completed that includes macroscopic modeling of the overall global rate law for MPA oxidation in supercritical water (SCW...

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

    KAUST Repository

    Chaieb, Sahraoui

    2014-08-05

    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.

  2. Prospects for very large, sensitive water Cherenkov detectors for proton decay and neutrino oscillations search

    International Nuclear Information System (INIS)

    Cline, D.B.

    1982-01-01

    We discuss the possibility of constructing large water Cherenkov detectors with mass 10 5 to 10 6 tons that would be sensitive to a few hundred MeV - few GeV energy release. The 10 5 ton detector would be suitable for a search for certain proton decay modes whereas the 10 6 ton detector would act as an active shield for the proton decay detector and as a nu/sub e/, nu/sub μ/ and possibly nu/sub tau/ interaction detector. The neutrino physics would include a sensitive search for neutrino oscillations using atmospheric neutrinos. The location of this detector could be in the deep ocean near Hawaii or in a deep trench between Cuba and Haiti or perhaps deep lakes like Superior or Baikal if flexible containers are used

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

    International Nuclear Information System (INIS)

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

    1979-01-01

    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

  4. Kinetic isotopic fractionation during diffusion of ionic species in water

    Science.gov (United States)

    Richter, Frank M.; Mendybaev, Ruslan A.; Christensen, John N.; Hutcheon, Ian D.; Williams, Ross W.; Sturchio, Neil C.; Beloso, Abelardo D.

    2006-01-01

    Experiments specifically designed to measure the ratio of the diffusivities of ions dissolved in water were used to determine DLi/DK,D/D,D/D,D/D,andD/D. The measured ratio of the diffusion coefficients for Li and K in water (D Li/D K = 0.6) is in good agreement with published data, providing evidence that the experimental design being used resolves the relative mobility of ions with adequate precision to also be used for determining the fractionation of isotopes by diffusion in water. In the case of Li, we found measurable isotopic fractionation associated with the diffusion of dissolved LiCl (D/D=0.99772±0.00026). This difference in the diffusion coefficient of 7Li compared to 6Li is significantly less than that reported in an earlier study, a difference we attribute to the fact that in the earlier study Li diffused through a membrane separating the water reservoirs. Our experiments involving Mg diffusing in water found no measurable isotopic fractionation (D/D=1.00003±0.00006). Cl isotopes were fractionated during diffusion in water (D/D=0.99857±0.00080) whether or not the co-diffuser (Li or Mg) was isotopically fractionated. The isotopic fractionation associated with the diffusion of ions in water is much smaller than values we found previously for the isotopic fractionation of Li and Ca isotopes by diffusion in molten silicate liquids. A major distinction between water and silicate liquids is that water surrounds dissolved ions with hydration shells, which very likely play an important but still poorly understood role in limiting the isotopic fractionation associated with diffusion.

  5. 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)

    1995-09-26

    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.

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

    KAUST Repository

    Hisatomi, Takashi; Takanabe, Kazuhiro; Domen, Kazunari

    2014-01-01

    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

  7. Proton exchange membrane fuel cells

    CERN Document Server

    Qi, Zhigang

    2013-01-01

    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

  8. Calculation of the protons stopping power in water using dielectric formalism in the MELF-GOS approach

    International Nuclear Information System (INIS)

    Ribeiro, Franciane; Mazer, Amanda Cristina; Hormaza, Joel Mesa

    2016-01-01

    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)

  9. Influence of surfactants on gas-hydrate formation' kinetics in water-oil emulsion

    Science.gov (United States)

    Zemenkov, Yu D.; Shirshova, A. V.; Arinstein, E. A.; Shuvaev, A. N.

    2018-05-01

    The kinetics of gas hydrate formation of propane in a water-oil emulsion is experimentally studied when three types of surfactants (SAA (surface acting agent)) - anionic type emulsifiers - are added to the aqueous phase. It is shown that all three types of surfactants decelerate the growth of the gas-hydrate in the emulsion and can be considered as anti-agglutinating and kinetic low-dose inhibitors. The most effective inhibitor of hydrate formation in water-oil emulsion of SV-102 surfactant was revealed. For comparison, experimental studies of gas-hydrate formation under the same conditions for bulk water have been carried out. It is shown that in bulk water, all the surfactants investigated act as promoters (accelerators) of hydrate formation. A qualitative explanation of the action mechanisms of emulsifiers in the process of gas-hydrate formation in water-oil emulsion is given.

  10. Water equivalent thickness values of materials used in beams of protons, helium, carbon and iron ions.

    Science.gov (United States)

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

    2010-05-07

    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.

  11. The generation of absorbed dose profiles of proton beam in water using Geant4 code

    International Nuclear Information System (INIS)

    Christovao, Marilia T.; Campos, Tarcisio Passos R. de

    2007-01-01

    The present article approaches simulations on the proton beam radiation therapy, using an application based on the code GEANT4, with Open GL as a visualization drive and JAS3 (Java Analysis Studio) analysis data tools systems, implementing the AIDA interfaces. The proton radiotherapy is adapted to treat cancer or other benign tumors that are close to sensitive structures, since it allows precise irradiation of the target with high doses, while the health tissues adjacent to vital organs and tissues are preserved, due to physical property of dose profile. GEANT4 is a toolkit for simulating the transport of particles through matter, in complex geometries. Taking advantage of the object-oriented project features, the user can adapt or extend the tool in all domain, due to the flexibility of the code, providing a subroutine's group for materials definition, geometries and particles properties in agreement with the user's needs to generate the Monte Carlo simulation. In this paper, the parameters of beam line used in the simulation possess adjustment elements, such as: the range shifter, composition and dimension; the beam line, energy, intensity, length, according with physic processes applied. The simulation result is the depth dose profiles on water, dependent on the various incident beam energy. Starting from those profiles, one can define appropriate conditions for proton radiotherapy in ocular region. (author)

  12. The Effect of Isotopic Substitution on Quantum Proton Transfer Across Short Water Bridges in Biological Systems

    Science.gov (United States)

    Blazejewski, Jacob; Schultz, Chase; Mazzuca, James

    2015-03-01

    Many biological systems utilize water chains to transfer charge over long distances by means of an excess proton. This study examines how quantum effects impact these reactions in a small model system. The model consists of a water molecule situated between an imidazole donor and acceptor group, which simulate a fixed amino acid backbone. A one dimensional energy profile is evaluated using density functional theory at the 6-31G*/B3LYP level, which generates a barrier with a width of 0.6 Å and a height of 20.7 kcal/mol. Quantum transmission probability is evaluated by solving the time dependent Schrödinger equation on a grid. Isotopic effects are examined by performing calculations with both hydrogen and deuterium. The ratio of hydrogen over the deuterium shows a 130-fold increase in transmission probability at low temperatures. This indicates a substantial quantum tunneling effect. The study of higher dimensional systems as well as increasing the number of water molecules in the chain will be necessary to fully describe the proton transfer process. Alma College Provost's Office.

  13. Proton-Coupled Electron Transfer and a Tyrosine-Histidine Pair in a Photosystem II-Inspired β-Hairpin Maquette: Kinetics on the Picosecond Time Scale.

    Science.gov (United States)

    Pagba, Cynthia V; McCaslin, Tyler G; Chi, San-Hui; Perry, Joseph W; Barry, Bridgette A

    2016-02-25

    Photosystem II (PSII) and ribonucleotide reductase employ oxidation and reduction of the tyrosine aromatic ring in radical transport pathways. Tyrosine-based reactions involve either proton-coupled electron transfer (PCET) or electron transfer (ET) alone, depending on the pH and the pKa of tyrosine's phenolic oxygen. In PSII, a subset of the PCET reactions are mediated by a tyrosine-histidine redox-driven proton relay, YD-His189. Peptide A is a PSII-inspired β-hairpin, which contains a single tyrosine (Y5) and histidine (H14). Previous electrochemical characterization indicated that Peptide A conducts a net PCET reaction between Y5 and H14, which have a cross-strand π-π interaction. The kinetic impact of H14 has not yet been explored. Here, we address this question through time-resolved absorption spectroscopy and 280-nm photolysis, which generates a neutral tyrosyl radical. The formation and decay of the neutral tyrosyl radical at 410 nm were monitored in Peptide A and its variant, Peptide C, in which H14 is replaced by cyclohexylalanine (Cha14). Significantly, both electron transfer (ET, pL 11, L = lyonium) and PCET (pL 9) were accelerated in Peptide A and C, compared to model tyrosinate or tyrosine at the same pL. Increased electronic coupling, mediated by the peptide backbone, can account for this rate acceleration. Deuterium exchange gave no significant solvent isotope effect in the peptides. At pL 9, but not at pL 11, the reaction rate decreased when H14 was mutated to Cha14. This decrease in rate is attributed to an increase in reorganization energy in the Cha14 mutant. The Y5-H14 mechanism in Peptide A is reminiscent of proton- and electron-transfer events involving YD-H189 in PSII. These results document a mechanism by which proton donors and acceptors can regulate the rate of PCET reactions.

  14. Estimation and correction of produced light from prompt gamma photons on luminescence imaging of water for proton therapy dosimetry

    Science.gov (United States)

    Yabe, Takuya; Komori, Masataka; Toshito, Toshiyuki; Yamaguchi, Mitsutaka; Kawachi, Naoki; Yamamoto, Seiichi

    2018-02-01

    Although the luminescence images of water during proton-beam irradiation using a cooled charge-coupled device camera showed almost the same ranges of proton beams as those measured by an ionization chamber, the depth profiles showed lower Bragg peak intensities than those measured by an ionization chamber. In addition, a broad optical baseline signal was observed in depths that exceed the depth of the Bragg peak. We hypothesize that this broad baseline signal originates from the interaction of proton-induced prompt gamma photons with water. These prompt gamma photons interact with water to form high-energy Compton electrons, which may cause luminescence or Cherenkov emission from depths exceeding the location of the Bragg peak. To clarify this idea, we measured the luminescence images of water during the irradiations of protons in water with minimized parallax errors, and also simulated the produced light by the interactions of prompt gamma photons with water. We corrected the measured depth profiles of the luminescence images by subtracting the simulated distributions of the produced light by the interactions of prompt gamma photons in water. Corrections were also conducted using the estimated depth profiles of the light of the prompt gamma photons, as obtained from the off-beam areas of the luminescence images of water. With these corrections, we successfully obtained depth profiles that have almost identical distributions as the simulated dose distributions for protons. The percentage relative height of the Bragg peak with corrections to that of the simulation data increased to 94% from 80% without correction. Also, the percentage relative offset heights of the deeper part of the Bragg peak with corrections decreased to 0.2%-0.4% from 4% without correction. These results indicate that the luminescence imaging of water has potential for the dose distribution measurements for proton therapy dosimetry.

  15. Molecular dynamics simulations of proton-ordered water confined in low-diameter carbon nanotubes.

    Science.gov (United States)

    Li, Shujuan; Schmidt, Burkhard

    2015-03-21

    The present work deals with molecular dynamics simulations of water confined in single-walled carbon nanotubes (CNTs), with emphasis on the proton-ordering of water and its polarization. First, the water occupancy of open-ended armchair and zigzag CNTs immersed in water under ambient NPT conditions is calculated for various water models, and for varying Lennard-Jones parameters of the water-carbon interaction. As a function of the CNT diameter, the water density displays several oscillations before converging to the bulk value. Based on these results, the water structures encapsulated in 10 nm long armchair CNTs (n,n) with 5 ≤ n ≤ 10, are investigated under NVT conditions. Inside the smallest nanotubes (n = 5, 6) highly ferroelectric (FE), quasi-one-dimensional water chains are found while inside the other CNTs water molecules assemble into single-walled ice nanotubes (INTs). There are several, near-degenerate minimum energy INT structures: single helical structures were found for 7 ≤ n ≤ 10, in all cases in FE arrangement. In addition, a double helical INT structure was found for n = 8 with an even higher polarization. Prism-like structures were found only for 8 ≤ n ≤ 10 with various FE, ferrielectric (FI), and antiferroelectric (AF, n = 9, 10) proton ordering. The coexistence of the nearly iso-energetic FE, FI, and AF INT structures separated by high barriers renders the molecular dynamics highly metastable, typically with nanosecond timescales at room temperature. Hence, the replica exchange simulation method is used to obtain populations of different INT states at finite temperatures. Many of the FE INT structures confined in low-diameter CNTs are still prevalent at room temperature. Both helix-helix and helix-prism structural transitions are detected which can be either continuous (around 470 K for n = 8) or discontinuous (at 218 K for n = 9). Also melting-like transitions are found in which the INT structures are disrupted leading to a loss of FE

  16. Growth Kinetics of the Homogeneously Nucleated Water Droplets: Simulation Results

    International Nuclear Information System (INIS)

    Mokshin, Anatolii V; Galimzyanov, Bulat N

    2012-01-01

    The growth of homogeneously nucleated droplets in water vapor at the fixed temperatures T = 273, 283, 293, 303, 313, 323, 333, 343, 353, 363 and 373 K (the pressure p = 1 atm.) is investigated on the basis of the coarse-grained molecular dynamics simulation data with the mW-model. The treatment of simulation results is performed by means of the statistical method within the mean-first-passage-time approach, where the reaction coordinate is associated with the largest droplet size. It is found that the water droplet growth is characterized by the next features: (i) the rescaled growth law is unified at all the considered temperatures and (ii) the droplet growth evolves with acceleration and follows the power law.

  17. Kinetic model for predicting the composition of chlorinated water discharged from power plant cooling systems

    International Nuclear Information System (INIS)

    Lietzke, M.H.

    1977-01-01

    A kinetic model for predicting the composition of chlorinated water discharged from power plant cooling systems has been developed. The model incorporates the most important chemical reactions that are known to occur when chlorine is added to natural fresh waters. The simultaneous differential equations, which describe the rates of these chemical reactions, are solved numerically to give the composition of the water as a function of time. A listing of the computer program is included, along with a description of the input variables. A worked-out example illustrates the application of the program to an actual cooling system. An appendix contains a compilation of the known equilibrium and kinetic data for many of the chemical reactions that might be encountered in chlorinating natural fresh waters

  18. Kinetics of radiolysis of irradiated ligno celluloses into soluble products in water and rumen liquid

    International Nuclear Information System (INIS)

    Tukenmez, I.; Bakioglu, A.T.; Ersen, M.S.

    1997-01-01

    In order to increase the low bio hydrolysis of ligno celluloses in biotechnological and biological processes where these materials are used as raw materials and ruminant feed, the substrates were pretreated with irradiation to induce radiolytic depolymerisation and then kinetics of their radiolysis into soluble products in water and rumen liquid were analyzed. Wheat straw used as a representative lignocellulose substrate was irradiated at 0-2.5 MGy doses at 20''o''C with an optimum equilibrium humidity of 6.6% in Cs-137 gamma irradiator with a dose rate of 1.8 kGy/h, and soluablefractions in water and in situ rumen liquid were determined gravimetrically. Based on these data, a reaction mechanism was proposed for the radiolysis of ligno celluloses into soluble fractions. From the corresponding reaction rate equations with this mechanism a dose dependent kinetics was derived for the radiolysis of ligno celluloses into water/rumen liquid-soluble products. Defined by this kinetics, the threshold doses for the radiolysis of the substrate into water/rumen liquid-soluble products were respectively found 80.6 kGy and 186.0 kGy, and fractional radiolytic decomposition yields 0.193 MGy''-1''.It was emphasized that developed kinetic models may be used for the process design of irradiation pretreatments to improve the bio hydrolysis of ligno celluloses.(2figs. and 17 refs.)

  19. Water desorption kinetics of polymer composites with cellulose fibers as filler

    Czech Academy of Sciences Publication Activity Database

    Vacková, Taťana; Kroisová, D.; Špatenka, P.

    2009-01-01

    Roč. 48, č. 1 (2009), s. 68-76 ISSN 0022-2348 Institutional research plan: CEZ:AV0Z40500505 Keywords : polymer composites * water desorption kinetics * thermoplastic matrix Subject RIV: CD - Macromolecular Chemistry Impact factor: 0.716, year: 2009

  20. Quantitative description of proton exchange processes between water and endogenous and exogenous agents for WEX, CEST, and APT experiments.

    Science.gov (United States)

    Zhou, Jinyuan; Wilson, David A; Sun, Phillip Zhe; Klaus, Judith A; Van Zijl, Peter C M

    2004-05-01

    The proton exchange processes between water and solutes containing exchangeable protons have recently become of interest for monitoring pH effects, detecting cellular mobile proteins and peptides, and enhancing the detection sensitivity of various low-concentration endogenous and exogenous species. In this work, the analytic expressions for water exchange (WEX) filter spectroscopy, chemical exchange-dependent saturation transfer (CEST), and amide proton transfer (APT) experiments are derived by the use of Bloch equations with exchange terms. The effects of the initial states for the system, the difference between a steady state and a saturation state, and the relative contributions of the forward and backward exchange processes are discussed. The theory, in combination with numerical calculations, provides a useful tool for designing experimental schemes and assessing magnetization transfer (MT) processes between water protons and solvent-exchangeable protons. As an example, the case of endogenous amide proton exchange in the rat brain at 4.7 T is analyzed in detail. Copyright 2004 Wiley-Liss, Inc.

  1. Proton solvation and proton transfer in chemical and electrochemical processes

    International Nuclear Information System (INIS)

    Lengyel, S.; Conway, B.E.

    1983-01-01

    This chapter examines the proton solvation and characterization of the H 3 O + ion, proton transfer in chemical ionization processes in solution, continuous proton transfer in conductance processes, and proton transfer in electrode processes. Topics considered include the condition of the proton in solution, the molecular structure of the H 3 O + ion, thermodynamics of proton solvation, overall hydration energy of the proton, hydration of H 3 O + , deuteron solvation, partial molal entropy and volume and the entropy of proton hydration, proton solvation in alcoholic solutions, analogies to electrons in semiconductors, continuous proton transfer in conductance, definition and phenomenology of the unusual mobility of the proton in solution, solvent structure changes in relation to anomalous proton mobility, the kinetics of the proton-transfer event, theories of abnormal proton conductance, and the general theory of the contribution of transfer reactions to overall transport processes

  2. A review of proton exchange membrane water electrolysis on degradation mechanisms and mitigation strategies

    Science.gov (United States)

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

    2017-10-01

    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.

  3. Carbon Nitride Materials as Efficient Catalyst Supports for Proton Exchange Membrane Water Electrolyzers

    Directory of Open Access Journals (Sweden)

    Ana Belen Jorge

    2018-06-01

    Full Text Available Carbon nitride materials with graphitic to polymeric structures (gCNH were investigated as catalyst supports for the proton exchange membrane (PEM water electrolyzers using IrO2 nanoparticles as oxygen evolution electrocatalyst. Here, the performance of IrO2 nanoparticles formed and deposited in situ onto carbon nitride support for PEM water electrolysis was explored based on previous preliminary studies conducted in related systems. The results revealed that this preparation route catalyzed the decomposition of the carbon nitride to form a material with much lower N content. This resulted in a significant enhancement of the performance of the gCNH-IrO2 (or N-doped C-IrO2 electrocatalyst that was likely attributed to higher electrical conductivity of the N-doped carbon support.

  4. Direct fabrication of gas diffusion cathode by pulse electrodeposition for proton exchange membrane water electrolysis

    Science.gov (United States)

    Park, Hyanjoo; Choe, Seunghoe; Kim, Hoyoung; Kim, Dong-Kwon; Cho, GeonHee; Park, YoonSu; Jang, Jong Hyun; Ha, Don-Hyung; Ahn, Sang Hyun; Kim, Soo-Kil

    2018-06-01

    Pt catalysts for water electrolysis were prepared on carbon paper by using both direct current and pulse electrodeposition. Controlling the mass transfer of Pt precursor in the electrolyte by varying the deposition potential enables the formation of various Pt particle shapes such as flower-like and polyhedral particles. Further control of the deposition parameters for pulse electrodeposition resulted in changes to the particle size and density. In particular, the upper potential of pulse was found to be the critical parameter controlling the morphology of the particles and their catalytic activity. In addition to the typical electrochemical measurements, Pt samples deposited on carbon paper were used as cathodes for a proton exchange membrane water electrolyser. This single cell test revealed that our Pt particle samples have exceptional mass activity while being cost effective.

  5. Chloroform and trichloroethylene uptake from water into human skin in vitro: Kinetics and risk implications

    International Nuclear Information System (INIS)

    Bogen, K.T.; Keating, G.A.; Vogel, J.S.

    1995-03-01

    A model recently proposed by the US Environmental Protection Agency (EPA) predicts that short-term dermal uptakes of organic environmental water contaminants are proportional to the square root of exposure time. The model appears to underestimate dermal uptake, based on very limited in vivo uptake data obtained primarily using human subjects. To further assess this model, we examined in vitro dermal uptake kinetics for aqueous organic chemicals using accelerator mass spectrometry (AMS). Specifically, we examined the kinetics of in vitro dermal uptake of 14 C-labeled chloroform and trichloroethylene from dilute (5-ppb) aqueous solutions using full-thickness human cadaver skin exposed for (≤1 hr)

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

    Directory of Open Access Journals (Sweden)

    B.L. Hiran

    2016-11-01

    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.

  7. WE-H-BRA-01: BEST IN PHYSICS (THERAPY): Nano-Dosimetric Kinetic Model for Variable Relative Biological Effectiveness of Proton and Ion Beams

    Energy Technology Data Exchange (ETDEWEB)

    Abolfath, R; Bronk, L; Titt, U.; Grosshans, D; Mohan, R [The University of Texas MD Anderson Cancer Center, Houston, TX (United States); Helo, Y [University College London, London (United Kingdom); Schuemann, J [Massachusetts General Hospital, Boston, MA (United States)

    2016-06-15

    Purpose: Recent clonogenic cell survival and γH2AX studies suggest proton relative biological effectiveness (RBE) may be a non-linear function of linear energy transfer (LET) in the distal edge of the Bragg peak and beyond. We sought to develop a multiscale model to account for non-linear response phenomena to aid in the optimization of intensity-modulated proton therapy. Methods: The model is based on first-principle simulations of proton track structures, including secondary ions, and an analytical derivation of the dependence on particle LET of the linear-quadratic (LQ) model parameters α and β. The derived formulas are an extension of the microdosimetric kinetic (MK) model that captures dissipative track structures and non-Poissonian distribution of DNA damage at the distal edge of the Bragg peak and beyond. Monte Carlo simulations were performed to confirm the non-linear dose-response characteristics arising from the non-Poisson distribution of initial DNA damage. Results: In contrast to low LET segments of the proton depth dose, from the beam entrance to the Bragg peak, strong deviations from non-dissipative track structures and Poisson distribution in the ionization events in the Bragg peak distal edge govern the non-linear cell response and result in the transformation α=(1+c-1 L) α-x+2(c-0 L+c-2 L^2 )(1+c-1 L) β-x and β=(1+c-1 L)^2 β-x. Here L is the charged particle LET, and c-0,c-1, and c-2 are functions of microscopic parameters and can be served as fitting parameters to the cell-survival data. In the low LET limit c-1, and c-2 are negligible hence the linear model proposed and used by Wilkins-Oelfke for the proton treatment planning system can be retrieved. The present model fits well the recent clonogenic survival data measured recently in our group in MDACC. Conclusion: The present hybrid method provides higher accuracy in calculating the RBE-weighted dose in the target and normal tissues.

  8. WE-H-BRA-01: BEST IN PHYSICS (THERAPY): Nano-Dosimetric Kinetic Model for Variable Relative Biological Effectiveness of Proton and Ion Beams

    International Nuclear Information System (INIS)

    Abolfath, R; Bronk, L; Titt, U.; Grosshans, D; Mohan, R; Helo, Y; Schuemann, J

    2016-01-01

    Purpose: Recent clonogenic cell survival and γH2AX studies suggest proton relative biological effectiveness (RBE) may be a non-linear function of linear energy transfer (LET) in the distal edge of the Bragg peak and beyond. We sought to develop a multiscale model to account for non-linear response phenomena to aid in the optimization of intensity-modulated proton therapy. Methods: The model is based on first-principle simulations of proton track structures, including secondary ions, and an analytical derivation of the dependence on particle LET of the linear-quadratic (LQ) model parameters α and β. The derived formulas are an extension of the microdosimetric kinetic (MK) model that captures dissipative track structures and non-Poissonian distribution of DNA damage at the distal edge of the Bragg peak and beyond. Monte Carlo simulations were performed to confirm the non-linear dose-response characteristics arising from the non-Poisson distribution of initial DNA damage. Results: In contrast to low LET segments of the proton depth dose, from the beam entrance to the Bragg peak, strong deviations from non-dissipative track structures and Poisson distribution in the ionization events in the Bragg peak distal edge govern the non-linear cell response and result in the transformation α=(1+c_1 L) α_x+2(c_0 L+c_2 L^2 )(1+c_1 L) β_x and β=(1+c_1 L)^2 β_x. Here L is the charged particle LET, and c_0,c_1, and c_2 are functions of microscopic parameters and can be served as fitting parameters to the cell-survival data. In the low LET limit c_1, and c_2 are negligible hence the linear model proposed and used by Wilkins-Oelfke for the proton treatment planning system can be retrieved. The present model fits well the recent clonogenic survival data measured recently in our group in MDACC. Conclusion: The present hybrid method provides higher accuracy in calculating the RBE-weighted dose in the target and normal tissues.

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

    International Nuclear Information System (INIS)

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

    1995-01-01

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

  10. Electrode kinetics of a water vapor electrolysis cell

    Science.gov (United States)

    Jacobs, G.

    1974-01-01

    The anodic electrochemical behavior of the water vapor electrolysis cell was investigated. A theoretical review of various aspects of cell overvoltage is presented with special emphasis on concentration overvoltage and activation overvoltage. Other sources of overvoltage are described. The experimental apparatus controlled and measured anode potential and cell current. Potentials between 1.10 and 2.60 V (vs NHE) and currents between 0.1 and 3000 mA were investigated. Different behavior was observed between the standard cell and the free electrolyte cell. The free electrolyte cell followed typical Tafel behavior (i.e. activation overvoltage) with Tafel slopes of about 0.15, and the exchange current densities of 10 to the minus 9th power A/sq cm, both in good agreement with literature values. The standard cell exhibitied this same Tafel behavior at lower current densities but deviated toward lower than expected current densities at higher potentials. This behavior and other results were examined to determine their origin.

  11. Radionuclide behavior in water saturated porous media: Diffusion and infiltration coupling of thermodynamically and kinetically controlled radionuclide water - mineral interactions

    International Nuclear Information System (INIS)

    Spasennykh, M.Yu.; Apps, J.A.

    1995-05-01

    A model is developed describing one dimensional radionuclide transport in porous media coupled with locally reversible radionuclide water-mineral exchange reactions and radioactive decay. Problems are considered in which radionuclide transport by diffusion and infiltration processes occur in cases where radionuclide water-solid interaction are kinetically and thermodynamically controlled. The limits of Sr-90 and Cs-137 migration are calculated over a wide range of the problem variables (infiltration velocity, distribution coefficients, and rate constants of water-mineral radionuclide exchange reactions)

  12. Effects of soil water saturation on sampling equilibrium and kinetics of selected polycyclic aromatic hydrocarbons.

    Science.gov (United States)

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

    2017-10-01

    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 (K sampler/soil ) and the uptake rate constant (k u ) 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 K sampler/soil and k u 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 K sampler/soil and k u 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.

  13. Inverse kinetic solvent isotope effect in TiO2 photocatalytic dehalogenation of non-adsorbable aromatic halides: a proton-induced pathway.

    Science.gov (United States)

    Chang, Wei; Sun, Chunyan; Pang, Xibin; Sheng, Hua; Li, Yue; Ji, Hongwei; Song, Wenjing; Chen, Chuncheng; Ma, Wanhong; Zhao, Jincai

    2015-02-09

    An efficient redox reaction between organic substrates in solution and photoinduced h(+) vb /e(-) cb on the surface of photocatalysts requires the substrates or solvent to be adsorbed onto the surface, and is consequentially marked by a normal kinetic solvent isotope effect (KSIE ≥ 1). Reported herein is a universal inverse KSIE (0.6-0.8 at 298 K) for the reductive dehalogenation of aromatic halides which cannot adsorb onto TiO2 in a [D0 ]methanol/[D4 ]methanol solution. Combined with in situ ATR-FTIR spectroscopy investigations, a previously unknown pathway for the transformation of these aromatic halides in TiO2 photocatalysis was identified: a proton adduct intermediate, induced by released H(+) /D(+) from solvent oxidation, accompanies a change in hybridization from sp(2) to sp(3) at a carbon atom of the aromatic halides. The protonation event leads these aromatic halides to adsorb onto the TiO2 surface and an ET reaction to form dehalogenated products follows. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. The calculation of proton and secondary electron stopping powers in liquid water

    International Nuclear Information System (INIS)

    Marouane, Abdelhak; Inchaouh, Jamal; Ouaskit, Said; Fathi, Ahmed

    2012-01-01

    The stopping power of energetic protons in liquid water has been calculated using a new model based on different theoretical and semi-empirical approaches. In this model, we consider the relativistic corrections along with the electronic and nuclear stopping power. The present work accounts for the different interactions made with electrons and nuclei inside the target. Interactions of the incident particle with the target's electrons dominate in the high energy regime; in the low energy regime, the interactions of the projectile with the target nuclei contribute importantly and are included in the calculation. We also compute the stopping cross sections and the stopping power of secondary electrons ejected from proton and hydrogen ionization impact, and generated by hydrogen electron loss processes. The consideration of secondary electrons' stopping power can contribute to the study of nano-dosimetry. Our results are in good agreement with existing experimental data. This calculation model can be useful for different applications in medical physics and space radiation health, such as hadron therapy for cancer treatment or radiation protection for astronauts. - Highlights: ► We discussed the stopping cross sections at the Bragg peak region of primary and secondary processes. ► We considered the corrections of incident particle energy focusing on the Rudds semi-empirical model. ► We calculated the electronic and nuclear stopping power, and we deduced the total stopping power. ► We calculated the stopping power of the secondary electrons.

  15. Kinetics of trace metal removal from tidal water by mangrove sediments under different redox conditions

    International Nuclear Information System (INIS)

    Suzuki, K.N.; Machado, E.C.; Machado, W.; Bellido, A.V.B.; Bellido, L.F.; Osso, J.A.; Lopes, R.T.

    2014-01-01

    The extent in which redox conditions can affect the removal kinetics of 58 Co and 65 Zn from tidal water by mangrove sediments was evaluated in microcosm experiments, simulating a tidal flooding period of 6 h. The average half-removal time (t 1/2 ) of 58 Co from overlaying water was slightly higher (7.3 h) under an N 2 -purged water column than under an aerated water column (5.4 h). A lower difference was found for 65 Zn (1.9 h vs. 1.5 h, respectively). Average removals of 58 Co activities from water were 54.6% (N 2 treatment) and 43.5% (aeration treatment), whereas these values were 88.0% and 92.7% for 65 Zn, respectively. Very contrasting sorption kinetics of different radiotracers occurred, while more oxidising conditions favoured only a slightly higher removal. Average 58 Co and 65 Zn inventories within sediments were 30.4% and 18.8% higher in the aeration treatment, respectively. A stronger particle-reactive behaviour was found for 65 Zn that was less redox-sensitive and more efficiently removed by sediments than 58 Co. - Highlights: ► Radiotracer experiments evidenced the role of mangrove sediments in trapping trace metals. ► Very contrasting removal kinetics from tidal water were observed for 65 Zn and 58 Co. ► Nearly 40%–50% of 58 Co activities and nearly 90% of 65 Zn activities in overlying water were removed. ► 65 Zn showed a stronger particle-reactive behaviour than observed for 58 Co. ► 58 Co was more sensitive to redox conditions in tidal water than observed for 65 Zn

  16. Tunneling Kinetics and Nonadiabatic Proton-Coupled Electron Transfer in Proteins: The Effect of Electric Fields and Anharmonic Donor-Acceptor Interactions.

    Science.gov (United States)

    Salna, Bridget; Benabbas, Abdelkrim; Russo, Douglas; Champion, Paul M

    2017-07-20

    A proper description of proton donor-acceptor (D-A) distance fluctuations is crucial for understanding tunneling in proton-coupled electron transport (PCET). The typical harmonic approximation for the D-A potential results in a Gaussian probability distribution, which does not appropriately reflect the electronic repulsion forces that increase the energetic cost of sampling shorter D-A distances. Because these shorter distances are the primary channel for thermally activated tunneling, the analysis of tunneling kinetics depends sensitively on the inherently anharmonic nature of the D-A interaction. Thus, we have used quantum chemical calculations to account for the D-A interaction and developed an improved model for the analysis of experimental tunneling kinetics. Strong internal electric fields are also considered and found to contribute significantly to the compressive forces when the D-A distance distribution is positioned below the van der Waals contact distance. This model is applied to recent experiments on the wild type (WT) and a double mutant (DM) of soybean lipoxygenase-1 (SLO). The compressive force necessary to prepare the tunneling-active distribution in WT SLO is found to fall in the ∼ nN range, which greatly exceeds the measured values of molecular motor and protein unfolding forces. This indicates that ∼60-100 MV/cm electric fields, aligned along the D-A bond axis, must be generated by an enzyme conformational interconversion that facilitates the PCET tunneling reaction. Based on the absolute value of the measured tunneling rate, and using previously calculated values of the electronic matrix element, the population of this tunneling-active conformation is found to lie in the range 10 -5 -10 -7 , indicating this is a rare structural fluctuation that falls well below the detection threshold of recent ENDOR experiments. Additional analysis of the DM tunneling kinetics leads to a proposal that a disordered (high entropy) conformation could be

  17. Ozonation and H2O2/UV treatment of clofibric acid in water: a kinetic investigation.

    Science.gov (United States)

    Andreozzi, Roberto; Caprio, Vincenzo; Marotta, Raffaele; Radovnikovic, Anita

    2003-10-31

    The presence of pharmaceuticals or their active metabolites in surface and ground waters has been recently reported as mainly due to an incomplete removal of these pollutants in sewage treatment plants (STP). Advanced oxidation processes may represent a suitable tool to reduce environmental release of these species by enhancing the global efficiency of reduction of pharmaceuticals in the municipal sewage plant effluents. The present work aims at assessing the kinetics of abatement from aqueous solutions of clofibric acid (a metabolite of the blood lipid regulator clofibrate) which has been found in surface, ground and drinking waters. Ozonation and hydrogen peroxide photolysis are capable of fast removal of this species in aqueous solution, with an almost complete conversion of the organic chlorine content into chloride ions for the investigated reaction conditions. A validation of assessed kinetics at clofibric acid concentrations as low as those found in STP effluents is presented for both systems.

  18. Development of Less Water-Dependent Radiation Grafted Proton Exchange Membranes for Fuel Cells

    Energy Technology Data Exchange (ETDEWEB)

    Nasef, M M; Ahmad, A; Saidi, H; Dahlan, K Z.M. [Institute of Hydrogen Economy, Energy Research Alliance (ERA), International Campus, Univeristi Teknologi Malaysia, Jalan Semarak, Kuala Lumpur (Malaysia); Radiation Processing Division, Malaysian Nuclear Agency, Bangi, Kajang (Malaysia)

    2012-09-15

    The aim of these studies was the development of proton exchange membranes for polymer electrolyte membrane (PEM) fuel cell operated above 100{sup o}C, in order to obtain less water dependent, high quality and cheap electrolyte membrane. Sulfonic acid membranes were prepared by radiation induced grafting (RIG) of sodium styrene sulfonate (SSS) onto electron beam (EB) irradiated poly(vinylidene fluoride) (PVDF) films in a single step reaction for the first time using synergetic effect of acid addition to grafting mixture under various grafting conditions. The fuel cell related properties of the membranes were evaluated and the in situ performance was tested in a single H{sub 2}/O{sub 2} fuel cell under dynamic conditions and compared with a similar sulfonated polystyrene PVDF membrane obtained by two-step conventional RIG method i.e. grafting of styrene and subsequent sulfonation. The newly obtained membrane (degree of grafting, G% = 53) showed an improved performance and higher stability together with a cost reduction mainly as a result of elimination of sulfonation reaction. Acid-base composite membranes were also studied. EB pre-irradiated poly(ethylene-co-tetrafluoroethylene) (ETFE) films were grafted with N-vinyl pyridine (NVP). The effects of monomer concentration, dose, reaction time, film thickness, temperature and film storage time on G% were investigated. The membranes were subsequently doped with phosphoric acid under controlled condition. The proton conductivity of these membranes was investigated under low water conditions in correlation with the variation in G% and temperature (30-130{sup o}C). The performance of 34 and 49% grafted and doped membranes was tested in a single fuel cell at 130{sup o}C under dynamic conditions with 146 and 127 mW/cm{sup 2} power densities. The polarization, power density characteristics and the initial stability of the membrane showed a promising electrolyte candidate for fuel cell operation above 100 deg. C. (author)

  19. Water droplet accumulation and motion in PEM (Proton Exchange Membrane) fuel cell mini-channels

    International Nuclear Information System (INIS)

    Carton, J.G.; Lawlor, V.; Olabi, A.G.; Hochenauer, C.; Zauner, G.

    2012-01-01

    Effective water management is one of the key strategies for improving low temperature PEM (Proton Exchange Membrane) fuel cell performance and durability. Phenomena such as membrane dehydration, catalyst layer flooding, mass transport and fluid flow regimes can be affected by the interaction, distribution and movement of water in flow plate channels. In this paper a literature review is completed in relation to PEM fuel cell water flooding. It is clear that droplet formation, movement and interaction with the GDL (Gas Diffusion Layer) have been studied extensively. However slug formation and droplet accumulation in the flow channels has not been analysed in detail. In this study, a CFD (Computational Fluid Dynamic) model and VOF (Volume of Fluid) method is used to simulate water droplet movement and slug formation in PEM fuel cell mini-channels. In addition, water slug visualisation is recorded in ex situ PEM fuel cell mini-channels. Observation and simulation results are discussed with relation to slug formation and the implications to PEM fuel cell performance. -- Highlights: ► Excess water in mini-channels from the collision and coalescence of droplets can directly form slugs in PEM fuel cells. ► Slugs can form at low flow rates so increasing the flow rate can reduce the size and frequency of slugs. ► One channel of a double serpentine mini-channel may become blocked due to the redistribution of airflow and pressure caused by slug formation. ► Correct GDL and mini-channel surface coatings are essential to reduce slug formation and stagnation. ► Having geometry changes (bends and steps) in the flow fields can disrupt slug movement and avoid channel blockages.

  20. On the nuclear halo of a proton pencil beam stopping in water

    International Nuclear Information System (INIS)

    Gottschalk, Bernard; Cascio, Ethan W; Daartz, Juliane; Wagner, Miles S

    2015-01-01

    The dose distribution of a proton beam stopping in water has components due to basic physics and may have others from beam contamination. We propose the concise terms core for the primary beam, halo (see Pedroni et al 2005 Phys. Med. Biol. 50 541–61) for the low dose region from charged secondaries, aura for the low dose region from neutrals, and spray for beam contamination.We have measured the dose distribution in a water tank at 177 MeV under conditions where spray, therefore radial asymmetry, is negligible. We used an ADCL calibrated thimble chamber and a Faraday cup calibrated integral beam monitor so as to obtain immediately the absolute dose per proton. We took depth scans at fixed distances from the beam centroid rather than radial scans at fixed depths. That minimizes the signal range for each scan and better reveals the structure of the core and halo.Transitions from core to halo to aura are already discernible in the raw data. The halo has components attributable to coherent and incoherent nuclear reactions. Due to elastic and inelastic scattering by the nuclear force, the Bragg peak persists to radii larger than can be accounted for by Molière single scattering. The radius of the incoherent component, a dose bump around midrange, agrees with the kinematics of knockout reactions.We have fitted the data in two ways. The first is algebraic or model dependent (MD) as far as possible, and has 25 parameters. The second, using 2D cubic spline regression, is model independent. Optimal parameterization for treatment planning will probably be a hybrid of the two, and will of course require measurements at several incident energies.The MD fit to the core term resembles that of the PSI group (Pedroni et al 2005), which has been widely emulated. However, we replace their T(w), a mass stopping power which mixes electromagnetic (EM) and nuclear effects, with one that is purely EM, arguing that protons that do not undergo hard single scatters continue to lose energy

  1. On the nuclear halo of a proton pencil beam stopping in water

    Science.gov (United States)

    Gottschalk, Bernard; Cascio, Ethan W.; Daartz, Juliane; Wagner, Miles S.

    2015-07-01

    The dose distribution of a proton beam stopping in water has components due to basic physics and may have others from beam contamination. We propose the concise terms core for the primary beam, halo (see Pedroni et al 2005 Phys. Med. Biol. 50 541-61) for the low dose region from charged secondaries, aura for the low dose region from neutrals, and spray for beam contamination. We have measured the dose distribution in a water tank at 177 MeV under conditions where spray, therefore radial asymmetry, is negligible. We used an ADCL calibrated thimble chamber and a Faraday cup calibrated integral beam monitor so as to obtain immediately the absolute dose per proton. We took depth scans at fixed distances from the beam centroid rather than radial scans at fixed depths. That minimizes the signal range for each scan and better reveals the structure of the core and halo. Transitions from core to halo to aura are already discernible in the raw data. The halo has components attributable to coherent and incoherent nuclear reactions. Due to elastic and inelastic scattering by the nuclear force, the Bragg peak persists to radii larger than can be accounted for by Molière single scattering. The radius of the incoherent component, a dose bump around midrange, agrees with the kinematics of knockout reactions. We have fitted the data in two ways. The first is algebraic or model dependent (MD) as far as possible, and has 25 parameters. The second, using 2D cubic spline regression, is model independent. Optimal parameterization for treatment planning will probably be a hybrid of the two, and will of course require measurements at several incident energies. The MD fit to the core term resembles that of the PSI group (Pedroni et al 2005), which has been widely emulated. However, we replace their T(w), a mass stopping power which mixes electromagnetic (EM) and nuclear effects, with one that is purely EM, arguing that protons that do not undergo hard single scatters continue to lose

  2. Kinetics and mechanism for degradation of dichlorvos by permanganate in drinking water treatment.

    Science.gov (United States)

    Liu, Chao; Qiang, Zhimin; Adams, Craig; Tian, Fang; Zhang, Tao

    2009-08-01

    The degradation kinetics and mechanism of dichlorvos by permanganate during drinking water treatment were investigated. The reaction of dichlorvos with permanganate was of second-order overall with negligible pH dependence and an activation energy of 29.5 kJ x mol(-1). At pH 7.0 and 25 degrees C, the rate constant was 25.2+/-0.4M(-1)s(-1). Dichlorvos was first degraded to trimethyl phosphate (TMP) and dimethyl phosphate (DMP) simultaneously which approximately accounted for or=95% with respect to phosphorus mass, respectively. Further oxidation of DMP generated a final byproduct, monomethyl phosphate (MMP). MMP was for the first time identified as a major byproduct in chemical oxidation of dichlorvos. The kinetic model based on degradation mechanism and determined reaction rate constants allowed us to predict the evolution of dichlorvos and its byproduct concentrations during permanganate pre-oxidation process at water treatment plants. These results suggest that even though the dichlorvos concentration in surface water complies with the surface water quality standards of China (50 microg L(-1)), its concentration after conventional water treatment will most probably exceed the drinking water quality standards (1 microg L(-1)). Moreover, luminescent bacteria test shows that the acute toxicity of dichlorvos solution evidently increased after permanganate oxidation.

  3. Reactions of plutonium and uranium with water: Kinetics and potential hazards

    International Nuclear Information System (INIS)

    Haschke, J.M.

    1995-12-01

    The chemistry and kinetics of reactions between water and the metals and hydrides of plutonium and uranium are described in an effort to consolidate information for assessing potential hazards associated with handling and storage. New experimental results and data from literature sources are presented. Kinetic dependencies on pH, salt concentration, temperature and other parameters are reviewed. Corrosion reactions of the metals in near-neutral solutions produce a fine hydridic powder plus hydrogen. The corrosion rate for plutonium in sea water is a thousand-fold faster than for the metal in distilled water and more than a thousand-fold faster than for uranium in sea water. Reaction rates for immersed hydrides of plutonium and uranium are comparable and slower than the corrosion rates for the respective metals. However, uranium trihydride is reported to react violently if a quantity greater than twenty-five grams is rapidly immersed in water. The possibility of a similar autothermic reaction for large quantities of plutonium hydride cannot be excluded. In addition to producing hydrogen, corrosion reactions convert the massive metals into material forms that are readily suspended in water and that are aerosolizable and potentially pyrophoric when dry. Potential hazards associated with criticality, environmental dispersal, spontaneous ignition and explosive gas mixtures are outlined

  4. Separation of oily materials in radioactive waste waters by flotation. Flotation kinetics

    International Nuclear Information System (INIS)

    Flores E, R.M.; Ortiz O, H.B.

    2003-01-01

    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 -1 ) and with modified anionic polyacrylamide (1.5 mgL -1 ) (pH = 7, G 1 = 300 s -1 and G 2 = 30 s -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 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 -1 , on the other hand, the concentration of the 60 Co at the end of the flotation process resulted smaller than 0.008 Bq/ml, as long as the one 54 Mn were not detectable. (Author)

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

    International Nuclear Information System (INIS)

    Salgado, R.; Pereira, V.J.; Carvalho, G.; Soeiro, R.; Gaffney, V.; Almeida, C.; Cardoso, V. Vale; Ferreira, E.; Benoliel, M.J.

    2013-01-01

    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

  6. 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: gs.carvalho@fct.unl.pt [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

    2013-01-15

    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.

  7. 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)

    2015-05-01

    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.

  8. Evaluation of self-water-removal in a dead-ended proton exchange membrane fuel cell

    International Nuclear Information System (INIS)

    Wan, Zhongmin; Liu, Jing; Luo, Zhiping; Tu, Zhengkai; Liu, Zhichun; Liu, Wei

    2013-01-01

    Highlights: ► Operation characteristics in a dead-ended PEM fuel cell were addressed. ► Modified flow channel was used to realize water removal. ► A novel method by condensing the moisture in the stack end was introduced. - Abstract: In this paper, the operation characteristic of a dead-ended proton exchange membrane fuel cell (PEMFC) placed with vertical orientation is investigated. The relationship between the channel geometry and the wettability of the gas diffusion layer (GDL) surface is theoretically analyzed. Based on the theoretical analysis, straight flow channels with 2.0 mm width and 1.0 mm depth are used for the experimental investigation and the moisture is condensed at the stack end to improve water removal. The results show that the designed fuel cell can operate for about 1 h at 800 mA cm −2 and the performance of the cell decreases with the increase in the operation temperature. Moreover, the recovered liquid water is corresponded closely to the theoretical values

  9. On the Effect of Clamping Pressure and Method on the Current Mapping of Proton Exchange Membrane Water Electrolysis

    DEFF Research Database (Denmark)

    Al Shakhshir, Saher; Zhou, Fan; Kær, Søren Knudsen

    The degradation of the electrochemical reaction of the proton exchange membrane water electrolysis (PEMWE) can be characterized using in-situ current mapping measurements (CMM). CMM is significantly affected by the amount of clamping pressure and method. In this work the current is mapped...

  10. Dynamic behavior of liquid water transport in a tapered channel of a proton exchange membrane fuel cell cathode

    NARCIS (Netherlands)

    Akhtar, N.; Kerkhof, P.J.A.M.

    2011-01-01

    A numerical model of a proton exchange membrane fuel cell (PEMFC) cathode with a tapered channel design has been developed in order to examine the dynamic behavior of liquid water transport. Three-dimensional, transient simulations employing the level-set method (available in COMSOL 3.5a, a

  11. Dose distribution of secondary radiation in a water phantom for a proton pencil beam-EURADOS WG9 intercomparison exercise

    Czech Academy of Sciences Publication Activity Database

    Stolarczyk, L.; Trinkl, S.; Romero-Exposito, M.; Mojzeszek, N.; Ambrožová, Iva; Domingo, C.; Davídková, Marie; Farah, J.; Klodowska, M.; Kneževic, Z.; Liszka, M.; Majer, M.; Miljanic, S.; Ploc, Ondřej; Schwarz, M.; Harrison, R. M.; Olko, P.

    2018-01-01

    Roč. 63, č. 8 (2018), č. článku 085017. ISSN 0031-9155 Institutional support: RVO:61389005 Keywords : passive detectors * neutron dosimetry * gamma radiation dosimetry * water phantom measurements * secondary radiation measurements * pencil beam scanning proton radiotherapy Subject RIV: FP - Other Medical Disciplines OBOR OECD: Radiology, nuclear medicine and medical imaging Impact factor: 2.742, year: 2016

  12. Predicting liquid water saturation through differently structured cathode gas diffusion media of a proton exchange Membrane Fuel Cell

    NARCIS (Netherlands)

    Akhtar, N.; Kerkhof, P.J.A.M.

    2012-01-01

    The role of gas diffusion media with differently structured properties have been examined with emphasis on the liquid water saturation within the cathode of a proton exchange membrane fuel cell (PEMFC). The cathode electrode consists of a gas diffusion layer (GDL), a micro-porous layer and a

  13. Amide proton transfer (APT) imaging of brain tumors at 7 T : The role of tissue water T1 -Relaxation properties

    NARCIS (Netherlands)

    Khlebnikov, V; Polders, Daniel; Hendrikse, J; Robe, Pierre A.; Voormolen, Eduard H; Luijten, Peter R; Klomp, DWJ; Hoogduin, Hans

    PURPOSE: To provide insight into the effect of water T1 relaxation (T1wat ) on amide proton transfer (APT) contrast in tumors. Three different metrics of APT contrast-magnetization transfer ratio (MTRRex ), relaxation-compensated MTRRex (AREX), and traditional asymmetry (MTRasym )-were compared in

  14. 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

    2007-01-01

    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...

  15. DNA-Accelerated Copper Catalysis of Friedel-Crafts Conjugate Addition/Enantioselective Protonation Reactions in Water

    NARCIS (Netherlands)

    García-Fernández, Almudena; Megens, Rik P.; Villarino, Lara; Roelfes, Gerard

    2016-01-01

    DNA-induced rate acceleration has been identified as one of the key elements for the success of the DNA-based catalysis concept. Here we report on a novel DNA-based catalytic Friedel-Crafts conjugate addition/enantioselective protonation reaction in water, which represents the first example of a

  16. Kinetic stability of the dysprosium(3) complex with tetraazaporphine in acetic acid-water and acetic acid-methanol mixtures

    International Nuclear Information System (INIS)

    Khelevina, O.G.; Vojnov, A.A.

    1999-01-01

    Water-soluble dysprosium tetraazaporphine with acetylacetonate-ion as extraligand is synthesized for the first time. Its kinetic stability in acetic acid solutions is investigated. It is shown that the complex is dissociated with formation of free tetraazaporphine. Kinetic parameters of dissociation reaction are determined [ru

  17. Wetting kinetics of water nano-droplet containing non-surfactant nanoparticles: A molecular dynamics study

    International Nuclear Information System (INIS)

    Lu, Gui; Hu, Han; Sun, Ying; Duan, Yuanyuan

    2013-01-01

    In this Letter, dynamic wetting of water nano-droplets containing non-surfactant gold nanoparticles on a gold substrate is examined via molecular dynamics simulations. The results show that the addition of non-surfactant nanoparticles hinders the nano-second droplet wetting process, attributed to the increases in both surface tension of the nanofluid and friction between nanofluid and substrate. The droplet wetting kinetics decreases with increasing nanoparticle loading and water-particle interaction energy. The observed wetting suppression and the absence of nanoparticle ordering near the contact line of nano-sized droplets differ from the wetting behaviors reported from nanofluid droplets of micron size or larger

  18. A kinetic study of the reaction of water vapor and carbon dioxide on uranium

    International Nuclear Information System (INIS)

    Santon, J.P.

    1964-09-01

    The kinetic study of the reaction of water vapour and carbon dioxide with uranium has been performed by thermogravimetric methods at temperatures between 160 and 410 deg G in the first case, 350 and 1050 deg C in the second: Three sorts of uranium specimens were used: uranium powder, thin evaporated films, and small spheres obtained from a plasma furnace. The experimental results led in the case of water vapour, to a linear rate of reaction controlled by diffusion at the lower temperatures, and by a surface reaction at the upper ones. In the case of carbon dioxide, a parabolic law has been found, controlled by diffusional processes. (author) [fr

  19. Water absorption and biodegradation kinetics of highly filled EOC-FS biocomposites

    Science.gov (United States)

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

    2017-12-01

    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.

  20. Modeling of radiocesium transport kinetics in system water-aquatic plants

    International Nuclear Information System (INIS)

    Svadlenkova, M.

    1988-01-01

    Compartment models were used to describe the kinetics of the transport of radionuclides in the system water-biomass of aquatic plants. Briefly described are linear models and models with time variable parameters. The model was tested using data from a locality in the environs of the Bohunice nuclear power plant. Cladophora glomerata algae were the monitored plants, 137 Cs the monitored radionuclide. The models may be used when aquatic plants serve as bioindicators of the radioactive contamination of surface waters, for monitoring the transport of radionuclides in food chains. (M.D.). 10 refs

  1. Calculations and measurements of the scintillator-to-water stopping power ratio of liquid scintillators for use in proton radiotherapy

    International Nuclear Information System (INIS)

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

    2015-01-01

    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

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

    Science.gov (United States)

    Laureys, David

    2014-01-01

    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. PMID:24532061

  3. Microbial species diversity, community dynamics, and metabolite kinetics of water kefir fermentation.

    Science.gov (United States)

    Laureys, David; De Vuyst, Luc

    2014-04-01

    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.

  4. NMR water-proton spin-lattice relaxation time of human red blood cells and red blood cell suspensions

    International Nuclear Information System (INIS)

    Sullivan, S.G.; Rosenthal, J.S.; Winston, A.; Stern, A.

    1988-01-01

    NMR water-proton spin-lattice relaxation times were studied as probes of water structure in human red blood cells and red blood cell suspensions. Normal saline had a relaxation time of about 3000 ms while packed red blood cells had a relaxation time of about 500 ms. The relaxation time of a red blood cell suspension at 50% hematocrit was about 750 ms showing that surface charges and polar groups of the red cell membrane effectively structure extracellular water. Incubation of red cells in hypotonic saline increases relaxation time whereas hypertonic saline decreases relaxation time. Relaxation times varied independently of mean corpuscular volume and mean corpuscular hemoglobin concentration in a sample population. Studies with lysates and resealed membrane ghosts show that hemoglobin is very effective in lowering water-proton relaxation time whereas resealed membrane ghosts in the absence of hemoglobin are less effective than intact red cells. 9 refs.; 3 figs.; 1 table

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

    Directory of Open Access Journals (Sweden)

    Stephan Loew

    2011-01-01

    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.

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

    DEFF Research Database (Denmark)

    Kuznetsov, A.M.; Ulstrup, Jens

    2004-01-01

    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...... of model molecular potentials, and with reference to the excess proton conductivity in aqueous solution....

  7. 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: pzhang@nmemc.org.cn [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)

    2016-03-15

    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

  8. 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

    2016-01-01

    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...... 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...... signal received gives valuable insight into heat and mass transfer phenomena in a PEMFC....

  9. Adsorption kinetics of c-Fos and c-Jun to air-water interfaces.

    Science.gov (United States)

    Del Boca, Maximiliano; Nobre, Thatyane Morimoto; Zaniquelli, Maria Elisabete Darbello; Maggio, Bruno; Borioli, Graciela A

    2007-11-01

    The kinetics of adsorption to air-water interfaces of the biomembrane active transcription factors c-Fos, c-Jun and their mixtures is investigated. The adsorption process shows three distinct stages: a lag time, a fast pseudo zero-order stage, and a halting stage. The initial stage determines the course of the process, which is concentration dependent until the end of the fast stage. We show that c-Fos has faster adsorption kinetics than c-Jun over all three stages and that the interaction between both proteins is apparent in the adsorption profiles of the mixtures. Protein molecular reorganization at the interface determines the transition to the final adsorption stage of the pure proteins as well as that of the mixtures.

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

    Directory of Open Access Journals (Sweden)

    Stanis³aw J. Pogorzelski

    2001-12-01

    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.

  11. Kinetics of the high- to low-density amorphous water transition

    International Nuclear Information System (INIS)

    Koza, M M; Schober, H; Fischer, H E; Hansen, T; Fujara, F

    2003-01-01

    In situ neutron diffraction experiments have been carried out to study the kinetics of the transformation of high-density amorphous (HDA) water into its low-density amorphous state at temperatures 87 K ≤ T ≤ 110 K. It is found that three different stages are comprised in this transformation, namely an annealing process of the high-density matrix followed by a first-order-like transition into a low-density state, which can be further annealed at higher temperatures T ≤ 127 K. The annealing kinetics of the HDA state follows the logarithm of time as found in other systems showing polyamorphism. According to the theory of transformation by nucleation and growth the apparent first-order transition follows an Avrami-Kolmogorov behaviour. An energy barrier ΔE ∼ 33 k Jmol -1 is estimated from the temperature dependence of this transition

  12. KINETICS OF THE PHOTOCATALYTIC DEGRADATION OF SELECTED ORGANIC MICROPOLLUTANTS IN THE WATER ENVIROMENT

    Directory of Open Access Journals (Sweden)

    Edyta Anna Kudlek

    2017-04-01

    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.

  13. Kinetic model for the radical degradation of tri-halonitromethane disinfection byproducts in water

    International Nuclear Information System (INIS)

    Mezyk, Stephen P.; Mincher, Bruce J.; Cooper, William J.; Kirkham Cole, S.; Fox, Robert V.; Gardinali, Piero R.

    2012-01-01

    The halonitromethanes (HNMs) are byproducts of the ozonation and chlorine/chloramine treatment of drinking waters. Although typically occurring at low concentrations HNMs have high cytotoxicity and mutagenicity, and may therefore represent a significant human health hazard. In this study, we have investigated the radical based mineralization of fully-halogenated HNMs in water using the congeners bromodichloronitromethane and chlorodibromonitromethane. We have combined absolute reaction rate constants for their reactions with the hydroxyl radical and the hydrated electron as measured by electron pulse radiolysis and analytical measurements of stable product concentrations obtained by 60 Co steady-state radiolysis with a kinetic computer model that includes water radiolysis reactions and halide/nitrogen oxide radical chemistry to fully elucidate the reaction pathways of these HNMs. These results are compared to our previous similar study of the fully chlorinated HNM chloropicrin. The full optimized computer model, suitable for predicting the behavior of this class of compounds in irradiated drinking water, is provided. - Highlights: ► Radical-based mineralization of aqueous halonitromethane disinfection byproducts. ► Constructed kinetic computer model for tri-halogenated halonitromethane removal. ► Model predicted that superoxide reaction is unimportant for halonitromethanes. ► Measured superoxide reaction with chloropicrin was negligibly slow, 4 M −1 s −1 . ► Determined that superoxide reaction with nitrate also insignificant at ∼10 4 M −1 s −1 .

  14. Pulse radiolysis of porphyrin and ferriporphyrin solutions in 2-propanol-carbon tetrachloride systems. Protonation and ligand exchange kinetics

    International Nuclear Information System (INIS)

    Brault, D.; Neta, P.

    1983-01-01

    Pulse radiolysis of aqueous and nonaqueous 2-propanol-acetone-carbon tetrachloride mixtures has been investigated by means of conductivity measurements and spectrophotometry. In these solvent mixtures, a pulse of hydrochloric acid originating from either primary events of solvent radiolysis or from further reactions of carbon tetrachloride with radicals derived from 2-propanol and acetone, is produced within ca 100 nanoseconds. Further production of hydrochloric acid occurs as a result of chain reactions involving hydrogen abstraction by CCl 3 or CCl 3 O 2 radicals. These latter radicals appear to be much more reactive and are likely to be involved in the reaction unless the solutions have been thoroughly deoxygenated. Protonation Reactions of porphyrins and ferriporphyrins, which do not react rapidly with the above radicals, were followed by means of spectrophotometric measurements. In turn, these reactions may be used to monitor hydrochloric acid formation. Spectrophotometric measurements on porphyrins corroborate conductivity results, although a quantitative comparison is not feasible because of differences in solvent properties. 6 figures

  15. Pressure control of a proton beam-irradiated water target through an internal flow channel-induced thermosyphon.

    Science.gov (United States)

    Hong, Bong Hwan; Jung, In Su

    2017-07-01

    A water target was designed to enhance cooling efficiency using a thermosyphon, which is a system that uses natural convection to induce heat exchange. Two water targets were fabricated: a square target without any flow channel and a target with a flow channel design to induce a thermosyphon mechanism. These two targets had the same internal volume of 8 ml. First, visualization experiments were performed to observe the internal flow by natural convection. Subsequently, an experiment was conducted to compare the cooling performance of both water targets by measuring the temperature and pressure. A 30-MeV proton beam with a beam current of 20 μA was used to irradiate both targets. Consequently, the target with an internal flow channel had a lower mean temperature and a 50% pressure drop compared to the target without a flow channel during proton beam irradiation. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. Kinetics of the reaction between H· and superheated water probed with muonium

    Energy Technology Data Exchange (ETDEWEB)

    Alcorn, C. [Mount Allison Univ., Sackville, NB (Canada); Brodovitch, J.-C. [Simon Fraser Univ., Burnaby, BC (Canada); Ghandi, K.; Kennedy, A. [Mount Allison Univ., Sackville, NB (Canada); Percival, P.W. [Simon Fraser Univ., Burnaby, BC (Canada); TRIUMF, Vancouver, BC (Canada); Smith, M. [Mount Allison Univ., Sackville, NB (Canada)

    2011-07-01

    Safe operation of a supercritical water cooled reactor requires knowledge of the reaction kinetics of transient species formed by the radiolysis of water in the temperature range 300-650{sup o}C. By using a light isotope of the H·atom, it is possible to study its chemistry in water over this range of temperatures. Arguably, the most important reaction to study is that of the H·atom with the bulk solvent. This reaction could provide an in situ source of H{sub 2} gas, which is added to CANDU reactors to suppress oxidative corrosion. The work described here concerns studies of the reaction of muonium with H{sub 2}O and D{sub 2}O at temperatures up to 450{sup o}C.

  17. Kinetics of the reaction between H· and superheated water probed with muonium

    International Nuclear Information System (INIS)

    Alcorn, C.; Brodovitch, J.-C.; Ghandi, K.; Kennedy, A.; Percival, P.W.; Smith, M.

    2011-01-01

    Safe operation of a supercritical water cooled reactor requires knowledge of the reaction kinetics of transient species formed by the radiolysis of water in the temperature range 300-650"oC. By using a light isotope of the H·atom, it is possible to study its chemistry in water over this range of temperatures. Arguably, the most important reaction to study is that of the H·atom with the bulk solvent. This reaction could provide an in situ source of H_2 gas, which is added to CANDU reactors to suppress oxidative corrosion. The work described here concerns studies of the reaction of muonium with H_2O and D_2O at temperatures up to 450"oC.

  18. Isotopic modeling of water and sodium distribution and exchange kinetics in 7 stable hemodialysis patients

    International Nuclear Information System (INIS)

    Chamoiseau, S.; Bertrou, L.; Pujo, J.M.; Massol, M.

    1988-01-01

    Sequential serum sampling over 24 h. has been performed in 7 hemodialysis patients after simultaneous intra-venous injection of tritiated water and 24 Na. Each time-activity curve fits a biexponential pattern. A compartment analysis leads to describe either a simple but incomplete single compartment model or a much more satisfactory open two-compartment mamillary model featuring 2 intercompartment transfer rate constants k 21 and k 12 , and a loss out of the system, k 01 . These constants can be related to intrabody resistances to sodium and water transfers. Compartment analysis allows a comprehensive quantitated description of the exchange and transfer kinetics of sodium and water throughout the system. Evidence for a sodium reservoir, probably located in bone, can be drawn from the results and leads to propose a strategy for a targetted bone sodium removal [fr

  19. 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)

    2016-07-01

    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)

  20. 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

    2015-01-01

    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...

  1. Studies on kinetics of water quality factors to establish water transparency model in Neijiang River, China.

    Science.gov (United States)

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

    2014-05-01

    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.

  2. 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)

    2004-07-01

    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)

  3. 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: kirschnd@bc.edu [Boston College, Chestnut Hill, MA 02467 (United States)

    2014-12-01

    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.

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

    Science.gov (United States)

    Zhao, Lei; Cheng, Jiangtao

    2017-09-07

    In this paper, we report molecular kinetic analyses of water spreading on hydrophobic surfaces via molecular dynamics simulation. The hydrophobic surfaces are composed of amorphous polytetrafluoroethylene (PTFE) with a static contact angle of ~112.4° for water. On the basis of the molecular kinetic theory (MKT), the influences of both viscous damping and solid-liquid retarding were analyzed in evaluating contact line friction, which characterizes the frictional force on the contact line. The unit displacement length on PTFE was estimated to be ~0.621 nm and is ~4 times as long as the bond length of C-C backbone. The static friction coefficient was found to be ~[Formula: see text] Pa·s, which is on the same order of magnitude as the dynamic viscosity of water, and increases with the droplet size. A nondimensional number defined by the ratio of the standard deviation of wetting velocity to the characteristic wetting velocity was put forward to signify the strength of the inherent contact line fluctuation and unveil the mechanism of enhanced energy dissipation in nanoscale, whereas such effect would become insignificant in macroscale. Moreover, regarding a liquid droplet on hydrophobic or superhydrophobic surfaces, an approximate solution to the base radius development was derived by an asymptotic expansion approach.

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

    International Nuclear Information System (INIS)

    Machet, A.; Galtayries, A.; Zanna, S.; Marcus, P.; Jolivet, P.; Scott, P.; Foucault, M.; Combrade, P.

    2004-01-01

    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 2 O 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 2 O 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)

  6. Free chlorine and monochloramine inactivation kinetics of Aspergillus and Penicillium in drinking water.

    Science.gov (United States)

    Ma, Xiao; Bibby, Kyle

    2017-09-01

    Fungi are near-ubiquitous in potable water distribution systems, but the disinfection kinetics of commonly identified fungi are poorly studied. In the present study, laboratory scale experiments were conducted to evaluate the inactivation kinetics of Aspergillus fumigatus, Aspergillus versicolor, and Penicillium purpurogenum by free chlorine and monochloramine. The observed inactivation data were then fit to a delayed Chick-Watson model. Based on the model parameter estimation, the Ct values (integrated product of disinfectant concentration C and contact time t over defined time intervals) for 99.9% inactivation of the tested fungal strains ranged from 48.99 mg min/L to 194.7 mg min/L for free chlorine and from 90.33 mg min/L to 531.3 mg min/L for monochloramine. Fungal isolates from a drinking water system (Aspergillus versicolor and Penicillium purpurogenum) were more disinfection resistant than Aspergillus fumigatus type and clinical isolates. The required 99.9% inactivation Ct values for the tested fungal strains are higher than E. coli, a commonly monitored indicator bacteria, and within a similar range for bacteria commonly identified within water distribution systems, such as Mycobacterium spp. and Legionella spp. Copyright © 2017 Elsevier Ltd. All rights reserved.

  7. ETHANOL-WATER ADSORPTION ON COMMERCIAL 3A ZEOLITES: KINETIC AND THERMODYNAMIC DATA

    Directory of Open Access Journals (Sweden)

    M.J. Carmo

    1997-09-01

    Full Text Available Dehydration of ethanol via adsorption using molecular sieves has recently been suggested as a promising alternative to the conventional separation methods for ethanol-water mixtures. 3A zeolites possess selective micropores whereon, due to the small size of their pores, the water molecules are adsorbed while the ethanol molecules are excluded. The scope of this work was, hence, the thermodynamic and kinetic study of ethanol-water adsorption on commercial zeolites of different origins, with the aim to select the best one. For the thermodynamic study, a thermostated bath was used at four different temperatures, where the data obtained by the static method could be correlated by means of a nonlinear isotherm. The kinetic data were obtained in a circulating finite liquid bath cell, where the effect of the temperature and of the mean diameter of the adsorbent particles on the rate of adsorption was studied. The results obtained in this way, expressed through uptake rate curves, showed that the adsorption rates were strongly dependent on the parameters studied. On comparing the adsorption rates among the adsorbents (commercial 3A zeolites, it could be concluded that, under the same operational conditions, exists a pronounced difference among them

  8. ELECTROCHEMICAL STUDIES OF URANIUM METAL CORROSION MECHANISM AND KINETICS IN WATER

    International Nuclear Information System (INIS)

    Boudanova, Natalya; Maslennikov, Alexander; Peretroukhine, Vladimir F.; Delegard, Calvin H.

    2006-01-01

    During long-term underwater storage of low burn-up uranium metal fuel, a corrosion product sludge forms containing uranium metal grains, uranium dioxide, uranates and, in some cases, uranium peroxide. Literature data on the corrosion of non-irradiated uranium metal and its alloys do not allow unequivocal prediction of the paragenesis of irradiated uranium in water. The goal of the present work conducted under the program 'CORROSION OF IRRADIATED URANIUM ALLOYS FUEL IN WATER' is to study the corrosion of uranium and uranium alloys and the paragenesis of the corrosion products during long-term underwater storage of uranium alloy fuel irradiated at the Hanford Site. The elucidation of the physico-chemical nature of the corrosion of irradiated uranium alloys in comparison with non-irradiated uranium metal and its alloys is one of the most important aspects of this work. Electrochemical methods are being used to study uranium metal corrosion mechanism and kinetics. The present part of work aims to examine and revise, where appropriate, the understanding of uranium metal corrosion mechanism and kinetics in water

  9. Modeling Adsorption Kinetics (Bio-remediation of Heavy Metal Contaminated Water)

    Science.gov (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.

  10. Molecular theory of mass transfer kinetics and dynamics at gas-water interface

    International Nuclear Information System (INIS)

    Morita, Akihiro; Garrett, Bruce C

    2008-01-01

    The mass transfer mechanism across gas-water interface is studied with molecular dynamics (MD) simulation. The MD results provide a robust and qualitatively consistent picture to previous studies about microscopic aspects of mass transfer, including interface structure, free energy profiles for the uptake, scattering dynamics and energy relaxation of impinging molecules. These MD results are quantitatively compared with experimental uptake measurements, and we find that the apparent inconsistency between MD and experiment could be partly resolved by precise decomposition of the observed kinetics into elemental steps. Remaining issues and future perspectives toward constructing a comprehensive multi-scale description of interfacial mass transfer are summarized.

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

    Science.gov (United States)

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

    2016-01-01

    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.

  12. Diffusion-kinetic theories for LET effects on the radiolysis of water

    International Nuclear Information System (INIS)

    Pimblott, S.M.; LaVerne, J.A.

    1994-01-01

    Diffusion-kinetic methods are used to investigate the effects of incident particle linear energy transfer (LET) on the radiolysis of water and aqueous solutions. Chemically realistic deterministic diffusion-kinetic calculations examining the scavenging capacity dependences of the scavenged yield of e aq - and of OH demonstrate that the scavenged yields are related to the underlying time-dependent kinetics in the absence of the scavenger by a simple Laplace transform relationship. This relationship is also shown to link the effect of an e eq - scavenger on the formation of H 2 with the time dependence of H 2 production in the absence of the scavenger. The simple Laplace relationship does not work well when applied to H 2 O 2 formation in high-LET particle tracks even though such a relationship is valid with low-LET particles. It is found that while the secondary reaction of H 2 O 2 with e aq - can be neglected in low-LET particle radiolysis, it is of considerable significance in the tracks produced by high-LET particles. The increased importance of this reaction with increasing LET is the major reason for the failure of the Laplace relationship for H 2 O 2 . 55 refs., 9 figs., 2 tabs

  13. 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

    2017-01-01

    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...... to migrate to negatively chargedcathode, where hydrogen is reduced. Meanwhile, oxygen is produced at the anode sideelectrode and escape as a gas with the circulating water. In the recent few years, PEMWE’s R&D has inched towards; operating conditions; such asincreased operating temperature and cathode...

  14. 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......-hoc and real time electrical signal of the fuel cell water balance by employing hot wire anemometry. The hot wire sensor is placed into a binary mixture of hydrogen and water vapour, and the voltage signal received gives valuable insight into heat and mass transfer phenomena in a PEMFC. A central question...

  15. Energy related germination and survival rates of water-imbibed Arabidopsis seeds irradiated with protons

    International Nuclear Information System (INIS)

    Qin, H.L.; Xue, J.M.; Lai, J.N.; Wang, J.Y.; Zhang, W.M.; Miao, Q.; Yan, S.; Zhao, W.J.; He, F.; Gu, H.Y.; Wang, Y.G.

    2006-01-01

    In order to investigate the influence of ion energy on the germination and survival rates, water-imbibed Arabidopsis seeds were irradiated with protons in atmosphere. The ion fluence used in this experiment was in the range of 4 x 10 9 -1 x 10 14 ions/cm 2 . The ion energy is from 1.1 MeV to 6.5 MeV. According to the structure of the seed and TRIM simulation, the ions with the energy of 6.5 MeV can irradiate the shoot apical meristem directly whereas the ions with the energy of 1.1 MeV cannot. The results showed that both the germination and survival rates decrease while increasing the ion fluence, and the fluence-respond curve for each energy has different character. Besides the shoot apical meristem (SAM), which is generally considered as the main radiobiological target, the existence of a secondary target around SAM is proposed in this paper

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

    Science.gov (United States)

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

    2018-03-01

    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. Proton transfer along water bridges in biological systems with density-functional tight-binding

    Science.gov (United States)

    Reiss, Krystle; Wise, Abigail; Mazzuca, James

    2015-03-01

    When examining the dynamics of charge transfer in high dimensional enzymatic systems, the cost of quantum mechanical treatment of electrons increases exponentially with the size of the system. As a semi-empirical method, density-functional tight-binding aids in shortening these calculation times, but can be inaccurate in the regime where bonds are being formed and broken. To address these inaccuracies with respect to proton transfer in an enzymatic system, DFTB is being used to calculate small model systems containing only a single amino acid residue donor, represented by an imidazole molecule, and a water acceptor. When DFTB calculations are compared to B3LYP geometry calculations of the donor molecule, we observe a bond angle error on the order of 1.2 degrees and a bond length error on the order of 0.011 Å. As we move forward with small donor-acceptor systems, comparisons between DFTB and B3LYP energy profiles will provide a better clue as to what extent improvements need to be made. To improve the accuracy of the DFTB calculations, the internuclear repulsion term may be altered. This would result in energy profiles that closely resemble those produced by higher-level theory. Alma College Provost's Office.

  18. Energy related germination and survival rates of water-imbibed Arabidopsis seeds irradiated with protons

    Energy Technology Data Exchange (ETDEWEB)

    Qin, H.L. [Key Laboratory of Heavy Ion Physics, MOE, Peking University, Beijing 100871 (China); Xue, J.M. [Key Laboratory of Heavy Ion Physics, MOE, Peking University, Beijing 100871 (China); Lai, J.N. [Key Laboratory of Heavy Ion Physics, MOE, Peking University, Beijing 100871 (China); Wang, J.Y. [Key Laboratory of Heavy Ion Physics, MOE, Peking University, Beijing 100871 (China); Zhang, W.M. [Key Laboratory of Heavy Ion Physics, MOE, Peking University, Beijing 100871 (China); Miao, Q. [Key Laboratory of Heavy Ion Physics, MOE, Peking University, Beijing 100871 (China); Yan, S. [Key Laboratory of Heavy Ion Physics, MOE, Peking University, Beijing 100871 (China); Zhao, W.J. [Key Laboratory of Heavy Ion Physics, MOE, Peking University, Beijing 100871 (China); He, F. [School of Life Science, Peking University, Beijing 100871 (China); Gu, H.Y. [School of Life Science, Peking University, Beijing 100871 (China); Wang, Y.G. [Key Laboratory of Heavy Ion Physics, MOE, Peking University, Beijing 100871 (China)]. E-mail: ygwang@pku.edu.cn

    2006-04-15

    In order to investigate the influence of ion energy on the germination and survival rates, water-imbibed Arabidopsis seeds were irradiated with protons in atmosphere. The ion fluence used in this experiment was in the range of 4 x 10{sup 9}-1 x 10{sup 14} ions/cm{sup 2}. The ion energy is from 1.1 MeV to 6.5 MeV. According to the structure of the seed and TRIM simulation, the ions with the energy of 6.5 MeV can irradiate the shoot apical meristem directly whereas the ions with the energy of 1.1 MeV cannot. The results showed that both the germination and survival rates decrease while increasing the ion fluence, and the fluence-respond curve for each energy has different character. Besides the shoot apical meristem (SAM), which is generally considered as the main radiobiological target, the existence of a secondary target around SAM is proposed in this paper.

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

    International Nuclear Information System (INIS)

    Suarez-Antola, Roberto

    2013-01-01

    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, jointly with other

  20. Iron oxidation kinetics and phosphorus immobilization at the groundwater-surface water interface

    Science.gov (United States)

    van der Grift, Bas; Rozemeijer, Joachim; Griffioen, Jasper; van der Velde, Ype

    2014-05-01

    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 surface waters is controlled strongly by biogeochemical nutrient cycling processes at the soil-water interface. The mechanisms and rates of the iron oxidation process with associated binding of phosphate during exfiltration of anaerobic Fe(II) bearing groundwater are among the key unknowns in P retention processes in surface waters in delta areas where the shallow groundwater is typically pH-neutral to slightly acid, anoxic, iron-rich. We developed an experimental field set-up to study the dynamics in Fe(II) oxidation and mechanisms of P immobilization at the groundwater-surface water interface 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. The exfiltrating groundwater was captured in in-stream reservoirs constructed in the ditch. Through continuous discharge measurements and weekly water quality sampling of groundwater, tube drain water, exfiltrated groundwater, and ditch water, we quantified Fe(II) oxidation kinetics and P immobilization processes across the seasons. This study showed that seasonal changes in climatic conditions affect the Fe(II) oxidation process. In winter time the dissolved iron concentrations in the in-stream reservoirs reached the levels of the anaerobic groundwater. In summer time, the dissolved iron concentrations of the water in the reservoirs are low, indicating that dissolved Fe(II) is completely oxidized prior to inflow into the reservoirs. Higher discharges, lower temperatures and lower pH of the exfiltrated groundwater in winter compared to summer shifts the location of the redox transition zone

  1. Effects of Water Molecule on CO Oxidation by OH: Reaction Pathways, Kinetic Barriers, and Rate Constants.

    Science.gov (United States)

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

    2017-07-06

    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.

  2. Production and characterization of protonated molecular clusters containing a given number of water molecules with the DIAM set-up

    International Nuclear Information System (INIS)

    Bruny, G.

    2010-01-01

    nano-scale characterization of irradiation in bio-molecular systems requires observation of novel features which are now achievable with the recent technical progress. This work is a central part in the development of DIAM which is a new experimental set-up devoted to irradiation of bio-molecular clusters at the Institut de Physique Nucleaire de Lyon. The development of the cluster source and of a double focusing mass spectrometer leads to the production of intense beams of mass selected protonated molecular clusters. Combined with this mass selected cluster beams an innovative detection technique is demonstrated in collision induced dissociation experiments. The results contribute to the knowledge of the stability and the structure of the small protonated water clusters and mixed clusters of water and pyridine. (author)

  3. Measurement of solute proton spin-lattice relaxation times in water using the 1,3,3,1 sequence

    International Nuclear Information System (INIS)

    Sankar, S.S.; Mole, P.A.; Coulson, R.L.

    1986-01-01

    1 H NMR spin-lattice relaxation times (T1) of the N-CH3 proton resonances of phosphocreatine (PCr) and creatine (Cr) in water solutions were obtained using the 1,3,3,1 pulse sequence. These T1 values were equivalent to those obtained in D 2 O and water using either the conventional inversion-recovery experiment or the 1,3,3,1 pulse sequence. Thus, the 1,3,3,1 sequence of proton NMR can provide an independent means along with phosphorous NMR for assess PCr and for the study of the creatine kinase reaction (PCr + ADP in equilibrium ATP + Cr) in aqueous solutions and perhaps in biological preparations

  4. Proton exchange membranes from sulfonated polyetheretherketone and sulfonated polyethersulfone-cardo blends: Conductivity, water sorption and permeation properties

    International Nuclear Information System (INIS)

    Li, Yongli; Nguyen, Quang Trong; Schaetzel, Pierre; Lixon-Buquet, Camille; Colasse, Laurent; Ratieuville, Vincent

    2013-01-01

    Five blend membranes were prepared by solvent evaporation from solutions of the synthesized sulfonated polyetheretherketone (SPEEK) and sulfonated polyethersulfone-cardo (SPESc). Their ion exchange capacity and degree of sulfonation determined by acid–base titration and by thermogravimetric analysis were consistent. The blends glass transition behavior obtained by differential scanning calorimetry suggests that the two sulfonated polymers are compatible in the whole composition range. The values of the activation energy for proton transport determined by conductivity measurements on the SPEEK-based blend membranes were in the range of 13–34 kJ mol −1 , which suggest a mixed transport mechanism that involves both proton jumps on ionic sites and water of hydration and diffusion of proton–water complex in hydrophilic domains. The water vapor sorption in the membranes exhibits sigmoid-shape isotherms which were well fitted by the “new dual mode sorption” model, and the fitted parameters values were successfully used to model the change in the water permeation flux with the upstream water activity using the first Fick's diffusion equation. The fast increase in the permeation flux beyond a critical value of activity (0.5) was owing to the exponential concentration-dependent diffusion coefficient. These modelings allowed us to show a strong increase in the limit diffusion coefficient of water and a decrease in the water-diffusion plasticization coefficient with the SPEEK content in the polymer blends

  5. Experimental Investigation of Adsorption Kinetics: Implications for Diurnals Variations of Martian Atmospheric Water.

    Science.gov (United States)

    Slank, R.; Farris, H. N.; Chevrier, V.

    2017-12-01

    Introduction: Ice at Mars' equatorial regions is unstable at geologically short timescales, due to factors like thermal properties of the regolith and depth [1]. The distribution of ice is governed by thermodynamics and kinetics, which largely depends on diffusive and adsorptive properties of the regolith [2] and are studied through simulation experiments on regolith analogs. Numerical models of water ice stability [3] often require kinetic parameters that are lacking for Mars relevant materials. Previous measurements were limited to clays [4] or did not account for temperature dependence [5]. Method: Measurements of input parameters are performed for different regoliths relevant to observations of the Martian surface: smectite, basalt, JSC-Mars 1, and nanophase ferric oxides [6]. While diffusive properties of some of these materials are well understood [7; 1; 8; 9], we seek to determine adsorption parameters, specifically the temperature dependencies for kinetics. Adsorption kinetic constants are derived from the change in mass of water adsorbed as a function of time on a thin layer ( 1mm thick) of regolith, resulting in minimum diffusion and maximum surface in contact with the atmosphere. The samples are baked for 24 hours at 100°C and then sealed in a desiccators placed in a freezer to cool the sample. All experiments are run in the Aries Mars Simulation Chamber. The chamber is evacuated to less that 1 mbar, filled with dry CO2 gas to atmospheric pressure, and chilled to the determined temperature. Once conditions are stable, the sample is measured and placed in the chamber. The sample is then exposed to a 6 mbar CO2 atmosphere at various temperatures (-12 to 3°C) and humidities (5 to 80%). Experiments are run for 4 to 8 hours, to allow the sample to reach steady state. During this time, mass, pressure, temperature, relative humidity, and water vapor pressure are recorded. References: [1] Beck, P. et al. (2010) JGR 115. [2] Chevrier, V.F. et al. (2008) Icarus

  6. Hydration kinetics of cement composites with varying water-cement ratio using terahertz spectroscopy

    Science.gov (United States)

    Ray, Shaumik; Dash, Jyotirmayee; Devi, Nirmala; Sasmal, Saptarshi; Pesala, Bala

    2015-03-01

    Cement is mixed with water in an optimum ratio to form concrete with desirable mechanical strength and durability. The ability to track the consumption of major cement constituents, viz., Tri- and Dicalcium Silicates (C3S, C2S) reacting with water along with the formation of key hydration products, viz., Calcium-Silicate-Hydrate (C-S-H) which gives the overall strength to the concrete and Calcium Hydroxide (Ca(OH)2), a hydration product which reduces the strength and durability, using an efficient technique is highly desirable. Optimizing the amount of water to be mixed with cement is one of the main parameters which determine the strength of concrete. In this work, THz spectroscopy has been employed to track the variation in hydration kinetics for concrete samples with different water-cement ratios, viz., 0.3, 0.4, 0.5 and 0.6. Results show that for the sample with water-cement ratio of 0.3, significant amount of the C3S and C2S remain unreacted even after the initial hydration period of 28 days while for the cement with water-cement ratio of 0.6, most of the constituents get consumed during this stage. Analysis of the formation of Ca(OH)2 has been done which shows that the concrete sample with water-cement ratio of 0.6 produces the highest amount of Ca(OH)2 due to higher consumption of C3S/C2S in presence of excess water which is not desirable. Samples with water-cement ratio of 0.4 and 0.5 show more controlled reaction during the hydration which can imply formation of an optimized level of desired hydration products resulting in a more mechanically strong and durable concrete.

  7. Tritiated water uptake kinetics in tissue-free water and organically-bound fractions of tomato plants

    International Nuclear Information System (INIS)

    Spencer, F.S.

    1984-03-01

    The kinetics of tritiated water (HTO) vapour uptake into tissue-free water tritium (TFWT) and organically bound tritium (OBT) fractions of tomato, Lycopersicon esculentum Mill., cv Vendor, were investigated under controlled growing conditions. Most uptake data fitted a first-order kinetic model, C t = C ∞ (1-e -kt ), where C t is the tritium concentration at time t, Ca the steady-state concentration and k the uptake rate constant. During atmospheric-HTO exposure with clean-water irrigation in open pots the TFWT k values were 0.024 ± 0.023 h -1 for new foliage, 0.104 ± 0.067 h -1 for old foliage and 0.042 ± to 0.136 h -1 for new green fruit. OBT uptake rate constants were 20 percent less for new foliage and 76 percent less for new green fruit. Under steady-state conditions the ratio of tritium specific activities of TWFT to atmospheric HTO were 0.43 in new foliage, 0.46 in old foliage and 0.19 in green fruit. Within the plant, OBT and TFWT ratios were 0.70 for new foliage, 0.63 for old foliage (maximum) and between 0.72 and 1.92 for green fruit. The greater than unity tritium specific activity ratios in green fruit were not attributed to tritium enrichment but rather to the translocation of foliar OBT to the growing fruit which contained lower specific activity TFWT derived from soil water

  8. Low-energy proton stopping power of N2, O2, and water vapor, and deviations from Bragg's rule

    International Nuclear Information System (INIS)

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

    1984-01-01

    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 N 2 , O 2 , 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

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

    Directory of Open Access Journals (Sweden)

    Suna Hongyan

    2016-12-01

    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.

  10. Removing polycyclic aromatic hydrocarbons from water using granular activated carbon: kinetic and equilibrium adsorption studies.

    Science.gov (United States)

    Eeshwarasinghe, Dinushika; Loganathan, Paripurnanda; Kalaruban, Mahatheva; Sounthararajah, Danious Pratheep; Kandasamy, Jaya; Vigneswaran, Saravanamuthu

    2018-05-01

    Polycyclic aromatic hydrocarbons (PAHs) constitute a group of highly persistent, toxic and widespread environmental micropollutants that are increasingly found in water. A study was conducted in removing five PAHs, specifically naphthalene, acenaphthylene, acenaphthene, fluorene and phenanthrene, from water by adsorption onto granular activated carbon (GAC). The pseudo-first-order (PFO) model satisfactorily described the kinetics of adsorption of the PAHs. The Weber and Morris diffusion model's fit to the data showed that there were faster and slower rates of intra-particle diffusion probably into the mesopores and micropores of the GAC, respectively. These rates were negatively related to the molar volumes of the PAHs. Batch equilibrium adsorption data fitted well to the Langmuir, Freundlich and Dubinin-Radushkevich models, of which the Freundlich model exhibited the best fit. The adsorption affinities were related to the hydrophobicity of the PAHs as determined by the log K ow values. Free energies of adsorption calculated from the Dubinin-Radushkevich model and the satisfactory kinetic data fitting to the PFO model suggested physical adsorption of the PAHs. Adsorption of naphthalene, acenaphthylene and acenaphthene in fixed-bed columns containing a mixture of GAC (0.5 g) + sand (24.5 g) was satisfactorily simulated by the Thomas model.

  11. Study of kinetics of reaction of lithium deuteride powder with O2, CO2 and water vapor

    International Nuclear Information System (INIS)

    Li Gan; Lu Guangda; Jing Wenyong; Qin Cheng

    2004-01-01

    The kinetics of reaction of lithium deuteride powder with O 2 , CO 2 and water vapor is studied. The experimental results show that lithium deuteride reacts with O 2 and CO 2 at very small reaction rate but with water vapor at comparatively larger rate at room temperature (≅28 degree C). The reaction process with water vapor could be described using the unreacted shrinking core model. The second-order kinetics is appropriate for the chemical reaction on the surface of lithium deuteride and reaction rate constant is 0.281 kPa -1 ·min -1

  12. Kinetics of the reaction between H· and superheated water probed with muonium

    International Nuclear Information System (INIS)

    Alcorn, Chris D.; Brodovitch, Jean-Claude; Percival, Paul W.; Smith, Marisa; Ghandi, Khashayar

    2014-01-01

    Highlights: • Rate constants for reactions of H with water resolve a controversy. • H reacts with superheated water via two channels. • The findings have important implications for the safety of some nuclear power reactors. - Abstract: Safe operation of supercritical water-cooled reactors requires knowledge of the kinetics of transient species formed by the radiolysis of water in the range 300–650 °C. Using muonium, it is possible to study aqueous H · atom chemistry over this temperature range. An important reaction to study is that of the H · atom with water itself, because it is a potential source of molecular H 2 . The concentration of H 2 is important to plant coolant chemistry, as H 2 is currently added to suppress oxidative corrosion in CANDU reactors. The reaction of muonium with H 2 O and D 2 O was studied experimentally up to 450 °C, and also via quantum chemical computations to investigate possible isotope effects. Our results suggest that although the H · atom abstraction from H 2 O is important at temperatures above 300 °C, the electron-producing channel (H · + H 2 O ⇌ H 3 O + + e aq - ) is significant at temperatures up to 300 °C, and becomes the dominant reaction channel at lower temperatures

  13. Kinetics of the reaction between H{sup ·} and superheated water probed with muonium

    Energy Technology Data Exchange (ETDEWEB)

    Alcorn, Chris D. [Department of Chemistry and Biochemistry, Mount Allison University, Sackville, New Brunswick E4L 1G8 (Canada); Brodovitch, Jean-Claude [Department of Chemistry, Simon Fraser University, Burnaby, British Columbia V5A 1S6 (Canada); Percival, Paul W. [Department of Chemistry, Simon Fraser University, Burnaby, British Columbia V5A 1S6 (Canada); TRIUMF, 4004 Wesbrook Mall, Vancouver, British Columbia V6T 2A3 (Canada); Smith, Marisa [Department of Chemistry and Biochemistry, Mount Allison University, Sackville, New Brunswick E4L 1G8 (Canada); Ghandi, Khashayar, E-mail: kghandi@mta.ca [Department of Chemistry and Biochemistry, Mount Allison University, Sackville, New Brunswick E4L 1G8 (Canada)

    2014-05-19

    Highlights: • Rate constants for reactions of H with water resolve a controversy. • H reacts with superheated water via two channels. • The findings have important implications for the safety of some nuclear power reactors. - Abstract: Safe operation of supercritical water-cooled reactors requires knowledge of the kinetics of transient species formed by the radiolysis of water in the range 300–650 °C. Using muonium, it is possible to study aqueous H{sup ·} atom chemistry over this temperature range. An important reaction to study is that of the H{sup ·} atom with water itself, because it is a potential source of molecular H{sub 2}. The concentration of H{sub 2} is important to plant coolant chemistry, as H{sub 2} is currently added to suppress oxidative corrosion in CANDU reactors. The reaction of muonium with H{sub 2}O and D{sub 2}O was studied experimentally up to 450 °C, and also via quantum chemical computations to investigate possible isotope effects. Our results suggest that although the H{sup ·} atom abstraction from H{sub 2}O is important at temperatures above 300 °C, the electron-producing channel (H{sup ·} + H{sub 2}O ⇌ H{sub 3}O{sup +} + e{sub aq}{sup -}) is significant at temperatures up to 300 °C, and becomes the dominant reaction channel at lower temperatures.

  14. PREFACE: Transport phenomena in proton conducting media Transport phenomena in proton conducting media

    Science.gov (United States)

    Eikerling, Michael

    2011-06-01

    , 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

  15. 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

    2012-08-01

    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.

  16. Morphology and Kinetics of Growth of CaCO3 Precipitates Formed in Saline Water at 30°C

    Science.gov (United States)

    Sui, Xin; Wang, Baohui; Wu, Haiming

    2018-02-01

    The crystallization kinetics and morphology of CaCO3 crystals precipitated from the high salinity oilfield water were studied. The crystallization kinetics measurements show that nucleation and nuclei growth obey the first order reaction kinetics. The induction period of precipitation is extended in the high salinity solutions. Morphological studies show that impurity ions remain mostly in the solution phase instead of filling the CaCO3 crystal lattice. The morphology of CaCO3 precipitates can be changed from a smooth surface (calcite) to rough spheres (vaterite), and spindle rod bundles, or spherical, ellipsoid, flowers, plates and other shapes (aragonite).

  17. Magnetization transfer from macromolecules to water protons in murine dental tissues as revealed by 500 MHz 1H-NMR

    International Nuclear Information System (INIS)

    Nakamura, Koji; Era, Seiichi; Nagai, Naoki; Sogami, Masaru; Takasaki, Akihiko; Kato, Kazuo.

    1997-01-01

    Although much is known about magnetization transfer phenomena in biological soft tissues, little is known about those in hard tissues. Using a 500 MHz 1 H-NMR spectrometer, we studied the spin-lattice relaxation time (T 1 (H 2 O)) and the intermolecular cross-relaxation times (T IS (H 2 O)) from irradiated macromolecular protons to observed water protons in murine lower incisors (hard tissue) and compared with those in murine lens tissue (soft tissue). Mean values for the water content (%) of murine lower incisors and lens tissue were 16.02±2.39 (n=14) and 67.20±4.60 (n=15), respectively. These findings were consistent with the large different in water content between soft tissues and hard tissues. T IS (H 2 O) values obtained by f 2 -irradiation at 7.13 or -4.00 ppm showed no significant difference between lower incisors and lens tissue. Plots of 1/T IS (H 2 O) values vs. tissue dry weight (W(%)) for lower incisor tissue approximated a straight line with slope approximately equal for that obtained for lens tissue. These results suggest that the state of water in hard tissue may be similar to that in soft tissues, in spite of the significant difference in water content. Thus, saturation transfer NMR techniques such as measurement of T IS (H 2 O) values may be applicable to the study of water-macromolecule interactions in both biological soft and hard tissues. (author)

  18. 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

    2012-01-01

    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...... variations affect gas and liquid water transport, and hence liquid water distribution and the risk of blocking active sites. Hence, water transport is studied under GDL compression in order to investigate the qualitative effects. Two simulation cases are compared; one with and one without compression....

  19. Study of coupled heat and water transfer in proton exchange membrane fuel cells by the way of internal measurements

    International Nuclear Information System (INIS)

    Thomas, A; Maranzana, G; Didierjean, S; Dillet, J; Lottin, O

    2012-01-01

    Measurements of electrode temperatures within a proton exchange membrane fuel cell were performed using platinum wires. A temperature difference of 7°C between the electrodes and the bipolar plates was observed for a cell operating at a current density of 1.5 A.cm −2 . These measurements show a strong non-uniformity of the temperature profile through membrane electrode assembly (MEA) that future phenomenological models must take into account. In addition, the simultaneous measurements of heat and water flux through the MEA leads to the conclusion that produced water crosses the diffusion layer in vapor phase. A very simple heat transfer model is proposed.

  20. Influential factors of formation kinetics of flocs produced by water treatment coagulants.

    Science.gov (United States)

    Wu, Chunde; Wang, Lin; Hu, Bing; Ye, Jian

    2013-05-01

    The growth rate and size of floc formation is of great importance in water treatment especially in coagulation process. The floc formation kinetics and the coagulation efficiency of synthetic water were investigated by using an on-line continuous optical photometric dispersion analyze and the analysis of water quality. Experimental conditions such as alum dosage, pH value for coagulation, stirring intensity and initial turbidity were extensively examined. The photometric dispersion analyze results showed that coagulation of kaolin suspensions with two coagulants (alum and polyaluminium chloride) could be taken as a two-phase process: slow and rapid growth periods. Operating conditions with higher coagulant doses, appropriate pH and average shear rate might be particularly advantageous. The rate of overall floc growth was mainly determined by a combination of hydraulic and water quality conditions such as pH and turbidity. The measurement of zeta potential indicates that polyaluminium chloride exhibited higher charge-neutralizing ability than alum and achieved lower turbidities than alum for equivalent Al dosages. Under the same operating conditions, the alum showed a higher grow rate, but with smaller floc size.

  1. 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; Christensen, Erik

    2012-01-01

    Proton exchange membrane water electrolysers operating at typically 80 °C or at further elevated temperatures suffer from insufficient catalyst activity and durability. In this work, antimony doped tin oxide nanoparticles were synthesized and further doped with an inorganic proton conducting phase...... 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...

  2. Sulfonated poly(fluorenyl ether ketone nitrile) electrolyte membrane with high proton conductivity and low water uptake

    Energy Technology Data Exchange (ETDEWEB)

    Tian, S.H.; Wang, S.J.; Xiao, M.; Meng, Y.Z. [State Key Laboratory of Optoelectronic Materials and Technologies/Institute of Optoelectronic and Functional Composite Materials, Sun Yat-sen University, Guangzhou 510275 (China); Shu, D. [School of Chemistry and Environmental, South China Normal University, Guangzhou 510006 (China)

    2010-01-01

    High molecular weight sulfonated poly(fluorenyl ether ketone nitrile)s with different equivalent weight (EW) from 681 to 369 g mequiv.{sup -1} are synthesized by the nucleophilic substitution polycondensation of various amounts of sulfonated difluorobenzophenone (SDFBP) and 2,6-difluorobenzonitrile (DFBN) with bisphenol fluorene (BPF). The synthesized copolymers are characterized by {sup 1}H NMR, FT-IR, TGA, and DSC techniques. The membranes cast from the corresponding copolymers exhibit superior thermal stability, good oxidative stability and high proton conductivity, but low water uptake due to the strong nitrile dipole interchain interactions that combine to limit swelling. Among all the membranes, the membrane with EW of 441 g mequiv.{sup -1} shows optimum properties of both high proton conductivity of 41.9 mS cm{sup -1} and low water uptake of 42.6%. Accordingly, That membrane is fabricated into a membrane electrode assembly (MEA) and evaluated in a single proton exchange membrane fuel cell (PEMFC). The experimental results indicate its similar cell performance as that of Nafion {sup registered} 117 at 70 C, but much better cell performance at higher temperatures. At the potential of 0.6 V, the current density of fuel cell using the prepared membrane and Nafion {sup registered} 117 is 0.46 and 0.25 A cm{sup -2}, respectively. The highest current density of the former reaches as high as 1.25 A cm{sup -2}. (author)

  3. Proton and aluminum binding properties of organic acids in surface waters of the northeastern U.S.

    Science.gov (United States)

    Fakhraei, Habibollah; Driscoll, Charles T

    2015-03-03

    A variety of mathematical estimators have been used to quantify the degree of protonation of naturally occurring organic acids. These estimators range from monoprotic, diprotic, and triprotic analog models to the discrete and continuous (Gaussian) distributions of a single proton binding-dissociation. Natural water samples from two long-term monitoring programs in the northeastern U.S. were used to quantify proton- and aluminum-binding properties of naturally occurring organic matter. Water chemistry observations were clustered into 0.05 pH intervals (over 3.75-7.35 pH range) and fit to a triprotic analog model. The model optimization indicates that about 5% of dissolved organic carbon participates in ion binding, and organic acids are composed of both strong and weak acids (i.e., pKa1 = 2.54, pKa2 = 6.19, and pKa3 = 7.52 for Adirondack samples). Binding between organic acids and aluminum can substantially influence the acid behavior of dissolved organic matter and the availability of the toxic form of aluminum (i.e., inorganic monomeric aluminum).

  4. Proton-proton bremsstrahlung

    International Nuclear Information System (INIS)

    Fearing, H.W.

    1990-01-01

    We summarize some of the information about the nucleon-nucleon force which has been obtained by comparing recent calculations of proton-proton bremsstrahlung with cross section and analyzing power data from the new TRIUMF bremsstrahlung experiment. Some comments are made as to how these results can be extended to neutron-proton bremsstrahlung. (Author) 17 refs., 6 figs

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

    Directory of Open Access Journals (Sweden)

    Xuesong Xu

    2018-01-01

    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.

  6. Kinetic model of water disinfection using peracetic acid including synergistic effects.

    Science.gov (United States)

    Flores, Marina J; Brandi, Rodolfo J; Cassano, Alberto E; Labas, Marisol D

    2016-01-01

    The disinfection efficiencies of a commercial mixture of peracetic acid against Escherichia coli were studied in laboratory scale experiments. The joint and separate action of two disinfectant agents, hydrogen peroxide and peracetic acid, were evaluated in order to observe synergistic effects. A kinetic model for each component of the mixture and for the commercial mixture was proposed. Through simple mathematical equations, the model describes different stages of attack by disinfectants during the inactivation process. Based on the experiments and the kinetic parameters obtained, it could be established that the efficiency of hydrogen peroxide was much lower than that of peracetic acid alone. However, the contribution of hydrogen peroxide was very important in the commercial mixture. It should be noted that this improvement occurred only after peracetic acid had initiated the attack on the cell. This synergistic effect was successfully explained by the proposed scheme and was verified by experimental results. Besides providing a clearer mechanistic understanding of water disinfection, such models may improve our ability to design reactors.

  7. Kinetics of the hydrogen production reaction in a copper-chlorine water splitting plant

    International Nuclear Information System (INIS)

    Zamfirescu, C.; Naterer, G.F.; Dincer, I.

    2009-01-01

    The exothermic reaction of HCl with particulate Cu occurs during hydrogen production step in the thermochemical copper-chlorine (Cu-Cl) water splitting cycle. In this paper, this chemical reaction is modeled kinetically, and a parametric study is performed to determine the influences of particle size, temperature and molar ratios on the reaction kinetics. It is determined that the residence time of copper particles varies between 10 and 100 s, depending on the operating conditions. The hydrogen conversion at equilibrium varies between 55 and 85%, depending on the reaction temperature. The heat flux at the particle surface, caused by the exothermic enthalpy of reaction, reaches about 3,000 W/m 2 when the particle shrinks to 0.1% from its initial size. A numerical algorithm is developed to solve the moving boundary Stefan problem with a chemical reaction. It predicts the shrinking of copper particles based on the hypothesis that the chemical reaction and heat transfer are decoupled. The model allows for estimation of the temperature of the copper particle, assumed spherical, in the radial direction. The maximum temperature at the interface is higher than the melting point of CuCl by 10-50 o C, depending on the assumed operating conditions. (author)

  8. Propagation of biochirality: crossovers and nonclassical crystallization kinetics of aspartic acid in water.

    Science.gov (United States)

    Lee, Tu; Lin, Yu Kun; Tsai, Ya Chung; Lee, Hung Lin

    2013-11-01

    All experimental procedures discussed could be treated as a screening tool for probing the existence of molecular association among the chiral molecules and the solvent system. The molecular association phases of a racemic conglomerate solution (CS) and a racemic compound solution (RCS), and the templating effect of aspartic acid solid surface were observed to minimize the chance of redissolving racemic conglomerate and racemic compound aspartic acid in water and reforming an RCS in crossovers experiments. Only 1 %wt% of l-aspartic acid was adequate enough to induce a transformation from a racemic compound aspartic acid to a racemic conglomerate aspartic acid. This would make the propagation of biochirality more feasible and sound. However, tetrapeptide, (l-aspartic acid)4 , failed to induce enantioseparation as templates purely by crystallization. Nonclassical crystallization theory was needed to take into account the existence of a CS. Fundamental parameters of the crystallization kinetics such as the induction time, interfacial energy, Gibbs energetic barrier, nucleation rate, and critical size of stable nuclei of: (i) racemic compound aspartic acid, (ii) racemic compound aspartic acid seeded with 1 %wt% l-aspartic acid, (iii) racemic conglomerate aspartic acid, and (iv) l-aspartic acid were evaluated and compared with different initial supersaturation ratios. Morphological studies of crystals grown from the crystallization kinetics were also carried out. © 2013 Wiley Periodicals, Inc.

  9. How the shape of an H-bonded network controls proton-coupled water activation in HONO formation.

    Science.gov (United States)

    Relph, Rachael A; Guasco, Timothy L; Elliott, Ben M; Kamrath, Michael Z; McCoy, Anne B; Steele, Ryan P; Schofield, Daniel P; Jordan, Kenneth D; Viggiano, Albert A; Ferguson, Eldon E; Johnson, Mark A

    2010-01-15

    Many chemical reactions in atmospheric aerosols and bulk aqueous environments are influenced by the surrounding solvation shell, but the precise molecular interactions underlying such effects have rarely been elucidated. We exploited recent advances in isomer-specific cluster vibrational spectroscopy to explore the fundamental relation between the hydrogen (H)-bonding arrangement of a set of ion-solvating water molecules and the chemical activity of this ensemble. We find that the extent to which the nitrosonium ion (NO+)and water form nitrous acid (HONO) and a hydrated proton cluster in the critical trihydrate depends sensitively on the geometrical arrangement of the water molecules in the network. Theoretical analysis of these data details the role of the water network in promoting charge delocalization.

  10. Oxidation kinetics of model compounds of metabolic waste in supercritical water

    Science.gov (United States)

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

    1990-01-01

    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.

  11. Protons and how they are transported by proton pumps

    DEFF Research Database (Denmark)

    Buch-Pedersen, Morten Jeppe; Pedersen, Bjørn Panyella; Nissen, Poul

    2008-01-01

    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....

  12. Chlorine dioxide oxidation of Escherichia coli in water - A study of the disinfection kinetics and mechanism.

    Science.gov (United States)

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

    2017-06-07

    This study investigated the kinetics and mechanism of chlorine dioxide (ClO 2 ) 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 (10 5 -10 7 cfu/mL). The effects of ClO 2 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 C avg Hom model. Transmission Electron Microscopy images of the bacteria cells exposed to lethal concentrations of ClO 2 indicated very little observable morphological damage to the outer membranes of the cells. ClO 2 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.

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

    DEFF Research Database (Denmark)

    Hedegaard, Mathilde Jørgensen; Albrechtsen, Hans-Jørgen

    2014-01-01

    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...

  14. Efficient hydrogen production on MoNi4 electrocatalysts with fast water dissociation kinetics

    Science.gov (United States)

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

    2017-05-01

    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.

  15. Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water

    Science.gov (United States)

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

    2014-11-01

    The retention of phosphorus in surface waters through 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 into 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 surface 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 a 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 immobilization of dissolved P during the initial stage of the Fe(II) oxidation process which results in P-depleted water before Fe(II) is completely 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

  16. Study of the multiplication and kinetic effects of salt mixtures and salt blanket micromodels on thermal neutron spectra of heavy water MAKET facility

    International Nuclear Information System (INIS)

    Titarenko, Yu.E.; Batyaev, V.F.; Borovlev, S.P.; Gladkikh, N.G.; Igumnov, M.M.; Legostaev, V.O.; Karpikhin, E.I.; Konev, V.N.; Kushnerev, Yu.T.; Ryazhsky, V.I.; Spiridonov, V.G.; Chernyavsky, E.V.; Shvedov, O.V.

    2009-10-01

    The main goal of the Project is to study and evaluate nuclear characteristics of materials and isotopes involved in processes of irradiated nuclear fuel transmutation. This principal task is subdivided into 9 subtasks subject to the neutron or proton source used, the type of the nuclear process under study, isotope collection, characteristics of which are to be investigated, etc. In the presented extract of the Project Activity report the measurements there were used the MAKET zero-power heavy-water reactor in the measurements there was employed a large set of minor actinide samples highly enriched with the main isotope. The samples were obtained with mass-separator SM-2 (VNIIEF). At the heavy-water reactor MAKET (ITEP) there were measured multiplying and kinetic characteristics of salt mixtures basing on the spectra of fast and thermal neutrons. The salt mixtures of zirconium and sodium fluorides were available in salt blanket models (SBM) of cylindrical shape. There were measured the neutron spectra formed by this micro-model as well as the effective fission cross-sections of neptunium, plutonium, americium and curium isotopes caused by SBM neutrons. The neutron spectra in the measurement positions were determined from activation reaction rates. (author)

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

    KAUST Repository

    Chaieb, Saharoui; Holt, Christopher R.

    2014-01-01

    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

  18. 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.

    2015-01-01

    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

  19. Analysis of coupled proton and water transport in a PEM fuel cell using the binary friction membrane model

    International Nuclear Information System (INIS)

    Carnes, B.; Djilali, N.

    2006-01-01

    Transport of liquid water within a polymer electrolyte membrane (PEM) is critical to the operation of a PEM fuel cell, due to the strong dependence of the membrane transport coefficients on water content. In addition, enhanced predictive abilities are particularly significant in the context of passive air breathing fuel cell designs where lower water contents will prevail in the membrane. We investigate and analyze the numerical predictions of a recently proposed rational model for transport of protons and water in a PEM, when compared to a widely used empirical model. While the performance is similar for a saturated membrane, for PEMs with low water content, the difference in computed current density and membrane water crossover can be substantial. The effects of coupling partially saturated gas diffusion electrodes (GDLs) with the membrane are studied in both a 1D and 2D context. In addition, a simplified 1D analytical membrane water transport model is validated against the complete 1D model predictions. Our numerical results predict a higher current density and more uniform membrane hydration using a dry cathode instead of a dry anode, and illustrate that the strongest 2D effects are for water vapor transport

  20. A water activity based model of heterogeneous ice nucleation kinetics for freezing of water and aqueous solution droplets.

    Science.gov (United States)

    Knopf, Daniel A; Alpert, Peter A

    2013-01-01

    Immersion freezing of water and aqueous solutions by particles acting as ice nuclei (IN) is a common process of heterogeneous ice nucleation which occurs in many environments, especially in the atmosphere where it results in the glaciation of clouds. Here we experimentally show, using a variety of IN types suspended in various aqueous solutions, that immersion freezing temperatures and kinetics can be described solely by temperature, T, and solution water activity, a(w), which is the ratio of the vapour pressure of the solution and the saturation water vapour pressure under the same conditions and, in equilibrium, equivalent to relative humidity (RH). This allows the freezing point and corresponding heterogeneous ice nucleation rate coefficient, J(het), to be uniquely expressed by T and a(w), a result we term the a(w) based immersion freezing model (ABIFM). This method is independent of the nature of the solute and accounts for several varying parameters, including cooling rate and IN surface area, while providing a holistic description of immersion freezing and allowing prediction of freezing temperatures, J(het), frozen fractions, ice particle production rates and numbers. Our findings are based on experimental freezing data collected for various IN surface areas, A, and cooling rates, r, of droplets variously containing marine biogenic material, two soil humic acids, four mineral dusts, and one organic monolayer acting as IN. For all investigated IN types we demonstrate that droplet freezing temperatures increase as A increases. Similarly, droplet freezing temperatures increase as the cooling rate decreases. The log10(J(het)) values for the various IN types derived exclusively by Tand a(w), provide a complete description of the heterogeneous ice nucleation kinetics. Thus, the ABIFM can be applied over the entire range of T, RH, total particulate surface area, and cloud activation timescales typical of atmospheric conditions. Lastly, we demonstrate that ABIFM can

  1. Proton transfer through hydrogen bonds in two-dimensional water layers: A theoretical study based on ab initio and quantum-classical simulations

    International Nuclear Information System (INIS)

    Bankura, Arindam; Chandra, Amalendu

    2015-01-01

    The dynamics of proton transfer (PT) through hydrogen bonds in a two-dimensional water layer confined between two graphene sheets at room temperature are investigated through ab initio and quantum-classical simulations. The excess proton is found to be mostly solvated as an Eigen cation where the hydronium ion donates three hydrogen bonds to the neighboring water molecules. In the solvation shell of the hydronium ion, the three coordinated water molecules with two donor hydrogen bonds are found to be properly presolvated to accept a proton. Although no hydrogen bond needs to be broken for transfer of a proton to such presolvated water molecules from the hydronium ion, the PT rate is still found to be not as fast as it is for one-dimensional chains. Here, the PT is slowed down as the probability of finding a water with two donor hydrogen bonds in the solvation shell of the hydronium ion is found to be only 25%-30%. The hydroxide ion is found to be solvated mainly as a complex anion where it accepts four H-bonds through its oxygen atom and the hydrogen atom of the hydroxide ion remains free all the time. Here, the presolvation of the hydroxide ion to accept a proton requires that one of its hydrogen bonds is broken and the proton comes from a neighboring water molecule with two acceptor and one donor hydrogen bonds. The coordination number reduction by breaking of a hydrogen bond is a slow process, and also the population of water molecules with two acceptor and one donor hydrogen bonds is only 20%-25% of the total number of water molecules. All these factors together tend to slow down the hydroxide ion migration rate in two-dimensional water layers compared to that in three-dimensional bulk water

  2. Proton affinity of diastereoisomers of modified prolines using the kinetic method and density functional theory calculations: role of the cis/trans substituent on the endo/exo ring conformation.

    Science.gov (United States)

    Mezzache, S; Pepe, C; Karoyan, P; Fournier, F; Tabet, J-C

    2005-01-01

    The proton affinity (PA) of cis/trans-3-prolinoleucines and cis/trans-3-prolinoglutamic acids have been studied by the kinetic method and density functional theory (DFT) calculations. Several conformations of the neutral and the protonated modified prolines, in particular the endo and exo ring conformations, were analyzed with respect to their contribution to the PA values. When the substituent is an alkyl, both the diastereoisomers have the same PA value. However, the PA values for the diastereoisomers are different when the substituted chain contains functional groups (e.g. a carboxyl group). This variation in PA values could be attributed to the existence of intramolecular hydrogen bonds. Copyright (c) 2005 John Wiley & Sons, Ltd.

  3. 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

    2013-01-01

    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...... stack and BOP has been investigated in this study. The results show that humidification of the inlet air is of great importance. By decreasing the relative humidity of inlet air from 95% to 25%, the voltage can drop by 29%. In addition, elevated stack temperature can lead to a higher average cell...... voltage when membrane is fully hydrated otherwise it causes a drastic voltage drop in the stack. Furthermore, by substituting liquid water with water-ethylene glycol mixture of 50%, the mass flow of coolant increases by about 32-33% in the inner loop and 60-65% in the outer loop for all ranges of current...

  4. 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

    2015-01-01

    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...... expressions taken from the literature will be examined in detail, and it will be demonstrated that the power-law approach suggested by Hilpert is the only useful one for the current purposes because in this case the voltage response from the hot-wire sensor E/E0 shows the same dependency to the water balance...

  5. Chemical dynamics of the first proton-coupled electron transfer of water oxidation on TiO2 anatase.

    Science.gov (United States)

    Chen, Jia; Li, Ye-Fei; Sit, Patrick; Selloni, Annabella

    2013-12-18

    Titanium dioxide (TiO2) is a prototype, water-splitting (photo)catalyst, but its performance is limited by the large overpotential for the oxygen evolution reaction (OER). We report here a first-principles density functional theory study of the chemical dynamics of the first proton-coupled electron transfer (PCET), which is considered responsible for the large OER overpotential on TiO2. We use a periodic model of the TiO2/water interface that includes a slab of anatase TiO2 and explicit water molecules, sample the solvent configurations by first principles molecular dynamics, and determine the energy profiles of the two electronic states involved in the electron transfer (ET) by hybrid functional calculations. Our results suggest that the first PCET is sequential, with the ET following the proton transfer. The ET occurs via an inner sphere process, which is facilitated by a state in which one electronic hole is shared by the two oxygen ions involved in the transfer.

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

    International Nuclear Information System (INIS)

    Hosseinzadeh, Elham; Rokni, Masoud; Rabbani, Abid; Mortensen, Henrik Hilleke

    2013-01-01

    Highlights: ► Developing a general zero dimensional Proton Exchange Membrane Fuel Cell (PEMFC) model for a forklift. ► System performance with different cooling fluids. ► Water and thermal management of fuel cell system. ► Effect of inlet temperature, outlet temperature and temperature gradient on system performance. - Abstract: 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 stack and BOP has been investigated in this study. The results show that humidification of the inlet air is of great importance. By decreasing the relative humidity of inlet air from 95% to 25%, the voltage can drop by 29%. In addition, elevated stack temperature can lead to a higher average cell voltage when membrane is fully hydrated otherwise it causes a drastic voltage drop in the stack. Furthermore, by substituting liquid water with water–ethylene glycol mixture of 50%, the mass flow of coolant increases by about 32–33% in the inner loop and 60–65% in the outer loop for all ranges of current. The system can then be started up at about −25 °C with negligible change in the efficiency

  7. Kinetic Monte Carlo simulations of water ice porosity: extrapolations of deposition parameters from the laboratory to interstellar space

    Science.gov (United States)

    Clements, Aspen R.; Berk, Brandon; Cooke, Ilsa R.; Garrod, Robin T.

    2018-02-01

    Using an off-lattice kinetic Monte Carlo model we reproduce experimental laboratory trends in the density of amorphous solid water (ASW) for varied deposition angle, rate and surface temperature. Extrapolation of the model to conditions appropriate to protoplanetary disks and interstellar dark clouds indicate that these ices may be less porous than laboratory ices.

  8. Protein Exposed Hydrophobicity Reduces the Kinetic Barrier for Adsorption of Ovalbumin to the Air-Water Interface

    NARCIS (Netherlands)

    Wierenga, P.A.; Meinders, M.B.J.; Egmond, M.R.; Voragen, F.A.G.J.; Jongh, H.H.J. de

    2003-01-01

    Using native and caprylated ovalbumin, the role of exposed hydrophobicity on the kinetics of protein adsorption to the air - water interface is studied. First, changes in the chemical properties of the protein upon caprylation were characterized followed by measurement of the changes in adsorption

  9. Protein exposed hydrophobicity reduces the kinetic barrier for adsoption of ovalbumin to the air-water interface.

    NARCIS (Netherlands)

    Wierenga, P.A.; Meinders, M.B.J.; Egmond, M.R.; Voragen, A.G.J.

    2003-01-01

    Using native and caprylated ovalbumin, the role of exposed hydrophobicity on the kinetics of protein adsorption to the air-water interface is studied. First, changes in the chemical properties of the protein upon caprylation were characterized followed by measurement of the changes in adsorption

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

    Energy Technology Data Exchange (ETDEWEB)

    Hummel, David William, E-mail: hummeld@mcmaster.ca; Novog, David Raymond

    2016-03-15

    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

  11. Effects of water blanching on polyphenol reaction kinetics and quality of cocoa beans

    Science.gov (United States)

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

    2015-12-01

    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.

  12. Fluorescence kinetics of Trp-Trp dipeptide and its derivatives in water via ultrafast fluorescence spectroscopy.

    Science.gov (United States)

    Jia, Menghui; Yi, Hua; Chang, Mengfang; Cao, Xiaodan; Li, Lei; Zhou, Zhongneng; Pan, Haifeng; Chen, Yan; Zhang, Sanjun; Xu, Jianhua

    2015-08-01

    Ultrafast fluorescence dynamics of Tryptophan-Tryptophan (Trp-Trp/Trp2) dipeptide and its derivatives in water have been investigated using a picosecond resolved time correlated single photon counting (TCSPC) apparatus together with a femtosecond resolved upconversion spectrophotofluorometer. The fluorescence decay profiles at multiple wavelengths were fitted by a global analysis technique. Nanosecond fluorescence kinetics of Trp2, N-tert-butyl carbonyl oxygen-N'-aldehyde group-l-tryptophan-l-tryptophan (NBTrp2), l-tryptophan-l-tryptophan methyl ester (Trp2Me), and N-acetyl-l-tryptophan-l-tryptophan methyl ester (NATrp2Me) exhibit multi-exponential decays with the average lifetimes of 1.99, 3.04, 0.72 and 1.22ns, respectively. Due to the intramolecular interaction between two Trp residues, the "water relaxation" lifetime was observed around 4ps, and it is noticed that Trp2 and its derivatives also exhibit a new decay with a lifetime of ∼100ps, while single-Trp fluorescence decay in dipeptides/proteins shows 20-30ps. The intramolecular interaction lifetime constants of Trp2, NBTrp2, Trp2Me and NATrp2Me were then calculated to be 3.64, 0.93, 11.52 and 2.40ns, respectively. Candidate mechanisms (including heterogeneity, solvent relaxation, quasi static self-quenching or ET/PT quenching) have been discussed. Copyright © 2015. Published by Elsevier B.V.

  13. Fructose decomposition kinetics in organic acids-enriched high temperature liquid water

    Energy Technology Data Exchange (ETDEWEB)

    Li, Yinghua; Lu, Xiuyang; Yuan, Lei; Liu, Xin [Department of Chemical and Biochemical Engineering, Zhejiang University, Zheda Road 38, Hangzhou 310027, Zhejiang (China)

    2009-09-15

    Biomass continues to be an important candidate as a renewable resource for energy, chemicals, and feedstock. Decomposition of biomass in high temperature liquid water is a promising technique for producing industrially important chemicals such as 5-hydroxymethylfurfural (5-HMF), furfural, levulinic acid with high efficiency. Hexose, which is the hydrolysis product of cellulose, will be one of the most important starting chemicals in the coming society that is highly dependent on biomass. Taking fructose as a model compound, its decomposition kinetics in organic acids-enriched high temperature liquid water was studied in the temperature range from 180 C to 220 C under the pressure of 10 MPa to further improve reaction rate and selectivity of the decomposition reactions. The results showed that the reaction rate is greatly enhanced with the addition of organic acids, especially formic acid. The effects of temperature, residence time, organic acids and their concentrations on the conversion of fructose and yield of 5-HMF were investigated. The evaluated apparent activation energies of fructose decomposition are 126.8 {+-} 3.3 kJ mol{sup -1} without any catalyst, 112.0 {+-} 13.7 kJ mol{sup -1} catalyzed with formic acid, and 125.6 {+-} 3.8 kJ mol{sup -1} catalyzed with acetic acid, respectively, which shows no significant difference. (author)

  14. Kinetic model for reactivity in quaternary water-in-oil microemulsions.

    Science.gov (United States)

    García-Río, Luis; Hervella, Pablo

    2006-11-06

    A study was carried out on the nitrosation of piperazine (PIP) and N-methylbenzylamine (MeBzAm) by N-methyl-N-nitroso-p-toluenesulfonamide (MNTS) in quaternary microemulsions of tetradecyltrimethylammonium bromide (TTABr)/isooctane/alcohol/water, varying the nature and the concentration of the following alcohols: 1-pentanol, 1-hexanol, 1-heptanol, 1-octanol and 1-decanol keeping the [1-alcohol]/[TTABr] = 4 relationship constant. In addition a study was carried out on the influence of the alcohol concentration, working with molar relationships [1-hexanol]/[TTABr]=3, 4 and 5. On the basis of the molar volumes of the alcohol and surfactant and the concentration of alcohol at the interface it was possible to calculate the change in its volume with as varying compositions of the microemulsion. In order to interpret the experimental results a kinetic model was devised which takes into account the distribution of the reactants between the different pseudophases and the change in the volume of the interface. The rate constants at the interface of the microemulsion are lower than in pure water and are independent of the nature of the alcohol used as a cosurfactant and the molar relationship [alcohol]/[TTABr]. This independence indicates that the main role of the cosurfactant is to increase the volume of the interface with the consequent dilution of the reactants.

  15. Kinetic Study of Water Contaminants Adsorption by Bamboo Granular Activated and Non-Activated Carbon

    Directory of Open Access Journals (Sweden)

    Opololaoluwa Oladimarun Ijaola

    2013-10-01

    Full Text Available The adsorptive capacity of metal ions from surface water with activated and non-activated carbon derived from bamboo was investigated. The validation of adsorption kinetics of Cl, PO4 and Pb was done by pseudo-first and second order model while adsorption isotherms was proved by Langmuir and Freundlich isotherm model for activated and non- activated bamboo granular carbon. Generally, the amount of metal ions uptake increases with time and activation levels and the pH of bamboo granular carbon increase with activation. Similarly, the pore space of the activated carbon also increases with activation levels. The correlation coefficients (R2 show that the pseudo-second order model gave a better fit to the adsorption process with 0.9918 as the least value and 1.00 as the highest value as compared with the pseudo-first order with 0.813 as the highest value and 0 as the least. The Freundlich isotherm was more favorable when compared with the Langmuir isotherm in determining the adsorptive capacity of bamboo granular activated carbon. The study has shown that chemical activation increases the pore space, surface area and the pH of bamboo granular carbon which ultimately increases the adsorption rate of metal ions in the contaminated surface water.

  16. Real-Time Microscopic Monitoring of Flow, Voltage and Current in the Proton Exchange Membrane Water Electrolyzer.

    Science.gov (United States)

    Lee, Chi-Yuan; Li, Shih-Chun; Chen, Chia-Hung; Huang, Yen-Ting; Wang, Yu-Syuan

    2018-03-15

    Looking for alternative energy sources has been an inevitable trend since the oil crisis, and close attentioned has been paid to hydrogen energy. The proton exchange membrane (PEM) water electrolyzer is characterized by high energy efficiency, high yield, simple system and low operating temperature. The electrolyzer generates hydrogen from water free of any carbon sources (provided the electrons come from renewable sources such as solar and wind), so it is very clean and completely satisfies the environmental requirement. However, in long-term operation of the PEM water electrolyzer, the membrane material durability, catalyst corrosion and nonuniformity of local flow, voltage and current in the electrolyzer can influence the overall performance. It is difficult to measure the internal physical parameters of the PEM water electrolyzer, and the physical parameters are interrelated. Therefore, this study uses micro-electro-mechanical systems (MEMS) technology to develop a flexible integrated microsensor; internal multiple physical information is extracted to determine the optimal working parameters for the PEM water electrolyzer. The real operational data of local flow, voltage and current in the PEM water electrolyzer are measured simultaneously by the flexible integrated microsensor, so as to enhance the performance of the PEM water electrolyzer and to prolong the service life.

  17. Analytical calculation of electrolyte water content of a Proton Exchange Membrane Fuel Cell for on-board modelling applications

    Science.gov (United States)

    Ferrara, Alessandro; Polverino, Pierpaolo; Pianese, Cesare

    2018-06-01

    This paper proposes an analytical model of the water content of the electrolyte of a Proton Exchange Membrane Fuel Cell. The model is designed by accounting for several simplifying assumptions, which make the model suitable for on-board/online water management applications, while ensuring a good accuracy of the considered phenomena, with respect to advanced numerical solutions. The achieved analytical solution, expressing electrolyte water content, is compared with that obtained by means of a complex numerical approach, used to solve the same mathematical problem. The achieved results show that the mean error is below 5% for electrodes water content values ranging from 2 to 15 (given as boundary conditions), and it does not overcome 0.26% for electrodes water content above 5. These results prove the capability of the solution to correctly model electrolyte water content at any operating condition, aiming at embodiment into more complex frameworks (e.g., cell or stack models), related to fuel cell simulation, monitoring, control, diagnosis and prognosis.

  18. Comparison of one-dimensional and point kinetics for various light water reactor transients

    International Nuclear Information System (INIS)

    Naser, J.A.; Lin, C.; Gose, G.C.; McClure, J.A.; Matsui, Y.

    1985-01-01

    The object of this paper is to compare the results from the three kinetics options: 1) point kinetics; 2) point kinetics by not changing the shape function; and 3) one-dimensional kinetics for various transients on both BWRs and PWRs. A systematic evaluation of the one-dimensional kinetics calculation and its alternatives is performed to determine the status of these models and to identify additional development work. In addition, for PWRs, the NODEP-2 - NODETRAN and SIMULATE - SIMTRAN paths for calculating kinetics parameters are compared. This type of comparison has not been performed before and is needed to properly evaluate the RASP methodology of which these codes are a part. It should be noted that RASP is in its early pre-release stage and this is the first serious attempt to examine the consistency between these two similar but different methods of generating physics parameters for the RETRAN computer code

  19. 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

    2016-01-01

    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...... number Nu range between m = 0.137 and m = 0.246. In general, it is shown that applying hot wire anemometry yields in fact very clear voltage readings with high frequency, and it can be used as a diagnosis tool in various fuel cell applications....

  20. Advanced methodology to simulate boiling water reactor transient using coupled thermal-hydraulic/neutron-kinetic codes

    Energy Technology Data Exchange (ETDEWEB)

    Hartmann, Christoph Oliver

    2016-06-13

    Coupled Thermal-hydraulic/Neutron-kinetic (TH/NK) simulations of Boiling Water Reactor transients require well validated and accurate simulation tools. The generation of cross-section (XS) libraries, depending on the individual thermal-hydraulic state parameters, is of paramount importance for coupled simulations. Problem-dependent XS-sets for 3D core simulations are being generated mainly by well validated, fast running commercial and user-friendly lattice codes such as CASMO and HELIOS. In this dissertation a computational route, based on the lattice code SCALE6/TRITON, the cross-section interface GenPMAXS, the best-estimate thermal-hydraulic system code TRACE and the core simulator PARCS, for best-estimate simulations of Boiling Water (BWR) transients has been developed and validated. The computational route has been supplemented by a subsequent uncertainty and sensitivity study based on Monte Carlo sampling and propagation of the uncertainties of input parameters to the output (SUSA code). The analysis of a single BWR fuel assembly depletion problem with PARCS using SCALE/TRITON cross-sections has been shown a good agreement with the results obtained with CASMO cross-section sets. However, to compensate the deficiencies of the interface program GenPMAXS, PYTHON scripts had to be developed to incorporate missing data, as the yields of Iodine, Xenon and Promethium, into the cross-section-data sets (PMAXS-format) generated by GenPMAXS from the SCALE/TRITON output. The results of the depletion analysis of a full BWR core with PARCS have indicated the importance of considering history effects, adequate modeling of the reflector region and the control rods, as the PARCS simulations for depleted fuel and all control rods inserted (ARI) differs significantly at the fuel assembly top and bottom. Systematic investigations with the coupled codes TRACE/PARCS have been performed to analyse the core behaviour at different thermal conditions using nuclear data (XS

  1. Corrosion of target and structural materials in water irradiated by an 800 MeV proton beam

    International Nuclear Information System (INIS)

    Butt, D.P.; Kanner, G.S.; Lillard, R.S.

    1996-01-01

    Radiation enhanced, aqueous corrosion of solid neutron-targets such as tungsten or tantalum, or target cladding or structural materials such as superalloys and stainless steels, is a significant concern in accelerator-driven transmutation technologies. In this paper we briefly describe our current methods for control and in situ monitoring of corrosion in accelerator cooling water loops. Using floating, electrochemical impedance spectroscopy (EIS), we have measured the corrosion rates of aluminum 6061, copper, Inconel 718, and 304L stainless steel in the flow loop of a water target irradiated by a μamp, 800 MeV proton beam. Impedance spectroscopy allows us to model the corrosion process of a material as an equivalent electrical circuit. Thus the polarization resistance, which is inversely proportional to the corrosion rate, can be extracted from the frequency response of a metal specimen. During a three month period, without the use of corrosion mitigation techniques, we observed increases of several orders of magnitude in the water conductivity and the corrosion rates. The increase in corrosion is at least partially attributed to a build up of peroxide in our pseudo-closed loop system. In this paper we also briefly describe our second generation experiments, scheduled to begin in late 1996. In these experiments we plan to measure the corrosion rates of tungsten, tantalum, Inconel 718, 316L and 304L stainless steel, HT-9 austenitic stainless steel, and aluminum 5053. Two or three electrode probes of each material are being placed directly in the proton beam, in a high neutron flux region, or a significant distance from the high radiation area. We will be measuring corrosion rates, changes in pH and conductivity, and we will be establishing parameters for filtration and mitigation of corrosion. We will also discuss our ideas for making in situ measurements of water radiolysis using optical and laser diagnostic techniques

  2. Kinetics of corrosion products release from nickel-base alloys corroding in primary water conditions. A new modeling of release

    International Nuclear Information System (INIS)

    Carrette, F.; Guinard, L.; Pieraggi, B.

    2002-01-01

    The radioactivity in the primary circuit arises mainly from the activation of corrosion products in the core of pressurised water reactors; corrosion products dissolve from the oxide scales developed on steam generator tubes of alloy 690. The controlling and modelling of this process require a detailed knowledge of the microstructure and chemical composition of oxide scales as well as the kinetics of their corrosion and dissolution. Alloy 690 was studied as tubes and sheets, with three various surface states (as-received, cold-worked, electropolished). Corrosion tests were performed at 325 C and 155 bar in primary water conditions (B/Li - 1000/2 ppm, [H 2 ] 30 cm 3 .kg -1 TPN, [O 2 ] < 5 ppb); test durations ranged between 24 and 2160 hours. Corrosion tests in the TITANE loop provided mainly corrosion and oxidation kinetics, and tests in the BOREAL loop yielded release kinetics. This study revealed asymptotic type kinetics. Characterisation of the oxide scales grown in representative conditions of the primary circuit was performed by several techniques (SEM, TEM, SIMS, XPS, GIXRD). These analyses revealed the essential role of the fine grained cold-worked scale present on as-received and cold-worked materials. This scale controls the corrosion and release phenomena. The kinetic study and the characterisation of the oxide scales contributed to the modelling of the corrosion/release process. A growth/dissolution model was proposed for corrosion product scales grown in non-saturated dynamic fluid. This model provided the temporal evolution of oxide scales and release kinetics for different species (Fe, Ni, Cr). The model was validated for several surface states and several alloys. (authors)

  3. Peroxone mineralization of chemical oxygen demand for direct potable water reuse: Kinetics and process control.

    Science.gov (United States)

    Wu, Tingting; Englehardt, James D

    2015-04-15

    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.

  4. Kinetic studies of the acylation of pig muscle–d-glyceraldehyde 3-phosphate dehydrogenase by 1,3-diphosphoglycerate and of proton uptake and release in the overall enzyme mechanism

    Science.gov (United States)

    Harrigan, P. J.; Trentham, D. R.

    1973-01-01

    In the presence of NAD+ the acylation by 1,3-diphosphoglycerate of the four active sites of pig muscle d-glyceraldehyde 3-phosphate dehydrogenase can be monitored at 365nm by the disappearance of the absorption band present in the binary complex of NAD+ and the enzyme. A non-specific salt effect decreased the acylation rate 25-fold when the ionic strength was increased from 0.10 to 1.0. This caused acylation to be the rate-limiting process in the enzyme-catalysed reductive dephosphorylation of 1,3-diphosphoglycerate at high ionic strength at pH8. The salt effect permitted investigation of the acylation over a wide range of conditions. Variation of pH from 5.4 to 8.6 produced at most a two-fold change in the acylation rate. One proton was taken up per site acylated at pH8.0. By using a chromophoric H+ indicator the rate of proton uptake could be monitored during the acylation and was also almost invariant in the pH range 5.5–8.5. Transient kinetic studies of the overall enzyme-catalysed reaction indicated that acylation was the process involving proton uptake at pH8.0. The enzyme mechanism is discussed in the light of these results. PMID:4360248

  5. Dose distribution of secondary radiation in a water phantom for a proton pencil beam—EURADOS WG9 intercomparison exercise

    Science.gov (United States)

    Stolarczyk, L.; Trinkl, S.; Romero-Expósito, M.; Mojżeszek, N.; Ambrozova, I.; Domingo, C.; Davídková, M.; Farah, J.; Kłodowska, M.; Knežević, Ž.; Liszka, M.; Majer, M.; Miljanić, S.; Ploc, O.; Schwarz, M.; Harrison, R. M.; Olko, P.

    2018-04-01

    Systematic 3D mapping of out-of-field doses induced by a therapeutic proton pencil scanning beam in a 300  ×  300  ×  600 mm3 water phantom was performed using a set of thermoluminescence detectors (TLDs): MTS-7 (7LiF:Mg,Ti), MTS-6 (6LiF:Mg,Ti), MTS-N (natLiF:Mg,Ti) and TLD-700 (7LiF:Mg,Ti), radiophotoluminescent (RPL) detectors GD-352M and GD-302M, and polyallyldiglycol carbonate (PADC)-based (C12H18O7) track-etched detectors. Neutron and gamma-ray doses, as well as linear energy transfer distributions, were experimentally determined at 200 points within the phantom. In parallel, the Geant4 Monte Carlo code was applied to calculate neutron and gamma radiation spectra at the position of each detector. For the cubic proton target volume of 100  ×  100  ×  100 mm3 (spread out Bragg peak with a modulation of 100 mm) the scattered photon doses along the main axis of the phantom perpendicular to the primary beam were approximately 0.5 mGy Gy‑1 at a distance of 100 mm and 0.02 mGy Gy‑1 at 300 mm from the center of the target. For the neutrons, the corresponding values of dose equivalent were found to be ~0.7 and ~0.06 mSv Gy‑1, respectively. The measured neutron doses were comparable with the out-of-field neutron doses from a similar experiment with 20 MV x-rays, whereas photon doses for the scanning proton beam were up to three orders of magnitude lower.

  6. Stomatal kinetics and photosynthetic gas exchange along a continuum of isohydric to anisohydric regulation of plant water status.

    Science.gov (United States)

    Meinzer, Frederick C; Smith, Duncan D; Woodruff, David R; Marias, Danielle E; McCulloh, Katherine A; Howard, Ava R; Magedman, Alicia L

    2017-08-01

    Species' differences in the stringency of stomatal control of plant water potential represent a continuum of isohydric to anisohydric behaviours. However, little is known about how quasi-steady-state stomatal regulation of water potential may relate to dynamic behaviour of stomata and photosynthetic gas exchange in species operating at different positions along this continuum. Here, we evaluated kinetics of light-induced stomatal opening, activation of photosynthesis and features of quasi-steady-state photosynthetic gas exchange in 10 woody species selected to represent different degrees of anisohydry. Based on a previously developed proxy for the degree of anisohydry, species' leaf water potentials at turgor loss, we found consistent trends in photosynthetic gas exchange traits across a spectrum of isohydry to anisohydry. More anisohydric species had faster kinetics of stomatal opening and activation of photosynthesis, and these kinetics were closely coordinated within species. Quasi-steady-state stomatal conductance and measures of photosynthetic capacity and performance were also greater in more anisohydric species. Intrinsic water-use efficiency estimated from leaf gas exchange and stable carbon isotope ratios was lowest in the most anisohydric species. In comparisons between gas exchange traits, species rankings were highly consistent, leading to species-independent scaling relationships over the range of isohydry to anisohydry observed. © 2017 John Wiley & Sons Ltd.

  7. Effect of zinc additions on oxide rupture strain and repassivation kinetics of iron-based alloys in 288 C water

    International Nuclear Information System (INIS)

    Angeliu, T.M.; Andresen, P.L.

    1996-01-01

    The effect of Zn water chemistry additions on the mechanism of intergranular stress corrosion cracking (IGSCC) of Fe-based alloys in water at 288 C was evaluated in terms of the slip-dissolution model. In this model, an increase in the oxide film rupture strain or surface film repassivation kinetics improved resistance to IGSCC. The oxide rupture strain of type 304L (UNS S30403) stainless steel (SS) increased up to a factor of two in deaerated and 200 ppb oxygenated, high-purity water ( 300 h of exposure. Repassivation kinetics experiments showed Zn additions of ∼ 100 ppb increased the repassivation rate of an Fe-12% Cr alloys up to a factor of two in various deaerated water environments at 288 C. Life prediction modeling revealed that the combination of a more ductile oxide film and faster repassivation kinetics resulted in a reduction in the overall crack growth rate (CGR) by at least a factor of four. This factor of improvement was consistent with data from compact tension experiments in similar environments where CGR decreased as the Zn addition increased, with a greater decrease in CGR realized at lower pre-Zn CGR

  8. Adsorption of selected emerging contaminants onto PAC and GAC: Equilibrium isotherms, kinetics, and effect of the water matrix.

    Science.gov (United States)

    Real, Francisco J; Benitez, F Javier; Acero, Juan L; Casas, Francisco

    2017-07-03

    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.

  9. Viscosity of bound water and model of proton relaxation in fine-dispersed substances at the presence of adsorbed paramagnetic ions

    International Nuclear Information System (INIS)

    Fedodeev, V.I.

    1975-01-01

    A microviscosity model of proton relaxation in pure liquids and in solutions of paramagnetic ions is examined. It is shown that the influence of adsorbed paramagnetic centers on proton relaxation in finely dispersed substances is significantly weaker than in solutions. A 'two-phase' relaxation model is used in determining the parameters of the bound liquid (water) using nuclear magnetic resonance data. The relations obtained with the model are used to compute the viscosity of water in clay. The value is of the same order of magnitude as that obtained by other methods

  10. Viscosity of bound water and model of proton relaxation in fine-dispersed substances at the presence of adsorbed paramagnetic ions

    Energy Technology Data Exchange (ETDEWEB)

    Fedodeev, V I

    1975-09-01

    A microviscosity model of proton relaxation in pure liquids and in solutions of paramagnetic ions is examined. It is shown that the influence of adsorbed paramagnetic centers on proton relaxation in finely dispersed substances is significantly weaker than in solutions. A 'two-phase' relaxation model is used in determining the parameters of the bound liquid (water) using nuclear magnetic resonance data. The relations obtained with the model are used to compute the viscosity of water in clay. The value is of the same order of magnitude as that obtained by other methods.

  11. Theory of passive proton conductance in lipid bilayers.

    Science.gov (United States)

    Nagle, J F

    1987-10-01

    The large permeability of lipid bilayers to protons compared to other small ions calls for a special proton transport mechanism. At the present time, only mechanisms involving transient hydrogen-bonded chains of water can account for the experimental result that the conductance is nearly independent of pH. Three models involving transient hydrogen-bonded chains are discussed, including an outline of the kinetic calculations that lead to predictions of current versus voltage drop and current versus pH differences. These calculations can be compared to experiment to determine which, if any, of these models pertains to lipid bilayers.

  12. Fast neutron spectroscopy by gas proton-recoil methods at the light water reactor pressure vessel simulator

    International Nuclear Information System (INIS)

    Rogers, J.W.

    1980-10-01

    Fast neutron spectrum measurements were made in a Light Water Reactor (LWR) Pressure Vessel Simulator (PVS) to provide neutron spectral definition required to appropriately perform and interpret neutron dosimetry measurements related to fast neutron damage in LWR-PV steels. Proton-recoil proportional counter methods using hydrogen and methane gas-filled detectors were applied to obtain the proton spectra from which the neutron spectra were derived. Cylindrical and spherical geometry detectors were used to cover the neutron energy range between 50 keV and 2 MeV. Results show that the neutron spectra shift in energy distribution toward lower energy between the front and back of a PVS. The relative neutron flux densities increase in this energy range with increasing thickness of the steel. Neutron spectrum fine structure shapes and changes are observed. These results should assist in the generation of more accurate effective cross sections and fluences for use in LWR-PV fast neutron dosimetry and materials damage analyses

  13. A Water-Stable Proton-Conductive Barium(II)-Organic Framework for Ammonia Sensing at High Humidity.

    Science.gov (United States)

    Guo, Kaimeng; Zhao, Lili; Yu, Shihang; Zhou, Wenyan; Li, Zifeng; Li, Gang

    2018-06-07

    In view of environmental protection and the need for early prediction of major diseases, it is necessary to accurately monitor the change of trace ammonia concentration in air or in exhaled breath. However, the adoption of proton-conductive metal-organic frameworks (MOFs) as smart sensors in this field is limited by a lack of ultrasensitive gas-detecting performance at high relative humidity (RH). Here, the pellet fabrication of a water-stable proton-conductive MOF, Ba( o-CbPhH 2 IDC)(H 2 O) 4 ] n (1) ( o-CbPhH 4 IDC = 2-(2-carboxylphenyl)-1 H-imidazole-4,5-dicarboxylic acid) is reported. The MOF 1 displays enhanced sensitivity and selectivity to NH 3 gas at high RHs (>85%) and 30 °C, and the sensing mechanism is suggested. The electrochemical impedance gas sensor fabricated by MOF 1 is a promising sensor for ammonia at mild temperature and high RHs.

  14. Design change of tower cooling water system for proton accelerator research center

    International Nuclear Information System (INIS)

    Jeon, G. P.; Kim, J. Y.; Song, I. T.; Min, Y. S.; Mun, K. J.; Cho, J. S.; Nam, J. M.; Park, S. S.; Han, Y. G.

    2012-01-01

    The Tower Cooling Water System (TC) is designed to reject the heat load generated by operating the accelerators and the utility facilities through the component cooling water (CCW) heat exchangers. The circulating water discharged from the circulating water pumps passes through the CCW heat exchangers, the Chiller condenser and the air compressor, and the heated circulating water is return to the cooling tower for the heat removal. In this study, The design of Tower Cooling Water System is changed as follows : At First, The quantity of cells is changed into six in order to operate the cooling tower accurately correspond with condition of each equipment of head loads. The fans of cooling tower are controlled by the signal of TEW installed in the latter parts of it. The type of circulation water pump is modified to centrifugal pump and debris filter system is deleted

  15. Design change of tower cooling water system for proton accelerator research center

    Energy Technology Data Exchange (ETDEWEB)

    Jeon, G. P.; Kim, J. Y.; Song, I. T.; Min, Y. S.; Mun, K. J.; Cho, J. S.; Nam, J. M.; Park, S. S.; Han, Y. G. [KAERI, Daejeon (Korea, Republic of)

    2012-10-15

    The Tower Cooling Water System (TC) is designed to reject the heat load generated by operating the accelerators and the utility facilities through the component cooling water (CCW) heat exchangers. The circulating water discharged from the circulating water pumps passes through the CCW heat exchangers, the Chiller condenser and the air compressor, and the heated circulating water is return to the cooling tower for the heat removal. In this study, The design of Tower Cooling Water System is changed as follows : At First, The quantity of cells is changed into six in order to operate the cooling tower accurately correspond with condition of each equipment of head loads. The fans of cooling tower are controlled by the signal of TEW installed in the latter parts of it. The type of circulation water pump is modified to centrifugal pump and debris filter system is deleted.

  16. Kinetic and Thermodynamics studies for Castor Oil Extraction Using Subcritical Water Technology.

    Science.gov (United States)

    Abdelmoez, Wael; Ashour, Eman; Naguib, Shahenaz M; Hilal, Amr; Al Mahdy, Dalia A; Mahrous, Engy A; Abdel-Sattar, Essam

    2016-06-01

    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%).

  17. Estimation of the nucleation kinetics for the anti-solvent crystallisation of paracetamol in methanol/water solutions

    Science.gov (United States)

    Ó'Ciardhá, Clifford T.; Frawley, Patrick J.; Mitchell, Niall A.

    2011-08-01

    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.

  18. Direct Measurements of Quantum Kinetic Energy Tensor in Stable and Metastable Water near the Triple Point: An Experimental Benchmark.

    Science.gov (United States)

    Andreani, Carla; Romanelli, Giovanni; Senesi, Roberto

    2016-06-16

    This study presents the first direct and quantitative measurement of the nuclear momentum distribution anisotropy and the quantum kinetic energy tensor in stable and metastable (supercooled) water near its triple point, using deep inelastic neutron scattering (DINS). From the experimental spectra, accurate line shapes of the hydrogen momentum distributions are derived using an anisotropic Gaussian and a model-independent framework. The experimental results, benchmarked with those obtained for the solid phase, provide the state of the art directional values of the hydrogen mean kinetic energy in metastable water. The determinations of the direction kinetic energies in the supercooled phase, provide accurate and quantitative measurements of these dynamical observables in metastable and stable phases, that is, key insight in the physical mechanisms of the hydrogen quantum state in both disordered and polycrystalline systems. The remarkable findings of this study establish novel insight into further expand the capacity and accuracy of DINS investigations of the nuclear quantum effects in water and represent reference experimental values for theoretical investigations.

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

    Science.gov (United States)

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

    2017-02-07

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

    DEFF Research Database (Denmark)

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

    1994-01-01

    . 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...... and biochemical data published, suggest that only a small fraction (invisible.(ABSTRACT TRUNCATED AT 250 WORDS)...

  1. Removal of triclosan via peroxidases-mediated reactions in water: Reaction kinetics, products and detoxification

    International Nuclear Information System (INIS)

    Li, Jianhua; Peng, Jianbiao; Zhang, Ya; Ji, Yuefei; Shi, Huanhuan; Mao, Liang; Gao, Shixiang

    2016-01-01

    Highlights: • Enzymatic treatment of triclosan in water by soybean and horseradish peroxidases. • pH, H_2O_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_C_A_T and K_C_A_T/K_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_2O_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_2O_2 concentration, while the optimal pH and H_2O_2 concentration were 7.0 and 8 μM, respectively. 98% TCS was removed with only 0.1 U mL"−"1 SBP in 30 min reaction time, while an HRP dose of 0.3 U mL"−"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_C_A_T) and catalytic efficiency (K_C_A_T/K_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/wastewater treatment.

  2. 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: ecsxg@nju.edu.cn [State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing 210023 (China)

    2016-06-05

    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

  3. Measurement of proton momentum distributions using a direct geometry instrument

    International Nuclear Information System (INIS)

    Senesi, R; Andreani, C; Kolesnikov, A I

    2014-01-01

    We report the results of inelastic neutron scattering measurements on bulk water and ice using the direct geometry SEQUOIA chopper spectrometer at the Spallation Neutron Source (USA), with incident energy E i = 6 eV. In this set up the measurements allow to access the Deep Inelastic Neutron Scattering regime. The scattering is centred at the proton recoil energy given by the impulse approximation, and the shape of the recoil peak conveys information on the proton momentum distribution in the system. The comparison with the performance of inverse geometry instruments, such as VESUVIO at the ISIS source (UK), shows that complementary information can be accessed by the use of direct and inverse geometry instruments. Analysis of the neutron Compton profiles shows that the proton kinetic energy in ice at 271 K is larger than in room temperature liquid water, in agreement with previous measurements on VESUVIO

  4. Measurement of proton autoneutralization potential

    International Nuclear Information System (INIS)

    Garcia, M.

    1984-09-01

    A proton space charge having multi-MeV kinetic energy was injected through a thin ground plane to extract electrons and produce a time-dependent autoneutralization space potential. An electon-emitting floating-potential resistive divider was used to measure the space potential during 20 ns of the proton current pulse. During this time, proton kinetic energy fell from 10.6 MeV to 8.5 MeV and thus the space potential (taken as 1.09 x the floating potential) fell from 5.8 kV to 4.6 kV

  5. Kinetic model for predicting the concentrations of active halogens species in chlorinated saline cooling waters. Final report

    International Nuclear Information System (INIS)

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

    1981-08-01

    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. 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.

    1981-08-01

    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.

  7. Analyzing water soluble soil organics as Trifluoroacetyl derivatives by liquid state proton nuclear magnetic resonance

    Science.gov (United States)

    Felipe Garza Sanchez; Zakiya Holmes Leggett; Sabapathy Sankar

    2005-01-01

    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...

  8. Local area water removal analysis of a proton exchange membrane fuel cell under gas purge conditions.

    Science.gov (United States)

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

    2012-01-01

    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.

  9. Liquid Water Transport in the Reactant Channels of Proton Exchange Membrane Fuel Cells

    Science.gov (United States)

    Banerjee, Rupak

    Water management has been identified as a critical issue in the development of PEM fuel cells for automotive applications. Water is present inside the PEM fuel cell in three phases, i.e. liquid phase, vapor phase and mist phase. Liquid water in the reactant channels causes flooding of the cell and blocks the transport of reactants to the reaction sites at the catalyst layer. Understanding the behavior of liquid water in the reactant channels would allow us to devise improved strategies for removing liquid water from the reactant channels. In situ fuel cell tests have been performed to identify and diagnose operating conditions which result in the flooding of the fuel cell. A relationship has been identified between the liquid water present in the reactant channels and the cell performance. A novel diagnostic technique has been established which utilizes the pressure drop multiplier in the reactant channels to predict the flooding of the cell or the drying-out of the membrane. An ex-situ study has been undertaken to quantify the liquid water present in the reactant channels. A new parameter, the Area Coverage Ratio (ACR), has been defined to identify the interfacial area of the reactant channel which is blocked for reactant transport by the presence of liquid water. A parametric study has been conducted to study the effect of changing temperature and the inlet relative humidity on the ACR. The ACR decreases with increase in current density as the gas flow rates increase, removing water more efficiently. With increase in temperature, the ACR decreases rapidly, such that by 60°C, there is no significant ACR to be reported. Inlet relative humidity of the gases does change the saturation of the gases in the channel, but did not show any significant effect on the ACR. Automotive powertrains, which is the target for this work, are continuously faced with transient changes. Water management under transient operating conditions is significantly more challenging and has not

  10. 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:

    2009-01-01

    The perovskite BaCe(0.9 − x)ZrxY0.1O(3 − δ) has been prepared by solid state reaction at 1400 °C and conventional sintering at 1700 °C. Water uptake experiments performed between 400 and 600 °C, at a water vapour pressure of 0.02 atm, provide data on the concentration of protons incorporated in t...

  11. Kinetics of Corrosion Inhibition of Aluminum in Acidic Media by Water-Soluble Natural Polymeric Pectates as Anionic Polyelectrolyte Inhibitors.

    Science.gov (United States)

    Hassan, Refat M; Zaafarany, Ishaq A

    2013-06-17

    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.

  12. 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

    2013-06-01

    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.

  13. Kinetics of photocatalytic removal of 2-amino-5-chloropyridine from water

    Directory of Open Access Journals (Sweden)

    Abramović Biljana F.

    2004-01-01

    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.

  14. Study of the iron corrosion at the interface of different media (water, air) submitted to protons irradiation

    International Nuclear Information System (INIS)

    Lapuerta, S.

    2005-10-01

    During the deep geological disposal, stainless steel containers of the vitrified waste will be put in carbon steel overpacks. After the closing of the storage site, overpacks will be in contact with a humid air and a radioactive medium. After hundred years, overpacks could be in contact with water radiolysis in an anoxic medium. In this context, my PhD work is a fundamental study which is the understanding of the corrosion mechanisms of pure iron under proton irradiation. This corrosion is affected by the contact of iron with different atmospheres (air, nitrogen) and water. In the case of the atmospheric iron corrosion under irradiation, we have studied the influence of the proton beam flux. During this work, we have characterized the structure of the oxides formed at the iron surface. The structure formed does not correspond to iron oxides and hydroxides indexed. However, we have shown that the oxide structure is close to that of lepidocrocite and bernalite. Moreover, we have determined the oxygen diffusion coefficient in iron under irradiation and we have shown that the irradiation accelerates of 6 orders of magnitude the iron corrosion. In addition, the irradiations which were realized in different gas have put in evidence the negligible role of nitrates, and the importance of the O 2 /H 2 O coupling on the iron corrosion. Finally, we have shown the influence of the relative humidity, the maximum of the corrosion being observed for a relative humidity close to 45%. In the case of the iron corrosion in aqueous media under irradiation, the influence of the oxygen dissolved in water has been studied using a surface marker. We have put in evidence that the corrosion is twice more significant in aerated medium than in deaerated medium. Moreover, the influence of radicals has been shown. An irradiated sample is more corroded than a sample put in contact with a H 2 O 2 solution. Finally, the follow-up of the iron potential under irradiation have shown the majority role

  15. Kinetics of oxygen exchange between bisulfite ion and water as studied by oxygen-17 nuclear magnetic resonance spectroscopy

    International Nuclear Information System (INIS)

    Horner, D.A.

    1984-08-01

    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 2 + H 2 O right reversible H + + SHO 3 - . 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 3 - ) and the other with the proton bonded to an oxygen (SO 3 H - ). (The symbol SHO 3 - 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 3 H - , 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

  16. A Compilation of Rate Parameters of Water-Mineral Interaction Kinetics for Application to Geochemical Modeling

    Science.gov (United States)

    2004-03-01

    Eggleston C. M. (2002) Dissolution kinetics of magnesite in acidic solutions: A hydrothermal atomic force microscopy study assessing step kinetics and...glass dissolution: I. An experimental study of the dissolution rates of basaltic glass as a function of aqueous Al, Si and oxalic acid concentration at...Stillings L. L., Drever J. I., Brantley S. L., Sun Y., and Oxburgh R. (1996) Rates of feldspar dissolution at pH 3-7 with 0-8mM oxalic acid . Chem

  17. Proton migration along the membrane surface in the absence of charged or titratable groups

    International Nuclear Information System (INIS)

    Springer, A.

    2011-01-01

    Proton diffusion along membrane surfaces is thought to be essential for many cellular processes such as energy transduction. For example, proton diffusion along membrane surfaces is considered to be the dominant mechanism of proton exchange between membrane sites of high and low proton concentrations. For the investigation of this mechanism, kinetic experiments on proton diffusion are evaluated to determine the ability of lipid membranes to retain protons on their surfaces. Experiments on different lipid bilayer membranes (DPhPC, DPhPE and GMO) are performed under the influence of two types of mobile buffer molecules (Capso, NH4CL). During these experiments the surface diffusion of photolytically released protons is visualized in terms of fluorescence changes of a lipid bound pH-sensitive dye (DHPE +fluorescein). The protons under investigation are released by flash photolysis of a hydrophobic caged compound (DMCM, caged diethyl phosphate). The experimental data confirm the existence of an energy barrier, which prevents the protons from escaping into the bulk. So far this effect was attributed to the proton binding to titrateable groups (e.g. ethanolamine) or electrostatic forces created by charged moieties (e.g. phosphate groups) on the membrane/water interface. However, upon removal of the titrateable groups and charged moieties from the membrane surface, a significant energy barrier remained as indicated by the experiments with glycerol monooleate (GMO) bilayers. To estimate the size of the barrier a semi-analytical model is presented that describes the two and three dimensional proton diffusion and the related physical and chemical processes. Common models describe surface proton diffusion as a series of subsequent hopping processes between membrane-anchored buffer molecules. Our experiments provide evidence for an alternative model. We released membrane-bound caged protons by UV flashes and monitored their arrival at distant sites s by fluorescence

  18. Quantum nature of protons in water probed by scanning tunneling microscopy and spectroscopy

    Science.gov (United States)

    Guo, Jing; Lü, Jing-Tao; Feng, Yexin; Chen, Ji; Peng, Jinbo; Lin, Zeren; Meng, Xiangzhi; Wang, Zhichang; Li, Xin-Zheng; Wang, En-Ge; Jiang, Ying; Jing-Tao Lü Team; Xin-Zheng Li Team

    The complexity of hydrogen-bonding interaction largely arises from the quantum nature of light hydrogen nuclei, which has remained elusive for decades. Here we report the direct assessment of nuclear quantum effects on the strength of a single hydrogen bond formed at a water-salt interface, using tip-enhanced inelastic electron tunneling spectroscopy (IETS) based on a low-temperature scanning tunneling microscope (STM). The IETS signals are resonantly enhanced by gating the frontier orbitals of water via a chlorine-terminated STM tip, such that the hydrogen-bonding strength can be determined with unprecedentedly high accuracy from the redshift in the O-H stretching frequency of water. Isotopic substitution experiments combined with quantum simulations reveal that the anharmonic quantum fluctuations of hydrogen nuclei weaken the weak hydrogen bonds and strengthen the relatively strong ones. However, this trend can be completely reversed when the hydrogen bond is strongly coupled to the polar atomic sites of the surface.

  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)

    1997-09-01

    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. The protonation state of small carboxylic acids at the water surface from photoelectron spectroscopy

    Czech Academy of Sciences Publication Activity Database

    Ottosson, N.; Wernersson, Erik; Söderström, J.; Pokapanich, W.; Kaufmann, S.; Svensson, S.; Persson, I.; Öhrwall, G.; Björneholm, O.

    2011-01-01

    Roč. 13, č. 26 (2011), s. 12261-12267 ISSN 1463-9076 Institutional research plan: CEZ:AV0Z40550506 Keywords : water surface * carboxylic acids * photoelectron spectroscopy Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 3.573, year: 2011

  1. Kinetic model for predicting the composition of chlorinated water discharged from power plant cooling systems

    International Nuclear Information System (INIS)

    Lietzke, M.H.

    1977-01-01

    The results of applying a kinetic model to the chlorination data supplied by Commonwealth Edison on the once-through cooling system at the Quad Cities Nuclear Station provide a validation of the model. The two examples given demonstrate that the model may be applied to either once-through cooling systems or to cooling systems involving cooling towers

  2. Kinetic and equilibrium aspects of adsorption and desorption of class II hydrophobins HFBI and HFBII at silicon oxynitride/water and air/water interfaces.

    Science.gov (United States)

    Krivosheeva, Olga; Dėdinaitė, Andra; Linder, Markus B; Tilton, Robert D; Claesson, Per M

    2013-02-26

    Hydrophobins are relatively small globular proteins produced by filamentous fungi. They display unusual high surface activity and are implied as mediators of attachment to surfaces, which has resulted in high scientific and technological interest. In this work we focus on kinetic and equilibrium aspects of adsorption and desorption properties of two representatives of class II hydrophobins, namely HFBI and HFBII, at a negatively charged hydrophilic solid/water interface and at the air/water interface. The layers formed at the air/liquid interface were examined in a Langmuir trough, whereas layers formed at the solid/liquid interface were studied using dual polarization interferometry (DPI) under different flow conditions. For comparison, another globular protein, lysozyme, was also investigated. It was found that both the adsorbed amount and the adsorption kinetics were different for HFBI and HFBII, and the adsorption behavior of both hydrophobins on the negatively charged surface displayed some unusual features. For instance, even though the adsorption rate for HFBI was slowed down with increasing adsorbed amount as expected from packing constraints at the interface, the adsorption kinetics curves for HFBII displayed a region indicating adsorption cooperativity. Further, it was found that hydrophobin layers formed under flow partly desorbed when the flow was stopped, and the desorption rate for HFBII was enhanced in the presence of hydrophobins in solution.

  3. Electro-activity of cobalt and nickel complexes for the reduction of protons into di-hydrogen. Application to PEM water electrolysis

    International Nuclear Information System (INIS)

    Pantani, O.; Anxolabehere, E.; Aukauloo, A.; Millet, P.

    2006-01-01

    Proton exchange membrane (PEM) water electrolysis is a safe and efficient way to perform water splitting into di-hydrogen and di-oxygen. In a PEM water electrolyser, platinum is commonly used as electro-catalyst on the cathodic side of the cells, mostly because of its efficiency for hydrogen evolution. But for cost considerations, there is a need to find alternative low-cost electrocatalysts. Molecular chemistry offers the possibility of synthesizing new compounds for this purpose, such as transition metal complexes. Results obtained with nickel- and cobalt-oximes compounds are presented in this paper. They have been chemically (1H NMR, EPR) and electrochemically (voltametry, spectro-electrochemistry) characterized. Their ability to electrochemically reduce protons into di-hydrogen when they are either dissolved in solution or immobilized at the surface of a solid electrode is discussed. (authors)

  4. Transformation of ranitidine during water chlorination and ozonation: Moiety-specific reaction kinetics and elimination efficiency of NDMA formation potential.

    Science.gov (United States)

    Jeon, Dahee; Kim, Jisoo; Shin, Jaedon; Hidayat, Zahra Ramadhany; Na, Soyoung; Lee, Yunho

    2016-11-15

    Ranitidine can produce high yields of N-nitrosodimethylamine (NDMA) upon chloramination and its presence in water resources is a concern for water utilities using chloramine disinfection. This study assessed the efficiency of water chlorination and ozonation in transforming ranitidine and eliminating its NDMA formation potential (NDMA-FP) by determining moiety-specific reaction kinetics, stoichiometric factors, and elimination levels in real water matrices. Despite the fact that chlorine reacts rapidly with the acetamidine and thioether moieties of ranitidine (k>10(8)M(-1)s(-1) at pH 7), the NDMA-FP decreases significantly only when chlorine reacts with the less reactive tertiary amine (k=3×10(3)M(-1)s(-1) at pH 7) or furan moiety (k=81M(-1)s(-1) at pH 7). Ozone reacts rapidly with all four moieties of ranitidine (k=1.5×10(5)-1.6×10(6)M(-1)s(-1) at pH 7) and its reaction with the tertiary amine or furan moiety leads to complete elimination of the NDMA-FP. Treatments of ranitidine-spiked real water samples have shown that ozonation can efficiently deactivate ranitidine in water and wastewater treatment, while chlorination can be efficient for water containing low concentration of ammonia. This result can be applied to the other structurally similar, potent NDMA precursors. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. Post synthetic modification of MIL-101(Cr) for S-shaped isotherms and fast kinetics with water adsorption

    International Nuclear Information System (INIS)

    Teo, How Wei Benjamin; Chakraborty, Anutosh; Kayal, Sibnath

    2017-01-01

    Highlights: • Modification of parent MIL-101(Cr) metal organic framework (MOF) employing alkali metal ions (Li + , Na + , K + ). • Surface characteristics of the parent and alkali doped MIL-101(Cr) adsorbents. • Water uptakes are measured for the temperatures ranging from 25 °C to 60 °C under static and dynamic conditions. • Isotherms and kinetics data are fitted with Langmuir analogy models. • The 5% Li-doped MIL-101(Cr) is suitable for adsorption cooling. - Abstract: This article presents the surface characteristics of alkali (Li + , Na + , K + ) doped MIL-101(Cr) metal organic frameworks (MOFs), and the structural properties are evaluated by scanning electron micrography (SEM), X-ray diffraction (XRD), thermo-gravimetric analyser (TGA) and N 2 adsorption analysis. The amount of water uptakes are measured by a gravimetric analyser for the temperatures ranging from 298 K to 333 K and pressures up to the saturated conditions. The experimentally measured isotherms and kinetics data are fitted with the equations developed from the concept of Langmuir analogy. The isosteric heat of adsorption is calculated employing Van’t Hoff equation in the pressure-temperature-uptake co-ordinate systems. The hydrophobic length at low pressure regions is shortened by the addition of alkali dopants. It is observed that the alkali (Na, K and Li) ions on MIL-101(Cr) MOF increase the water uptakes at lower relative pressure region with fast kinetics. We have shown here that the alkali doped MIL-101(Cr) MOFs can be used as potential adsorbents for various low temperature heat transmission applications such as adsorption assisted heat pump, cooling and desalination.

  6. R1 correction in amide proton transfer imaging: indication of the influence of transcytolemmal water exchange on CEST measurements.

    Science.gov (United States)

    Li, Hua; Li, Ke; Zhang, Xiao-Yong; Jiang, Xiaoyu; Zu, Zhongliang; Zaiss, Moritz; Gochberg, Daniel F; Gore, John C; Xu, Junzhong

    2015-12-01

    Amide proton transfer (APT) imaging may potentially detect mobile proteins/peptides non-invasively in vivo, but its specificity may be reduced by contamination from other confounding effects such as asymmetry of non-specific magnetization transfer (MT) effects and spin-lattice relaxation with rate R1 (=1/T1). Previously reported spillover, MT and R1 correction methods were based on a two-pool model, in which the existence of multiple water compartments with heterogeneous relaxation properties in real tissues was ignored. Such simple models may not adequately represent real tissues, and thus such corrections may be unreliable. The current study investigated the effectiveness and accuracy of correcting for R1 in APT imaging via simulations and in vivo experiments using tumor-bearing rats subjected to serial injections of Gd-DTPA that produced different tissue R1 values in regions of blood-brain-barrier breakdown. The results suggest that conventional measurements of APT contrast (such as APT* and MTRasym ) may be significantly contaminated by R1 variations, while the R1 -corrected metric AREX* was found to be relatively unaffected by R1 changes over a broad range (0.4-1 Hz). Our results confirm the importance of correcting for spin-lattice relaxation effects in quantitative APT imaging, and demonstrate the reliability of using the observed tissue R1 for corrections to obtain more specific and accurate measurements of APT contrast in vivo. The results also indicate that, due to relatively fast transcytolemmal water exchange, the influence of intra- and extracellular water compartments on CEST measurements with seconds long saturation time may be ignored in tumors. Copyright © 2015 John Wiley & Sons, Ltd.

  7. Light particle production in spallation reactions induced by protons of 0.8-2.5 GeV incident kinetic energy

    International Nuclear Information System (INIS)

    Herbach, Claus-Michael; Enke, Michael; Boehm, Andreas

    2002-01-01

    Absolute production cross sections have been measured simultaneously for neutrons and light charged particles in 0.8-2.5 GeV proton induced spallation reactions for a series of target nuclei from aluminum up to uranium. The high detection efficiency both for neutral and charged evaporative particles provides an event-wise access to the amount of projectile energy dissipated into nuclear excitation. Various intra nuclear cascade plus evaporation models have been confronted with the experimental data showing large discrepancies for hydrogen and helium production. (author)

  8. 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

    2014-01-01

    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

  9. Kinetics of reactions of oxidation of carbon by carbon dioxide and water steam at high temperatures and low pressures

    International Nuclear Information System (INIS)

    Boulangier, Francois

    1956-01-01

    The first objective of this research thesis was to obtain new and reliable experimental results about the reaction kinetics of the oxidation of carbon by carbon dioxide and water steam, and to avoid some disturbing phenomena, for example and more particularly the appearance of electric discharges beyond 1900 K initiated by the filament thermoelectric emission. The author tried to identify the mechanism of the accelerating effect. It appears that previous experiments had been performed only in these disturbed conditions. At the lowest temperatures, the author highlighted the existence of a surface contamination by the desorption products from the apparatus [fr

  10. Kinetics of Ultrasound-Assisted Flavonoid Extraction from Agri-Food Solid Wastes Using Water/Glycerol Mixtures

    Directory of Open Access Journals (Sweden)

    Dimitris P. Makris

    2016-01-01

    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.

  11. Focus on adsorptive equilibrium, kinetics and thermodynamic components of petroleum produced water biocoagulation using novel Tympanotonos Fuscatus extract

    Directory of Open Access Journals (Sweden)

    Matthew Menkiti

    2018-03-01

    Full Text Available Adsorptive component of produced water (PW coagulation using Tympanotonos Fuscatus coagulant (TFC was studied. Influence of the following parameters: pH, coagulant dose, settling time, and temperature were investigated. The functional group, crystalline nature, morphological observation and thermal characteristics of the sample were evaluated. Equilibrium data were analyzed using Langmuir, Freundlich, Temkin, Frumkin, and Dubinin-Radushkevich (D-R adsorption isotherms. The kinetics data were fitted to reversible first order, pseudo-first-order, pseudo-second-order, elovich, intra-particle diffusion and Boyd kinetic models. Adsorption Gibbs energy, enthalpy and entropy were evaluated. Equilibrium data best fitted the Langmuir isotherm (R2 > 0.99; X2 < 1.6; SSE < 1.6. Reversible first order model correlated best to the kinetics data. The values of process average Gibb's free energy, enthalpy and entropy were 30.35, 27.88 and 0.1891 kJ/mol, respectively. The process was spontaneous, feasible and endothermic in nature. The maximum efficiency of 83.1% was favored at pH 2.0. This study indicated significant adsorptive component, while using Tympanotonos Fuscatus extract as readily available, renewable, ecofriendly bio – coagulant for efficient treatments of PW.

  12. Kinetic measurements of the hydrolytic degradation of cefixime: effect of Captisol complexation and water-soluble polymers.

    Science.gov (United States)

    Mallick, Subrata; Mondal, Arijit; Sannigrahi, Santanu

    2008-07-01

    We have taken kinetic measurements of the hydrolytic degradation of cefixime, and have studied the effect of Captisol complexation and water-soluble polymers on that degradation. The phase solubility of cefixime in Captisol was determined. Kinetic measurements were carried out as a function of pH and temperature. High-performance liquid chromatography (HPLC) was performed to assay all the samples of phase-solubility analysis and kinetic measurements. Chromatographic separation of the degradation products was also performed by HPLC. FT-IR spectroscopy was used to investigate the presence of any interaction between cefixime and Captisol and soluble polymer. The phase-solubility study showed A(L)-type behaviour. The pH-rate profile of cefixime exhibited a U-shaped profile whilst the degradation of cefixime alone was markedly accelerated with elevated temperature. A strong stabilizing influence of the cefixime-Captisol complexation and hypromellose was observed against aqueous mediated degradation, as compared with povidone and macrogol. The unfavourable effect of povidone and macrogol may have been due to the steric hindrance, which prevented the guest molecule from entering the cyclodextrin cavity, whereas hypromellose did not produce any steric hindrance.

  13. Water oxidation by photosystem II: H(2)O-D(2)O exchange and the influence of pH support formation of an intermediate by removal of a proton before dioxygen creation.

    Science.gov (United States)

    Gerencsér, László; Dau, Holger

    2010-11-30

    Understanding the chemistry of photosynthetic water oxidation requires deeper insight into the interrelation between electron transfer (ET) and proton relocations. In photosystem II membrane particles, the redox transitions of the water-oxidizing Mn complex were initiated by nanosecond laser flashes and monitored by absorption spectroscopy at 360 nm (A(360)). In the oxygen evolution transition (S(3) + hν → S(0) + O(2)), an exponential decrease in A(360) (τ(O(2)) = 1.6 ms) can be assigned to Mn reduction and O(2) formation. The corresponding rate-determining step is the ET from the Mn complex to a tyrosine radical (Y(Z)(ox)). We find that this A(360) decrease is preceded by a lag phase with a duration of 170 ± 40 μs (τ(lag) at pH 6.2), indicating formation of an intermediate before ET and O-O bond formation and corroborating results obtained by time-resolved X-ray spectroscopy. Whereas τ(O(2)) exhibits a minor kinetic isotope effect and negligible pH dependence, formation of the intermediate is slowed significantly both in D(2)O (τ(lag) increase of ∼140% in D(2)O) and at low pH (τ(lag) of 30 ± 20 μs at pH 7.0 vs τ(lag) of 470 ± 80 μs at pH 5.5). These findings support the fact that in the oxygen evolution transition an intermediate is created by deprotonation and removal of a proton from the Mn complex, after Y(Z)(ox) formation but before the onset of electron transfer and O-O bond formation.

  14. Water-soluble triazabutadienes that release diazonium species upon protonation under physiologically relevant conditions.

    Science.gov (United States)

    Kimani, Flora W; Jewett, John C

    2015-03-23

    Triazabutadienes are an understudied structural motif that have remarkable reactivity once rendered water-soluble. It is shown that these molecules readily release diazonium species in a pH-dependent manner in a series of buffer solutions with pH ranges similar to those found in cells. Upon further development, we expect that this process will be well suited to cargo-release strategies and organelle-specific bioconjugation reactions. These compounds offer one of the mildest ways of generating diazonium species in aqueous solutions. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Cesium, manganese and cobalt water-sediment transfer kinetics and diffusion into mangrove sediments inferred by radiotracer experiments

    International Nuclear Information System (INIS)

    Machado, E.C.; Machado, W.; Patchineelam, S.R.

    2012-01-01

    A study on the trace elements transfer from tidal water to mangrove sediments from Guanabara Bay (southeastern Brazil) was performed in laboratory microcosms. Sediment cores were covered with tidal water spiked with 137 Cs, 54 Mn and 57 Co during 5-h experiments, and water samples were taken at regular intervals to measure uptake kinetics at the sediment-water interface. At the end of the experiments, the uptake and diffusional penetration into the sediments was evaluated. Half-removal times from water to sediments were slightly higher for 137 Cs (3.4 ± 1.7 h) than observed for 54 Mn (2.3 ± 0.2 h) and 57 Co (2.6 ± 1.1 h). After these experiments, all radioisotopes presented decreasing activities with increasing sediment depth, being the distribution of 137 Cs indicative of higher diffusion within the upper 2 cm. This study on the removal of 137 Cs, 54 Mn and 57 Co from tidal water by mangrove sediments suggests that while 57 Co and 54 Mn presented closer behaviors, there was a slightly higher mobility of 137 Cs. (author)

  16. water alteration processes and kinetics of basaltic glasses, natural analogue of nuclear glasses

    International Nuclear Information System (INIS)

    Techer, I.; Advocat, Th.; Vernaz, E.; Lancelot, J.R.; Liotard, J.M.

    1997-01-01

    Dissolution experiments of a basaltic glass were carried out at 90 deg C for different reaction progresses. The initial dissolution rate was compared with values obtained for rhyolitic glass and the R7T7 nuclear glass. The activation energy was also determined by computing literature data. The results provide similar reactional mechanism for basaltic and nuclear glasses. Dissolution rates measured under saturation conditions were compared to theoretical dissolution rates. These ones were calculated using two kinetic models: the first rate equation is the Grambow's law which only takes into account ortho-silica acid activity; the second rate equation was proposed by Daux et al., where silica and aluminum are combined to formulate the affinity. The comparison between experimental and theoretical results point out that these two models are not appropriate to describe the alteration kinetic of basaltic glasses. (authors)

  17. Zirconium metal-water oxidation kinetics. III. Oxygen diffusion in oxide and alpha Zircaloy phases

    International Nuclear Information System (INIS)

    Pawel, R.E.

    1976-10-01

    The reaction of Zircaloy in steam at elevated temperature involves the growth of discrete layers of oxide and oxygen-rich alpha Zircaloy from the parent beta phase. The multiphase, moving boundary diffusion problem involved is encountered in a number of important reaction schemes in addition to that of Zircaloy-oxygen and can be completely (albeitly ideally) characterized through an appropriate model in terms of oxygen diffusion coefficients and equilibrium concentrations for the various phases. Conversely, kinetic data for phase growth and total oxygen consumption rates can be used to compute diffusion coefficients. Equations are developed that express the oxygen diffusion coefficients in the oxide and alpha phases in terms of the reaction rate constants and equilibrium solubility values. These equations were applied to recent experimental kinetic data on the steam oxidation of Zircaloy-4 to determine the effective oxygen diffusion coefficients in these phases over the temperature range 1000--1500 0 C

  18. Investigation of kinetics and absorption isotherm models for hydroponic phytoremediation of waters contaminated with sulfate.

    Science.gov (United States)

    Saber, Ali; Tafazzoli, Milad; Mortazavian, Soroosh; James, David E

    2018-02-01

    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.

  19. Transition state kinetics of Hg(II) adsorption at gibbsite-water interface

    International Nuclear Information System (INIS)

    Weerasooriya, Rohan; Tobschall, Heinz J.; Seneviratne, Wasana; Bandara, Atula

    2007-01-01

    Kinetics of adsorption plays a pivotal factor in determining the bio-availability and mobility of Hg(II) in the environment. The kinetics of Hg(II) adsorption on gibbsite was examined as a function of pH, temperature and electrolyte type. Adsorption of Hg(II) was highly non-linear where the rate of Hg(II) retention was rapid initially and was followed by gradual or somewhat slow retention behavior with increasing contact time. The respective rate constants designated as k 1 (S-1: fast step) and k 2 (S-2: slow step). Always k 1 follows the order: k 1 ClO 4 >=k 1 (NO 3 ) 4 >>k 1 Cl . Such a relationship was not observed for the S-2 route. A two-step reaction model with pseudo-first order kinetics successfully described the adsorption rates of Hg(II) on gibbsite. Arrhenius and Erying models determined the thermodynamic parameters at activation states, which correspond to S-1 and S-2 routes. In a given system, always the activation energies showed a decrease with the pH. Gibbs free energy (ΔG numbersign ), enthalpy (ΔH numbersign ), and entropy (ΔS numbersign ) values of activation states were almost similar both in NaClO 4 and NaNO 3 which signal a similar Hg(II) adsorptive mechanism on gibbsite. The configurations of different Hg(II)-surface complexes were elucidated by transmission vibration spectroscopy

  20. Role of the interaction processes in the depth-dose distribution of proton beams in liquid water

    International Nuclear Information System (INIS)

    Garcia-Molina, Rafael; Abril, Isabel; De Vera, Pablo; Kyriakou, Ioanna; Emfietzoglou, Dimitris

    2012-01-01

    We use a simulation code, based on Molecular Dynamics and Monte Carlo, to investigate the depth-dose profile and lateral radial spreading of swift proton beams in liquid water. The stochastic nature of the projectile-target interaction is accounted for in a detailed manner by including in a consistent way fluctuations in both the energy loss due to inelastic collisions and the angular deflection from multiple elastic scattering. Depth-variation of the projectile charge-state as it slows down into the target, due to electron capture and loss processes, is also considered. By selectively switching on/off these stochastic processes in the simulation, we evaluate the contribution of each one of them to the Bragg curve. Our simulations show that the inclusion of the energy-loss straggling sizeably affects the width of the Bragg peak, whose position is mainly determined by the stopping power. The lateral spread of the beam as a function of the depth in the target is also examined.

  1. 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

    2010-01-01

    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...... 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....... 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...

  2. New kinetic-spectrophotometric method for monitoring the concentration of iodine in river and city water samples.

    Science.gov (United States)

    Farmany, A; Khosravi, A; Abbasi, S; Cheraghi, J; Hushmandfar, R; Sobhanardakani, S; Noorizadeh, H; Mortazavi, S S

    2013-01-01

    A new kinetic method has been developed for the determination of iodine in water samples. The method is based on the catalytic effect of I(-) with the oxidation of Indigo Carmine (IC) by KBrO(3) in the sulfuric acid medium. The optimum conditions obtained are 0.16 M sulfuric acid, 1 × 10(-3) M of IC, 1 × 10(-2) M KBrO(3), reaction temperature of 35°C, and reaction time of 80 s at 612 nm. Under the optimized conditions, the method allowed the quantification of I(-) in a range of 12-375 ng/mL with a detection limit of 0.46 ng/mL. The method was applied to the determination of iodine in river and city water samples with the satisfactorily results.

  3. Validation of the kinetic model for predicting the composition of chlorinated water discharged from power plant cooling systems

    International Nuclear Information System (INIS)

    Lietzke, M.H.

    1977-01-01

    The purpose of this report is to present a validation of a previously described kinetic model which was developed to predict the composition of chlorinated fresh water discharged from power plant cooling systems. The model was programmed in two versions: as a stand-alone program and as a part of a unified transport model developed from consistent mathematical models to simulate the dispersion of heated water and radioisotopic and chemical effluents from power plant discharges. The results of testing the model using analytical data taken during operation of the once-through cooling system of the Quad Cities Nuclear Station are described. Calculations are also presented on the Three Mile Island Nuclear Station which uses cooling towers

  4. 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

    2017-02-01

    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.

  5. A Comparison of Alkaline Water and Mediterranean Diet vs Proton Pump Inhibition for Treatment of Laryngopharyngeal Reflux.

    Science.gov (United States)

    Zalvan, Craig H; Hu, Shirley; Greenberg, Barbara; Geliebter, Jan

    2017-10-01

    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

  6. Cs-134 transfer from water or food to the Ciprinid Tinca tinca Linnaeus: uptake and loss kinetics

    International Nuclear Information System (INIS)

    Corisco, J.A.G.; Carreiro, M.C.V.

    1991-01-01

    Experiments with 134 Cs and the fish Tinca tinca Linnaeus (fam. Cyprinidae), as a part of a more extensive work, concerning a simplified freshwater trophic chain using water from Fratel dam, (at Tejo River), were undertaken. Direct uptake from water, during a period of about 30 days, leads to a kinetics expressed by the power function: CF (t) = 0.58 t 0.781 (t in days), the concentration factor (CF) referred to wet weight. Retention study, showed the existence of two biological half-lives, Tb 1 = 7 days and Tb 2 = 87 days, which might concern respectively, the 134 Cs desorption from the transit organs and the loss of the assimilated isotope from the storage organs. In the accumulation through the food chain, using planktonic crustacean Daphnia magna Straus (Cladocera) as prey, a transfer factor (TF) related to wet weight of both fish and prey, is estimated through the power function: TF (t) = 0.022 t 0.578 (t in days). Finally, the retention study following the food pathway contamination, stresses the existence of one long term component, with half-life Tb = 61 days. The transfer factor kinetics seems to point out to a rather slow process, leading to lower 134 Cs concentration values, than the contamination through the water. The loss of the assimilated 134 Cs, uptaken through both pathways, water or food, is a slow process. The longer biological half-life is very important in Radiological Protection, once it may be attributed to the radionuclide loss from the muscular mass. (author)

  7. 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)

    2011-01-01

    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.

  8. 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.

    2001-06-04

    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.

  9. A combined molecular dynamics and Monte Carlo simulation of the spatial distribution of energy deposition by proton beams in liquid water

    Energy Technology Data Exchange (ETDEWEB)

    Garcia-Molina, Rafael [Departamento de Fisica, Centro de Investigacion en Optica y Nanofisica (CIOyN), Universidad de Murcia, E-30100 Murcia (Spain); Abril, Isabel [Departament de Fisica Aplicada, Universitat d' Alacant, E-03080 Alacant (Spain); Heredia-Avalos, Santiago [Departament de Fisica, Enginyeria de Sistemes i Teoria del Senyal, Universitat d' Alacant, E-03080 Alacant (Spain); Kyriakou, Ioanna; Emfietzoglou, Dimitris, E-mail: rgm@um.es [Medical Physics Laboratory, University of Ioannina Medical School, GR-45110 Ioannina (Greece)

    2011-10-07

    We have evaluated the spatial distribution of energy deposition by proton beams in liquid water using the simulation code SEICS (Simulation of Energetic Ions and Clusters through Solids), which combines molecular dynamics and Monte Carlo techniques and includes the main interaction phenomena between the projectile and the target constituents: (i) the electronic stopping force due to energy loss to target electronic excitations, including fluctuations due to the energy-loss straggling, (ii) the elastic scattering with the target nuclei, with their corresponding energy loss and (iii) the dynamical changes in projectile charge state due to electronic capture and loss processes. An important feature of SEICS is the accurate account of the excitation spectrum of liquid water, based on a consistent solid-state description of its energy-loss-function over the whole energy and momentum space. We analyse how the above-mentioned interactions affect the depth distribution of the energy delivered in liquid water by proton beams with incident energies of the order of several MeV. Our simulations show that the position of the Bragg peak is determined mainly by the stopping power, whereas its width can be attributed to the energy-loss straggling. Multiple elastic scattering processes contribute slightly only at the distal part of the Bragg peak. The charge state of the projectiles only changes when approaching the end of their trajectories, i.e. near the Bragg peak. We have also simulated the proton-beam energy distribution at several depths in the liquid water target, and found that it is determined mainly by the fluctuation in the energy loss of the projectile, evaluated through the energy-loss straggling. We conclude that a proper description of the target excitation spectrum as well as the inclusion of the energy-loss straggling is essential in the calculation of the proton beam depth-dose distribution.

  10. 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

    2016-01-01

    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 senso....... 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....

  11. A combined molecular dynamics and Monte Carlo simulation of the spatial distribution of energy deposition by proton beams in liquid water

    International Nuclear Information System (INIS)

    Garcia-Molina, Rafael; Abril, Isabel; Heredia-Avalos, Santiago; Kyriakou, Ioanna; Emfietzoglou, Dimitris

    2011-01-01

    We have evaluated the spatial distribution of energy deposition by proton beams in liquid water using the simulation code SEICS (Simulation of Energetic Ions and Clusters through Solids), which combines molecular dynamics and Monte Carlo techniques and includes the main interaction phenomena between the projectile and the target constituents: (i) the electronic stopping force due to energy loss to target electronic excitations, including fluctuations due to the energy-loss straggling, (ii) the elastic scattering with the target nuclei, with their corresponding energy loss and (iii) the dynamical changes in projectile charge state due to electronic capture and loss processes. An important feature of SEICS is the accurate account of the excitation spectrum of liquid water, based on a consistent solid-state description of its energy-loss-function over the whole energy and momentum space. We analyse how the above-mentioned interactions affect the depth distribution of the energy delivered in liquid water by proton beams with incident energies of the order of several MeV. Our simulations show that the position of the Bragg peak is determined mainly by the stopping power, whereas its width can be attributed to the energy-loss straggling. Multiple elastic scattering processes contribute slightly only at the distal part of the Bragg peak. The charge state of the projectiles only changes when approaching the end of their trajectories, i.e. near the Bragg peak. We have also simulated the proton-beam energy distribution at several depths in the liquid water target, and found that it is determined mainly by the fluctuation in the energy loss of the projectile, evaluated through the energy-loss straggling. We conclude that a proper description of the target excitation spectrum as well as the inclusion of the energy-loss straggling is essential in the calculation of the proton beam depth-dose distribution.

  12. H atom kinetics in superheated water studied by muon spin spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Percival, Paul W. [Department of Chemistry and TRIUMF, Simon Fraser University, 8888 University Drive, Burnaby BC, V5A 1S6 (Canada)]. E-mail: percival@sfu.ca; Brodovitch, Jean-Claude [Department of Chemistry and TRIUMF, Simon Fraser University, 8888 University Drive, Burnaby BC, V5A 1S6 (Canada); Ghandi, Khashayar [Department of Chemistry and TRIUMF, Simon Fraser University, 8888 University Drive, Burnaby BC, V5A 1S6 (Canada); McCollum, Brett M. [Department of Chemistry and TRIUMF, Simon Fraser University, 8888 University Drive, Burnaby BC, V5A 1S6 (Canada); McKenzie, Iain [Department of Chemistry and TRIUMF, Simon Fraser University, 8888 University Drive, Burnaby BC, V5A 1S6 (Canada)

    2007-08-15

    It is possible to study H atom chemistry in aqueous systems over a wide range of conditions, from standard to supercritical, using the exotic atom muonium (Mu) as an effective light isotope of hydrogen. The Mu rate constants exhibit marked non-Arrhenius behaviour, going through a maximum and fall-off as the density is reduced in the neighbourhood of the critical point, and subsequent recovery as the medium becomes more gas-like. This is illustrated with new kinetic data for the reaction of Mu with methanol.

  13. H atom kinetics in superheated water studied by muon spin spectroscopy

    International Nuclear Information System (INIS)

    Percival, Paul W.; Brodovitch, Jean-Claude; Ghandi, Khashayar; McCollum, Brett M.; McKenzie, Iain

    2007-01-01

    It is possible to study H atom chemistry in aqueous systems over a wide range of conditions, from standard to supercritical, using the exotic atom muonium (Mu) as an effective light isotope of hydrogen. The Mu rate constants exhibit marked non-Arrhenius behaviour, going through a maximum and fall-off as the density is reduced in the neighbourhood of the critical point, and subsequent recovery as the medium becomes more gas-like. This is illustrated with new kinetic data for the reaction of Mu with methanol

  14. Inter- and intra-annular proton exchange in gaseous benzylbenzenium ions (protonated diphenylmethane)

    OpenAIRE

    Kuck, Dietmar; Bäther, Wolfgang

    1986-01-01

    Two distinct proton exchange reactions occur in metastable gaseous benzylbenzenium ions, generated by isobutane chemical ionization of diphenylmethane and four deuterium-labelled analogues. Whereas the proton ring-walk at the benzenium moiety is fast giving rise to a completely random intraannular proton exchange, the interannular proton exchange is surprisingly slow and competes with the elimination of benzene. A kinetic isotope effect of kH/kD= 5 has been determined for the interannular pro...

  15. Kinetics and mechanism of hydrolysis of benzimidazolylcarbamates

    OpenAIRE

    Norberto, F. P.; Santos, S. P.; Iley, J.; Silva, D. B.; Corte Real, M.

    2007-01-01

    Synthesis of new 2-aminobenzimidazole-1-carbamates was accomplished by carbamoylation of 2-aminobenzimidazole using different substituted phenyl chloroformates. The aqueous hydrolysis of the new compounds was examined in the pH range 1-13 at 25 ºC. The evaluated kinetic parameters led to the conclusion that up to pH 4 reaction proceeds by a bimolecular attack of water to the N-protonated substrate. This is the first time this behavior is described for carbamates, and can be ascribed to the hi...

  16. Transformation of methylparaben during water chlorination: Effects of bromide and dissolved organic matter on reaction kinetics and transformation pathways.

    Science.gov (United States)

    Yoom, Hoonsik; Shin, Jaedon; Ra, Jiwoon; Son, Heejong; Ryu, Dongchoon; Kim, Changwon; Lee, Yunho

    2018-09-01

    The reaction kinetics, products, and pathways of methylparaben (MeP) during water chlorination with and without bromide (Br - ) were investigated to better understand the fate of parabens in chlorinated waters. During the chlorination of MeP-spiked waters without Br - , MeP was transformed into mono-Cl-MeP and di-Cl-MeP with apparent second-order rate constants (k app ) of 64M -1 s -1 and 243M -1 s -1 at pH7, respectively, while further chlorination of di-Cl-MeP was relatively slower (k app =1.3M -1 s -1 at pH7). With increasing Br - concentration, brominated MePs, such as mono-Br-MeP, Br-Cl-MeP, and di-Br-MeP, became major transformation products. The di-halogenated MePs (di-Cl-MeP, Br,Cl-MeP, and di-Br-MeP) showed relatively low reactivity to chlorine at pH7 (k app =1.3-4.6M -1 s -1 ) and bromine (k app =32-71M -1 s -1 ), which explains the observed high stability of di-halogenated MePs in chlorinated waters. With increasing pH from 7 to 8.5, the transformation of di-halogenated MePs was further slowed due to the decreasing reactivity of di-MePs to chlorine. The formation of the di-halogenated MePs and their further transformation become considerably faster at Br - concentrations higher than 0.5μM (40μg/L). Nonetheless, the accelerating effect of Br - diminishes in the presence of dissolved organic matter (DOM) extract (Suwannee River humic acid (SRHA)) due to a more rapid consumption of bromine by DOM than chlorine. The effect of Br - on the fate of MeP was less in the tested real water matrices, possibly due to a more rapid bromine consumption by the real water DOM compared to SRHA. A kinetic model was developed based on the determined species-specific second-order rate constants for chlorination/bromination of MeP and its chlorinated and brominated MePs and the transformation pathway information, which could reasonably simulate the transformation of MePs during the chlorination of water in the presence of Br - and selected DOM. Copyright © 2017 Elsevier B

  17. Evaluation of the rod ejection accident in Westinghouse Pressurized Water Reactors using spatial kinetics methods

    International Nuclear Information System (INIS)

    Risher, D.H. Jr.

    1975-01-01

    The consequences of a rod ejection accident are investigated in relation to the latest, high power density Westinghouse reactors. Limiting criteria are presented, based on experimental evidence, and if not exceeded these criteria will ensure that there will be no interference with core cooling capability, and radiation releases, if any, will be within the guidelines of 10CFR100. A basis is presented for the conservative selection of plant parameters to be used in the analysis, such that the analysis is applicable to a wide range of past, present, and future reactors. The calculational method employs a one-dimensional spatial kinetics computer code and a transient fuel heat transfer computer code to determine the hot spot fuel temperature versus time following a rod ejection. Using these computer codes, the most limiting hot channel factor (which does not cause the fuel damage limit criteria to be exceeded) has been determined as a function of the ejected rod worth. By this means, the limit criteria have been translated into ejected rod worths and hot channel factors which can be used effectively by the nuclear designer and safety analyst. The calculational method is shown to be conservative, compared to the results of a three-dimensional spatial kinetics analysis

  18. Removal of Pb from Water by Adsorption on Apple Pomace: Equilibrium, Kinetics, and Thermodynamics Studies

    Directory of Open Access Journals (Sweden)

    Piar Chand

    2013-01-01

    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.

  19. Manganese kinetics in the shore crab Carcinus maenas exposed via food and water

    International Nuclear Information System (INIS)

    Bjerregaard, P.; Hastrup, M.

    1999-01-01

    Oxygen depletion in marine water has been an increasing problem in many coastal areas due to eutrophication. Under hypoxic and anoxic conditions in bottom waters, the flux of manganese out of the sediment increases and substantial concentrations of dissolved manganese in the water column can be reached. Manganese liberated as Mn ++ from the sediment during hypoxic conditions is re-oxidised fairly slowly (in order of weeks) after reintroduction of oxygen to the water. Therefore, benthic organisms may encounter concurrent exposure to increased manganese concentrations and hypoxic condition

  20. Determination of kinetic coefficients for the reduction and removal of uranium from water by the Desulfovibrio desulfuricans bacteria

    International Nuclear Information System (INIS)

    Tucker, M.D.; Barton, L.L.; Thomson, B.M.

    1996-01-01

    Uranium contamination of groundwater and surface water from abandoned uranium mill tailings piles is a serious concern in many areas of the western United States. U(VI) is soluble in water and, as a result, is relatively mobile in the environment. U(IV), however, is generally insoluble in water and, therefore, is not subject to aqueous transport. In recent years, researchers have discovered that certain microorganisms, such as the sulfate-reducing bacteria Desuffiovibrio desulfricans, can mediate the reduction of U(VI) to U(IV) by anaerobic respiration. Although the ability of this microorganism to reduce U(VI) has been studied in some detail by previous researchers, the kinetics of the reaction have not been characterized. The purpose of this research was to perform kinetic studies on Desuffiovibrio desulfricans during simultaneous reduction of sulfate and uranium and to determine the mineral phase of uranium after it has been reduced. The studies were conducted in a laboratory-scale chemostat under substrate-limited growth conditions with pyruvate as the substrate. The maximum rate of substrate utilization (k) was determined to be 4.70 days -1 while the half-velocity constant (Ks) was 140 mg CODA. The yield coefficient (Y) was determined to be 0. 17 mg cells/mg COD while the endogenous decay coefficient (kd) was found to be 0.072 days -1 . After reduction, U(IV) precipitated from solution in the uraninite (UO 2 ) phase as predicted by thermodynamics. Uranium removal efficiency as high as 90% was achieved in the chemostat

  1. Kinetics of electron-induced decomposition of CF2Cl2 coadsorbed with water (ice): A comparison with CCl4

    International Nuclear Information System (INIS)

    Faradzhev, N.S.; Perry, C.C.; Kusmierek, D.O.; Fairbrother, D.H.; Madey, T.E.

    2004-01-01

    The kinetics of decomposition and subsequent chemistry of adsorbed CF 2 Cl 2 , activated by low-energy electron irradiation, have been examined and compared with CCl 4 . These molecules have been adsorbed alone and coadsorbed with water ice films of different thicknesses on metal surfaces (Ru; Au) at low temperatures (25 K; 100 K). The studies have been performed with temperature programmed desorption (TPD), reflection absorption infrared spectroscopy (RAIRS), and x-ray photoelectron spectroscopy (XPS). TPD data reveal the efficient decomposition of both halocarbon molecules under electron bombardment, which proceeds via dissociative electron attachment (DEA) of low-energy secondary electrons. The rates of CF 2 Cl 2 and CCl 4 dissociation increase in an H 2 O (D 2 O) environment (2-3x), but the increase is smaller than that reported in recent literature. The highest initial cross sections for halocarbon decomposition coadsorbed with H 2 O, using 180 eV incident electrons, are measured (using TPD) to be 1.0±0.2x10 -15 cm 2 for CF 2 Cl 2 and 2.5±0.2x10 -15 cm 2 for CCl 4 . RAIRS and XPS studies confirm the decomposition of halocarbon molecules codeposited with water molecules, and provide insights into the irradiation products. Electron-induced generation of Cl - and F - anions in the halocarbon/water films and production of H 3 O + , CO 2 , and intermediate compounds COF 2 (for CF 2 Cl 2 ) and COCl 2 , C 2 Cl 4 (for CCl 4 ) under electron irradiation have been detected using XPS, TPD, and RAIRS. The products and the decomposition kinetics are similar to those observed in our recent experiments involving x-ray photons as the source of ionizing irradiation

  2. Experimental study of water desorption isotherms and thin-layer convective drying kinetics of bay laurel leaves

    Science.gov (United States)

    Ghnimi, Thouraya; Hassini, Lamine; Bagane, Mohamed

    2016-12-01

    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.

  3. Proton therapy

    International Nuclear Information System (INIS)

    Smith, Alfred R

    2006-01-01

    Proton therapy has become a subject of considerable interest in the radiation oncology community and it is expected that there will be a substantial growth in proton treatment facilities during the next decade. I was asked to write a historical review of proton therapy based on my personal experiences, which have all occurred in the United States, so therefore I have a somewhat parochial point of view. Space requirements did not permit me to mention all of the existing proton therapy facilities or the names of all of those who have contributed to proton therapy. (review)

  4. Kinetic Requirements for the Measurement of Mesospheric Water Vapor at 6.8 (microns) under Non-LTE Conditions

    Science.gov (United States)

    Zhou, Daniel K.; Mlynczak, Martin G.; Lopez-Puertas, Manuel; Russell, James M., III

    1999-01-01

    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.

  5. 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.

    2008-01-01

    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,

  6. Kinetics of phenol degradation in water solutions under gamma-irradiation

    International Nuclear Information System (INIS)

    Guliyeva, U.A.; Gurbanov, M.A.; Abdullayev, E.T.

    2014-01-01

    Full text : In this work the chemical oxygen demand and change of phenol concentration at the radiolysis of aqueous solutions of phenol was studied. Irradiation conducted under gamma-irradiation of 60Co at static conditions and at room temperature. The main component is water, therefore the radiolysis process of water plays an important role in radiolytic degradation of phenol

  7. Using decomposition kinetics to model the removal of mine water pollutants in constructed wetlands

    Energy Technology Data Exchange (ETDEWEB)

    Tarutis, W J; Unz, R F [Pennsylvania State University, University Park, PA (United States)

    1994-01-01

    Although numerous mathematical models have been used to describe decomposition, few, if any, have been used to model the removal of pollutants in constructed wetlands. A steady state method based on decomposition kinetics and reaction stoichiometry has been developed which simulates the removal of ferrous iron entering wetlands constructed for mine drainage treatment. Input variables for the model include organic matter concentration, reaction rate coefficient, porosity and dry density, and hydraulic detection time. Application of the model assumes complete anaerobic conditions within the entire substrate profile, constant temperature, no additional organic matter input, and subsurface flow only. For these ideal conditions, model simulations indicate that wetlands constructed with readily decomposable substrates rich in organic carbon are initially capable of removing far greater amounts of iron than wetlands built with less biodegradable substrates. However, after three to five years of operation this difference becomes negligible. For acceptable long-term treatment performance, therefore, periodic additions of decomposable organic matter will be required.

  8. Zirconium metal-water oxidation kinetics. V. Oxidation of Zircaloy in high pressure steam

    International Nuclear Information System (INIS)

    Pawel, R.E.; Cathcart, J.V.; Campbell, J.J.; Jury, S.H.

    1977-12-01

    A series of scoping tests to determine the influence of steam pressure on the isothermal oxidation kinetics of Zircaloy-4 PWR tubing was undertaken. The oxidation experiments were conducted in flowing steam at 3.45, 6.90, and 10.34 MPa (500, 1000, and 1500 psi) at 905 0 C (1661 0 F), and at 3.45 and 6.90 MPa at 1101 0 C (2014 0 F). A comparison of the results of these experiments with those obtained for oxidation in steam at atmospheric pressure under similar conditions indicated that measurable enhancement of the oxidation rate occurred with increasing pressure at 905 0 C, but not at 1100 0 C

  9. Measurement of water kinetics with deuterium oxide in lactating dairy cows

    International Nuclear Information System (INIS)

    Odwongo, W.O.; Conrad, H.R.; Staubus, A.E.; Harrison, J.H.

    1985-01-01

    Following intravenous infusion with approximately 300 mg deuterium oxide per kg body weight, blood was drawn from lactating Holsteins (Trial 1, n = 4, and Trial 2, n = 5) at suitable intervals for up to 12 days while the cows were maintained on dietary regimens to which they were well adapted. Time results for deuterium oxide concentration in blood were described best by the three-compartment open model system, which showed that the central, shallow peripheral, and deep peripheral body water compartments contained 27.1, 25.0, and 23.2% body weight in trial 1 and 33.7, 27.1, and 19.9% body weight in trial 2. Total body water estimates averaged 75.3 and 80.7% body weight during trials 1 and 2. Estimates for biological half-life of water were 4.6 and 3.2 days and those for water turnover were 68.9 and 109.7 liters/day, respectively. The data fitted the two-compartment open model system when observations made prior to 25 min post-administration were excluded from the analyses, because the central and shallow peripheral compartments were apparently lumped into one. Blood sampling at 0.5, 1, and 1.5 days following infusion and thereafter at 1-day intervals was adequate for the estimates of the one compartment open model system. Estimates of total body water, water biological half-life, and water turnover were similar for the different models. It is concluded that the three-compartment open model provides greater detail and insight into the water dynamics of lactating dairy cows having regular access to food and water, whereas the two- and one-compartment open model systems provide good approximations only

  10. A method for analyzing the non-stationary nucleation and overall transition kinetics: A case of water

    International Nuclear Information System (INIS)

    Mokshin, Anatolii V.; Galimzyanov, Bulat N.

    2014-01-01

    We present the statistical method as a direct extension of the mean first-passage time concept to the analysis of molecular dynamics simulation data of a phase transformation. According to the method, the mean first-passage time trajectories for the first (i = 1) as well as for the subsequent (i = 2, 3, 4,…) nucleation events should be extracted that allows one to calculate the time-dependent nucleation rate, the critical value of the order parameter (the critical size), the waiting times for the nucleation events, and the growth law of the nuclei – i.e., all the terms, which are usually necessary to characterize the overall transition kinetics. There are no restrictions in the application of the method by the specific thermodynamic regions; and the nucleation rate parameters are extracted according to their basic definitions. The method differs from the Wedekind-Bartell scheme and its modification [A. V. Mokshin and B. N. Galimzyanov, J. Phys. Chem. B 116, 11959 (2012)], where the passage-times for the first (largest) nucleus are evaluated only and where the average waiting time for the first nucleation event is accessible instead of the true steady-state nucleation time scale. We demonstrate an efficiency of the method by its application to the analysis of the vapor-to-liquid transition kinetics in water at the different temperatures. The nucleation rate/time characteristics and the droplet growth parameters are computed on the basis of the coarse-grained molecular dynamics simulation data

  11. Kinetic Coupling of Water Splitting and Photoreforming on SrTiO 3 -Based Photocatalysts

    Energy Technology Data Exchange (ETDEWEB)

    Sanwald, Kai E. [Department of Chemistry and Catalysis Research Center, TU München, Lichtenbergstrasse 4, 85747 Garching, Germany; Berto, Tobias F. [Department of Chemistry and Catalysis Research Center, TU München, Lichtenbergstrasse 4, 85747 Garching, Germany; Jentys, Andreas [Department of Chemistry and Catalysis Research Center, TU München, Lichtenbergstrasse 4, 85747 Garching, Germany; Camaioni, Donald M. [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352, United States; Gutiérrez, Oliver Y. [Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352, United States; Lercher, Johannes A. [Department of Chemistry and Catalysis Research Center, TU München, Lichtenbergstrasse 4, 85747 Garching, Germany; Institute for Integrated Catalysis, Pacific Northwest National Laboratory, P.O. Box 999, Richland, Washington 99352, United States

    2018-02-26

    Coupling the anodic half-reactions of overall water splitting and oxygenate photoreforming (i.e., proton reduction and oxygenate oxidations) on Al-doped SrTiO3 decorated with a co-catalyst enables efficient photocatalytic H2 generation along with oxygenate conversion without accumulating undesired intermediates such as formaldehyde. The net H2-evolution rates result from the interplay between water oxidation, oxygenate oxidation, and the back-reaction of H2 and O2 to water. When the latter pathway is quantitatively suppressed (e.g., on RhCrOx co-catalyst or in excess of oxygenated hydrocarbons), the initial H2-evolution rates are independent of the oxygenate nature and concentration. This is a consequence of the reduction equivalents for H2-evolution provided by water oxidation compensating changes in the rates of oxygenate conversion. Thus, under conditions of suppressed back-reaction, water and oxygenate oxidations have equal quantum efficiencies. The selectivities to water and oxygenate oxidation depend on oxygenate nature and concentration. Transformations mediated by indirect hole transfer dominate as a result of the water oxidation at the anode and the associated intermediates generated in O2-evolution catalysis (e.g. ·OH, ·O and ·OOH). On the undecorated semiconductor, the O2 produced during overall water splitting is reductively activated to participate in glycerol oxidation without consuming evolved H2. Acknowledgements The authors would like to thank ESRF in Grenoble, France, for providing beam time at the ID26 station for XAFS experiments. K.E.S. gratefully acknowledges financial support by the Fond der Chemischen Industrie (FCI). J.A.L. and O.Y.G. acknowledge support for his contribution by the Laboratory Directed Research and Development Program at Pacific Northwest National Laboratory, a multi-program national laboratory operated by Battelle for the U.S. Department of Energy. The authors thank Xaver Hecht for BET measurements, Martin Neukamm for

  12. Proton permeation of lipid bilayers.

    Science.gov (United States)

    Deamer, D W

    1987-10-01

    Proton permeation of the lipid bilayer barrier has two unique features. First, permeability coefficients measured at neutral pH ranges are six to seven orders of magnitude greater than expected from knowledge of other monovalent cations. Second, proton conductance across planar lipid bilayers varies at most by a factor of 10 when pH is varied from near 1 to near 11. Two mechanisms have been proposed to account for this anomalous behavior: proton conductance related to contaminants of lipid bilayers, and proton translocation along transient hydrogen-bonded chains (tHBC) of associated water molecules in the membrane. The weight of evidence suggests that trace contaminants may contribute to proton conductance across planar lipid membranes at certain pH ranges, but cannot account for the anomalous proton flux in liposome systems. Two new results will be reported here which were designed to test the tHBC model. These include measurements of relative proton/potassium permeability in the gramicidin channel, and plots of proton flux against the magnitude of pH gradients. (1) The relative permeabilities of protons and potassium through the gramicidin channel, which contains a single strand of hydrogen-bonded water molecules, were found to differ by at least four orders of magnitude when measured at neutral pH ranges. This result demonstrates that a hydrogen-bonded chain of water molecules can provide substantial discrimination between protons and other cations. It was also possible to calculate that if approximately 7% of bilayer water was present in a transient configuration similar to that of the gramicidin channel, it could account for the measured proton flux. (2) The plot of proton conductance against pH gradient across liposome membranes was superlinear, a result that is consistent with one of three alternative tHBC models for proton conductance described by Nagle elsewhere in this volume.

  13. Absorbed dose to water determination with ionization chamber dosimetry and calorimetry in restricted neutron, photon, proton and heavy-ion radiation fields.

    Science.gov (United States)

    Brede, H J; Greif, K-D; Hecker, O; Heeg, P; Heese, J; Jones, D T L; Kluge, H; Schardt, D

    2006-08-07

    Absolute dose measurements with a transportable water calorimeter and ionization chambers were performed at a water depth of 20 mm in four different types of radiation fields, for a collimated (60)Co photon beam, for a collimated neutron beam with a fluence-averaged mean energy of 5.25 MeV, for collimated proton beams with mean energies of 36 MeV and 182 MeV at the measuring position, and for a (12)C ion beam in a scanned mode with an energy per atomic mass of 430 MeV u(-1). The ionization chambers actually used were calibrated in units of air kerma in the photon reference field of the PTB and in units of absorbed dose to water for a Farmer-type chamber at GSI. The absorbed dose to water inferred from calorimetry was compared with the dose derived from ionometry by applying the radiation-field-dependent parameters. For neutrons, the quantities of the ICRU Report 45, for protons the quantities of the ICRU Report 59 and for the (12)C ion beam, the recommended values of the International Atomic Energy Agency (IAEA) protocol (TRS 398) were applied. The mean values of the absolute absorbed dose to water obtained with these two independent methods agreed within the standard uncertainty (k = 1) of 1.8% for calorimetry and of 3.0% for ionometry for all types and energies of the radiation beams used in this comparison.

  14. Review: kinetics of water-soluble contrast media in the central nervous system

    International Nuclear Information System (INIS)

    Sage, M.R.

    1983-01-01

    In neuroradiology, intraarterial, intravenous, and intrathecal injections of water-soluble contrast media are made. With the growing importance of water-soluble myelography, interventional angiography, and enhanced computed tomography (CT), it is essential to have a clear understanding of the response of the nervous system to such procedures. The blood, cerebrospinal fluid (CSF), and extracellular fluid of the parenchyma form the fluid compartments of the brain with three interfaces between, namely, the blood-brain interface, the CSF-brain interface, and the blood-CSF interface. One of more of these interfaces are exposed to water-soluble contrast media after intraarterial, intravenous, or intrathecal administration. The behavior of water-soluble contrast media at these interfaces is discussed on the basis of local experience and a review of the literature

  15. Metal-porphyrin interactions. V. Kinetics of cyanide addition to a water soluble iron porphyrin dimer(1)

    Energy Technology Data Exchange (ETDEWEB)

    Hambright, P; Rishnamurthy, M K

    1975-01-01

    The kinetics of cyanide addition to the water-soluble oxybridged iron dimer of tetra (p-sulophenyl) porphin indicate that HCN is the reactant. The rate law is of the form: Rate = (3.8 +- 0.2) x 10/sup 4/ (Fe dimer) (HCN)/(1 + (3.1 +- 0.3) x 10/sup 10/ (H/sup +/)) at 25/sup 0/ ..mu.. = 0.7 (NaNO/sub 3/). The cyano iron dimer dissociates into dicyano iron monomers by two pathways, one first order in (H/sup +/), and one proportional to (H/sup +/)(CN/sup -/)/sup 2/. The mechanism of this dimer reaction is compared to iron porphyrin monomer systems.

  16. Simultaneous removal of potent cyanotoxins from water using magnetophoretic nanoparticle of polypyrrole: adsorption kinetic and isotherm study.

    Science.gov (United States)

    Hena, S; Rozi, R; Tabassum, S; Huda, A

    2016-08-01

    Cyanotoxins, microcystins and cylindrospermopsin, are potent toxins produced by cyanobacteria in potable water supplies. This study investigated the removal of cyanotoxins from aqueous media by magnetophoretic nanoparticle of polypyrrole adsorbent. The adsorption process was pH dependent with maximum adsorption occurring at pH 7 for microcystin-LA, LR, and YR and at pH 9 for microcystin-RR and cylindrospermopsin (CYN). Kinetic studies and adsorption isotherms reflected better fit for pseudo-second-order rate and Langmuir isotherm model, respectively. Thermodynamic calculations showed that the cyanotoxin adsorption process is endothermic and spontaneous in nature. The regenerated adsorbent can be successfully reused without appreciable loss of its original capacity.

  17. Measurement of activation reaction rate distribution on a mercury target with a lead-reflector and light-water-moderator for high energy proton bombardment using AGS accelerator

    International Nuclear Information System (INIS)

    Kasugai, Yoshimi; Takada, Hiroshi; Meigo, Shin-ichiro

    2001-02-01

    Characteristic of spallation neutrons driven by GeV protons from a mercury target with a lead-reflector and light-water-moderator was studied experimentally using the Alternating Gradient Synchrotron (AGS) facility of Brookhaven National Laboratory in a framework of the ASTE (AGS Spallation Target Experiment) collaboration. Several reaction rates along with the mercury target were measured with the activation method at incident proton energies of 1.94, 12 and 24 GeV. Indium, niobium, aluminum, cobalt, nickel and bismuth were used as activation detectors to cover the threshold energy of between 0.33 and 40.9 MeV. This report summarizes the experimental procedure with all the measured data. (author)

  18. Spin-locking vs. chemical exchange saturation transfer MRI for investigating chemical exchange process between water and labile metabolite protons

    Science.gov (United States)

    Jin, Tao; Autio, Joonas; Obata, Takayuki; Kim, Seong-Gi

    2010-01-01

    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

  19. Spin-locking versus chemical exchange saturation transfer MRI for investigating chemical exchange process between water and labile metabolite protons.

    Science.gov (United States)

    Jin, Tao; Autio, Joonas; Obata, Takayuki; Kim, Seong-Gi

    2011-05-01

    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.

  20. On kinetics of 90Sr exchange between Elodea and water surroundings

    International Nuclear Information System (INIS)

    Chebotina, N.Ya.; Yagov, A.P.

    1979-01-01

    The extraction of 90 Sr from elodea was studied in dependence on the of plant preexposition in isotope-bearing water. Elodea plants were submerged in 90 SrCl 2 solution with the concentration of 20 μCi/l for different periods of time (5 and 30 min; 1,5,10,50,100 and 400 h.); after that they were transfered into pure lake water which at first was changed every minute and then in 2,4,8,20,46,72 and 120 hours. Determined was the isotope content in disorbiny solution, and residual plant radioactivity. Radiometry of preparations was carried out 12-14 days after sampling by PST-100 device with BFL-T-25 counter. Periods of biological half-life of 90 Sr(Tsub(1/2) were determined graphically. It was shown that the retention durability of the isotope in plants increased with plant exposure time in Sr-bearing water. It was determined both by total quantity of radionuclide migrated from elodea into water media and forms of its retention in plants. At small plant expositions in radioactive solutions (from 5 min to 5 h) 90% of 90 Sr migrated during the experiment from elodea into water media, but at 400 hour exposition, only 56%. Two forms of radiostrontium bound with biosubstrate with different degree of retention durability were separated

  1. Advantages of chemical exchange-sensitive spin-lock (CESL) over chemical exchange saturation transfer (CEST) for hydroxyl- and amine-water proton exchange studies.

    Science.gov (United States)

    Jin, Tao; Kim, Seong-Gi

    2014-11-01

    The chemical exchange (CE) rate of endogenous hydroxyl and amine protons with water is often comparable to the difference in their chemical shifts. These intermediate exchange processes have been imaged by the CE saturation transfer (CEST) approach with low-power and long-duration irradiation. However, the sensitivity is not optimal and, more importantly, the signal is contaminated by slow magnetization transfer processes. Here, the properties of CEST signals are compared with those of a CE-sensitive spin-lock (CESL) technique irradiating at the labile proton frequency. First, using a higher power and shorter irradiation in CE-MRI, we obtain: (i) an increased selectivity to faster CE rates via a higher sensitivity to faster CEs and a lower sensitivity to slower CEs and magnetization transfer processes; and (ii) a decreased in vivo asymmetric magnetization transfer contrast measured at ±15 ppm. The sensitivity gain of CESL over CEST is higher for a higher power and shorter irradiation. Unlike CESL, CEST signals oscillate at a very high power and short irradiation. Second, time-dependent CEST and CESL signals are well modeled by analytical solutions of CE-MRI with an asymmetric population approximation, which can be used for quantitative CE-MRI and validated by simulations of Bloch-McConnell equations and phantom experiments. Finally, the in vivo amine-water proton exchange contrast measured at 2.5 ppm with ω1 = 500 Hz is 18% higher in sensitivity for CESL than CEST at 9.4 T. Overall, CESL provides better exchange rate selectivity and sensitivity than CEST; therefore, CESL is more suitable for CE-MRI of intermediate exchange protons. Copyright © 2014 John Wiley & Sons, Ltd.

  2. Advantages of Chemical Exchange-Sensitive Spin-Lock (CESL) Over Saturation Transfer (CEST) for Hydroxyl- and Amine-Water Proton Exchange Studies

    Science.gov (United States)

    Jin, Tao; Kim, Seong-Gi

    2014-01-01

    The chemical exchange (CE) rate of endogenous hydroxyl and amine protons with water is often comparable to the difference in their chemical shifts. These intermediate exchange (IMEX) processes have been imaged by the CE saturation transfer (CEST) approach with low-power and long-duration irradiation. However, its sensitivity is not optimal, and more importantly, the signal is contaminated by slow magnetization transfer processes. Here, the property of CEST signals is compared to a CE-sensitive spin-locking (CESL) technique irradiating at the labile proton frequency. Firstly, using a higher power and shorter irradiation in CE-MRI yields i) increasing selectivity to faster chemical exchange rates by higher sensitivity to faster exchanges and less sensitivity to slower CE and magnetization transfer processes, and ii) decreasing in vivo asymmetric magnetization transfer contrast measured at ±15 ppm. The sensitivity gain of CESL over CEST is higher for a higher-power and shorter irradiation. Unlike CESL, CEST signals oscillate at a very high power and short irradiation. Secondly, time-dependent CEST and CESL signals are well modeled by analytical solutions of CE-MRI with asymmetric population approximation (CEAPA), which can be used for quantitative CE-MRI, and validated by simulations of Bloch-McConnell equations and phantom experiments. Lastly, in vivo amine-water proton exchange contrast measured at 2.5 ppm with ω1 of 500 Hz is 18% higher in sensitivity for CESL than CEST at 9.4 T. Overall, CESL provides better exchange rate selectivity and sensitivity than CEST; therefore, CESL is more suitable for CE-MRI of IMEX protons. PMID:25199631

  3. Influence of the product gases on the kinetics of water vapour gasification as a function of pressure and temperature

    International Nuclear Information System (INIS)

    Muehlen, H.J.

    1983-01-01

    The reaction kinetics of coal gasification by using the process heat is investigated. Pressure, temperature and composition of the gasifying agent are varied. Starting from other models, a kinetic model is derived and tested for its applicability. (PW) [de

  4. Effect of Micellization on the Adsorption Kinetics of Polymeric Surfactants to the Solid/Water Interface

    Science.gov (United States)

    Toomey, Ryan; Tirrell, Matthew

    2002-03-01

    We have studied the adsorption kinetics of two classes of hydrophobic/ionic diblock copolymer surfactants in aqueous environments to understand the role that micellization plays in the adsorption process. The two systems studied were poly(t-butyl styrene)-block-poly(styrene sulfonate) (PtBS-b-PSS) and polystyrene-block-poly(acrylic acid) (PS-b-PAA). It is found that by changing the hydrophobicity of the adsorbing surface, micelle adsorption can be turned on or off. When micelle adsorption occurs, the initial adsorption rate is always slower than the supply rate of micelles to the surface, indicating “reaction-limited” adsorption. Since these micelles have essentially frozen cores, the adsorption cannot be explained by the release of unimers from the micelles. Rather, micelles directly adsorb, and they have to overcome the potential barrier imposed by their corona. Due to micellization, the adsorption rate can also be a complex function of ionic strength. A regime was found where the initial adsorption rate decreased with increasing ionic strength. This anomaly can be explained by the onset of micellization. As the salt concentration is increased, more micelles are formed. However micelles adsorb roughly an order of magnitude slower than free chains. Therefore, if increasing the ionic strength produces more micelles, the adsorption rate will simultaneously decrease.

  5. Kinetic model describing the UV/H2O2 photodegradation of phenol from water

    Directory of Open Access Journals (Sweden)

    Rubio-Clemente Ainhoa

    2017-01-01

    Full Text Available A kinetic model for phenol transformation through the UV/H2O2 system was developed and validated. The model includes the pollutant decomposition by direct photolysis and HO•, HO2• and O2 •- oxidation. HO• scavenging effects of CO3 2-, HCO3 -, SO4 2- and Cl- were also considered, as well as the pH changes as the process proceeds. Additionally, the detrimental action of the organic matter and reaction intermediates in shielding UV and quenching HO• was incorporated. It was observed that the model can accurately predict phenol abatement using different H2O2/phenol mass ratios (495, 228 and 125, obtaining an optimal H2O2/phenol ratio of 125, leading to a phenol removal higher than 95% after 40 min of treatment, where the main oxidation species was HO•. The developed model could be relevant for calculating the optimal level of H2O2 efficiently degrading the pollutant of interest, allowing saving in costs and time.

  6. KINETIC CONTROL OF OXIDATION STATE AT THERMODYNAMICALLY BUFFERED POTENTIALS IN SUBSURFACE WATERS

    Science.gov (United States)

    Dissolved oxygen (DO) and organic carbon (Corg) are among the highest- and lowest-potential reactants, respectively, of redox couples in natural waters. When DO and Corg are present in subsurface settings, other couples are drawn toward potentials imposed by them, generating a b...

  7. Coalescence kinetics of oil-in-water emulsions studied with microfluidics

    NARCIS (Netherlands)

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

    2013-01-01

    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

  8. Microfluidic methods to assess demulsification kinetics for oil-water-separation

    NARCIS (Netherlands)

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

    2012-01-01

    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

  9. Complex ion kinetics. Reaction rates on ion-exchange resins compared to those in water

    International Nuclear Information System (INIS)

    Liss, I.B.; Murmann, R.K.

    1975-01-01

    A comparison has been made between the rates in water and on an ion-exchange resin for the aquation of [(NH 3 ) 5 CoOReO 3 ] 2+ and [(H 2 O) 5 CrCl] 2+ and for the 18 O isotopic exchange of water with [(NH 3 ) 5 Co(OH 2 )] 3+ and ReO 4 - . The rate of water exchange on [(NH 3 ) 5 Co(OH 2 )] 3+ was not changed by association with Dowex 50W resins. Aquation of [(NH 3 ) 5 CoOReO 3 ] 2+ and water exchange on ReO 4 - had modified pH dependencies when associated with a resin. With the cobalt complex the rates were faster on the resin in the acidic region and slower on the resin in the basic region. A new term in the rate equation was observed when ReO 4 - was on the resin, first order in H + , while the other terms appear to be unchanged. Aquation of [(H 2 O) 5 CrCl] 2+ was much slower when it was absorbed on the resin. This was related to the known ionic strength effect of the reaction. (auth)

  10. Fe(II) oxidation kinetics and Fe hydroxyphosphate precipitation upon aeration of anaerobic (ground)water

    NARCIS (Netherlands)

    van der Grift, B.; Griffioen, J.; Behrends, T.; Wassen, M.J.; Schot, P.P.; Osté, Leonard

    2015-01-01

    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

  11. Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water

    NARCIS (Netherlands)

    Van Der Grift, B.; Rozemeijer, J. C.; Griffioen, J.; Van Der Velde, Y.

    2014-01-01

    The retention of phosphorus in surface waters through 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

  12. Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water.

    NARCIS (Netherlands)

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

    2014-01-01

    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 5 P immobilization along the flow-path

  13. Iron oxidation kinetics and phosphate immobilization along the flow-path from groundwater into surface water

    NARCIS (Netherlands)

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

    2014-01-01

    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

  14. Proton transfer events in GFP.

    Science.gov (United States)

    Di Donato, Mariangela; van Wilderen, Luuk J G W; Van Stokkum, Ivo H M; Stuart, Thomas Cohen; Kennis, John T M; Hellingwerf, Klaas J; van Grondelle, Rienk; Groot, Marie Louise

    2011-09-28

    Proton transfer is one of the most important elementary processes in biology. Green fluorescent protein (GFP) serves as an important model system to elucidate the mechanistic details of this reaction, because in GFP proton transfer can be induced by light absorption. Illumination initiates proton transfer through a 'proton-wire', formed by the chromophore (the proton donor), water molecule W22, Ser205 and Glu222 (the acceptor), on a picosecond time scale. To obtain a more refined view of this process, we have used a combined approach of time resolved mid-infrared spectroscopy and visible pump-dump-probe spectroscopy to resolve with atomic resolution how and how fast protons move through this wire. Our results indicate that absorption of light by GFP induces in 3 ps (10 ps in D(2)O) a shift of the equilibrium positions of all protons in the H-bonded network, leading to a partial protonation of Glu222 and to a so-called low barrier hydrogen bond (LBHB) for the chromophore's proton, giving rise to dual emission at 475 and 508 nm. This state is followed by a repositioning of the protons on the wire in 10 ps (80 ps in D(2)O), ultimately forming the fully deprotonated chromophore and protonated Glu222.

  15. Experimental and Kinetic Study on Lignin Depolymerization in Water/Formic Acid System

    Directory of Open Access Journals (Sweden)

    Qi Wang

    2017-10-01

    Full Text Available Microwave-assisted depolymerization of black-liquor lignin in formic acid was studied, concentrating on the yield of liquid fractions as bio-oil 1 (mainly aromatic monomers and bio-oil 2 (mainly aromatic oligomers and the distribution of the specific compositions. Bio-oil 1 (9.69% and bio-oil 2 (54.39% achieved their maximum yields under 160 °C with the reaction time of 30 min. The chemical compositions of bio-oil 1 and bio-oil 2 were respectively identified by means of Gas Chromatography-Mass Spectrometer (GC-MS and Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS. Ethanone, 1-(4-hydroxy-3-methoxyphenyl and Ethanone, 1-(4-hydrox-3,5-dimethoxyphenyl were evidenced to be the two prominent compounds in bio-oil 1. Production of aromatic oligomers with the molecular weight of 328, 342, 358, 378, 394, 424 and 454 identified by MALDI-TOF MS was substantially tuned with the reaction temperature. A two-separate-stage kinetic model was proposed to describe the acidic solvolysis of lignin assisted by microwave heating, where the first stage is dominated by the depolyerization of lignin to monomers and oligomers with the activation energy of 40.27 kJ·mol−1, and the second stage with the activation energy of 49.18 kJ·mol−1 is mainly ascribed to the repolymerization of first-stage produced compounds.

  16. Preparation and Characterization of Azadirachtin Alginate-Biosorbent Based Formulations: Water Release Kinetics and Photodegradation Study.

    Science.gov (United States)

    Flores-Céspedes, Francisco; Martínez-Domínguez, Gerardo P; Villafranca-Sánchez, Matilde; Fernández-Pérez, Manuel

    2015-09-30

    The botanical insecticide azadirachtin was incorporated in alginate-based granules to obtain controlled release formulations (CRFs). The basic formulation [sodium alginate (1.47%) - azadirachtin (0.28%) - water] was modified by the addition of biosorbents, obtaining homogeneous hybrid hydrogels with high azadirachtin entrapment efficiency. The effect on azadirachtin release rate caused by the incorporation of biosorbents such as lignin, humic acid, and olive pomace in alginate formulation was studied by immersion of the granules in water under static conditions. The addition of the biosorbents to the basic alginate formulation reduces the rate of release because the lignin-based formulation produces a slower release. Photodegradation experiments showed the potential of the prepared formulations in protecting azadirachtin against simulated sunlight, thus improving its stability. The results showed that formulation prepared with lignin provided extended protection. Therefore, this study provides a new procedure to encapsulate the botanical insecticide azadirachtin, improving its delivery and photostability.

  17. Crypt cell population kinetics in mouse jejunum under continuous beta irradiation from tritiated water

    International Nuclear Information System (INIS)

    Bhatia, A.L.; Gupta, M.L.; Saharan, B.R.

    1979-01-01

    The behaviour of crypt cell population in mouse jejunum under continuous beta irradiation from tritiated water (HTO) has been studied. Adult mice were maintained on tritiated drinking water of the activity of 1.25 μCi/ml, after priming injection. The crypts were studied at 1, 5, 7, 15 and 30 days after the initiation of treatment. It is observed that there is a partial recovery in proliferative activity after the first day of the treatment. Again there is a decrease in the crypt cells on the 7th day, after which this population appears to achieve a near-steady-state level at about 8% below normal at the last interval studied. Crypt cell population and mitotic figures showed a simultaneous dip and recovery, while dead cells showed inverse relationship. (orig.) [de

  18. WATER-GAS SHIFT KINETICS OVER IRON OXIDE CATALYSTS AT MEMBRANE REACTOR CONDITIONS; A

    International Nuclear Information System (INIS)

    Carl R.F. Lund

    2001-01-01

    This report covers the second year of a project investigating water-gas shift catalysts for use in membrane reactors. It has been established that a simple iron high temperature shift catalyst becomes ineffective in a membrane reactor because the reaction rate is severely inhibited by the build-up of the product CO(sub 2). During the past year, an improved microkinetic model for water-gas shift over iron oxide was developed. Its principal advantage over prior models is that it displays the correct asymptotic behavior at all temperatures and pressures as the composition approaches equilibrium. This model has been used to explore whether it might be possible to improve the performance of iron high temperature shift catalysts under conditions of high CO(sub 2) partial pressure. The model predicts that weakening the surface oxygen bond strength by less than 5% should lead to higher catalytic activity as well as resistance to rate inhibition at higher CO(sub 2) partial pressures. Two promoted iron high temperature shift catalysts were studied. Ceria and copper were each studied as promoters since there were indications in the literature that they might weaken the surface oxygen bond strength. Ceria was found to be ineffective as a promoter, but preliminary results with copper promoted FeCr high temperature shift catalyst show it to be much more resistant to rate inhibition by high levels of CO(sub 2). Finally, the performance of sulfided CoMo/Al(sub 2)O(sub 3) catalysts under conditions of high CO(sub 2) partial pressure was simulated using an available microkinetic model for water-gas shift over this catalyst. The model suggests that this catalyst might be quite effective in a medium temperature water-gas shift membrane reactor, provided that the membrane was resistant to the H(sub 2)S that is required in the feed

  19. Ir4+-Doped NiFe LDH to expedite hydrogen evolution kinetics as a Pt-like electrocatalyst for water splitting.

    Science.gov (United States)

    Chen, Qian-Qian; Hou, Chun-Chao; Wang, Chuan-Jun; Yang, Xiao; Shi, Rui; Chen, Yong

    2018-06-06

    NiFe-layered double hydroxide (NiFe LDH) is a state-of-the-art oxygen evolution reaction (OER) electrocatalyst, yet it suffers from rather poor catalytic activity for the hydrogen evolution reaction (HER) due to its extremely sluggish water dissociation kinetics, severely restricting its application in overall water splitting. Herein, we report a novel strategy to expedite the HER kinetics of NiFe LDH by an Ir4+-doping strategy to accelerate the water dissociation process (Volmer step), and thus this catalyst exhibits superior and robust catalytic activity for finally oriented overall water splitting in 1 M KOH requiring only a low initial voltage of 1.41 V delivering at 20 mA cm-2 for more than 50 h.

  20. Effect of material flexibility on the thermodynamics and kinetics of hydrophobically induced evaporation of water.

    Science.gov (United States)

    Altabet, Y Elia; Haji-Akbari, Amir; Debenedetti, Pablo G

    2017-03-28

    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.

  1. Oxygen isotope exchange kinetics between coexistent minerals and water in the Ertaibei granite pluton, northern Xinjiang

    Institute of Scientific and Technical Information of China (English)

    刘伟; 李志安; 赵志忠

    1996-01-01

    Coexistent minerals quartz, feldspar and biotite vary widely in δ18O value and display remarkable 18O/16O disequilibrium relations in the Ertaibei granite pluton, northern Xinjiang. The 18O/16O exchange reaction definitely occurred between granite and water. Initial δ18O values of the granite and exotic water are evaluated by the mass balance consideration. The results show that the 18O/16O exchange reaction is not necessarily accompanied by what geologists describe as petrological and mineralogiesl alteration effects, indicating that the exchange reaction occurs at a comparatively high temperature during subsolidus cooling of magmas. Exchange mechanism is mainly controlled by diffusion. It is demonstrated through quantitative modelling that the hydrothermal system associated with the Ertaibei pluton lived for 0.8-3 Ma, with a fluid flow rate of 3 × 10-14 mol · s-1 and water/rock (W/R) ratio of 0.79 - 3.08. Flow path and initial heterogeneity of the exotic metamorphic fluid are modelled with the δ1

  2. Hot water extraction with in situ wet oxidation: Kinetics of PAHs removal from soil

    International Nuclear Information System (INIS)

    Dadkhah, Ali A.; Akgerman, Aydin

    2006-01-01

    Finding environmentally friendly and cost-effective methods to remediate soils contaminated with polycyclic aromatic hydrocarbons (PAHs) is currently a major concern of researchers. In this study, a series of small-scale semi-continuous extractions - with and without in situ wet oxidation - were performed on soils polluted with PAHs, using subcritical water (i.e. liquid water at high temperatures and pressures, but below the critical point) as the removal agent. Experiments were performed in a 300 mL reactor using an aged soil sample. To find the desorption isotherms and oxidation reaction rates, semi-continuous experiments with residence times of 1 and 2 h were performed using aged soil at 250 deg. C and hydrogen peroxide as oxidizing agent. In all combined extraction and oxidation flow experiments, PAHs in the remaining soil after the experiments were almost undetectable. In combined extraction and oxidation no PAHs could be detected in the liquid phase after the first 30 min of the experiments. Based on these results, extraction with hot water, if combined with oxidation, should reduce the cost of remediation and can be used as a feasible alternative technique for remediating contaminated soils and sediments

  3. 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.

    2017-01-01

    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

  4. 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.

    2015-01-01

    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

  5. Tissue kinetics, ion transport, and recruitment of mitochondria-rich cells in the skin of the toad (Bufo bufo) in response to exposure to distilled water

    DEFF Research Database (Denmark)

    Budtz, Poul Egede; Christoffersen, Betina C.; Johansen, Jesper S.

    1995-01-01

    Mitochondria-rich cells (MRC) of the amphibian epidermis are responsible for active chloride uptake at low external salinity, and new MRCs are recruited in response to exposure to distilled (deionized) water. The time-course of this recruitment, the tissue kinetics and ion transport have been...

  6. 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

    2008-01-01

    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

  7. Influence of processes of structure formation in mixed solvent and anion nature on cadmium ions discharge kinetics from water-dimethylformamide electrolyte

    International Nuclear Information System (INIS)

    Kuznetsov, V.V.; Bozhenko, L.G.; Kucherenko, S.S.; Fedorova, O.V.

    1986-01-01

    Electrochemical reaction of cadmium ion discharge in water-dimethylformamide (DMF) solutions is studied. The influence of DMF concentration in the presence of different anions (ClO 4 - , F - , I - ) on both reaction kinetics and mechanism is discussed on the basis of structural transformations in the mixed solvent and near the surface electrode processes

  8. Effects of volatile fatty acid supply on their absorption and on water kinetics in the rumen of sheep sustained by intragastric infusions

    NARCIS (Netherlands)

    Lopez, S.; Hovell, F.D.D.; Dijkstra, J.; France, J.

    2003-01-01

    Three sheep fitted with a ruminal cannula and an abomasal catheter were used to study water kinetics and absorption of VFA infused continuously into the rumen. The effects of changing VFA concentrations in the rumen by shifting VFA infusion rates were investigated in an experiment with a 3 x 3 Latin

  9. Advanced oxidation of five contaminants in water by UV/TiO2: Reaction kinetics and byproducts identification.

    Science.gov (United States)

    Alvarez-Corena, Jose R; Bergendahl, John A; Hart, Fred L

    2016-10-01

    The extent and kinetics of degradation of 1,4 dioxane, n-nitrosodimethylamine (NDMA), tris-2-chloroethyl phosphate (TCEP), gemfibrozil, and 17β estradiol in a prepared aqueous matrix by means of UV/TiO2 (ultraviolet light/titanium dioxide) oxidation was evaluated. Degussa P25 TiO2 was employed as a photocatalyst excited by UV light in a 1 L water-jacketed batch photoreactor. The rate of degradation was modeled using a pseudo-first order rate model and the Langmuir-Hinshelwood rate model with a high correlation. Degradation rate constants were found to be maximum at pH 5.0 and 1.5 g L(-)(1) TiO2 dose. For these conditions first order rate constants, values were as follows: 0.29 min(-1) for 1,4 dioxane, 0.50 min(-1) for NDMA, 0.12 min(-1) for TCEP, 0.61 min(-1) for gemfibrozil, and 0.53 min(-1) for 17β estradiol. While for the Langmuir-Hinshelwood rate model, the following constants were found: 0.11 Lmg(-1) and 2.81 mgL(-1) min(-1) for 1,4 dioxane, 0.12 Lmg(-1) and 4.35 mgL(-1) min(-1) for NDMA, 0.06 Lmg(-1) and 1.79 mgL(-1) min(-1) for TCEP, 0.21 Lmg(-1) and 3.27 mgL(-1) min(-1) for gemfibrozil, and 0.15 Lmg(-1) and 3.43 mgL(-1) min(-1) for 17β estradiol. In addition, specific byproducts of degradation were identified using GC/MS analysis. The results obtained from the kinetics analysis showed that UV/TiO2 oxidation is a promising process for treating trace organic contaminants in water, but further research is needed to better understand how to incorporate these findings into pilot and full-scale designs. The toxicity of oxidation byproducts, and their potential for interacting with other compounds should be considered in the treatment of contaminated waters using the UV/TiO2 oxidation process. Copyright © 2016 Elsevier Ltd. All rights reserved.

  10. Estimation of Oxidation Kinetics and Oxide Scale Void Position of Ferritic-Martensitic Steels in Supercritical Water

    Directory of Open Access Journals (Sweden)

    Li Sun

    2017-01-01

    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.

  11. Influence of water on clumped-isotope bond reordering kinetics in calcite

    Science.gov (United States)

    Brenner, Dana C.; Passey, Benjamin H.; Stolper, Daniel A.

    2018-03-01

    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

  12. Water recovery and air humidification by condensing the moisture in the outlet gas of a proton exchange membrane fuel cell stack

    International Nuclear Information System (INIS)

    Wan, Z.M.; Wan, J.H.; Liu, J.; Tu, Z.K.; Pan, M.; Liu, Z.C.; Liu, W.

    2012-01-01

    Humidification is one of the most important factors for the operation of proton exchange membrane fuel cell (PEMFC). To maintain the membrane at hydrated state, plenty of water is needed for the state-of-the-art of PEMFC technology, especially in large power applications or long time operation. A condenser is introduced to separate liquid water from the air outlet for air self-sufficient in water of the stack in this study. The condensed temperature at the outlet of the condenser and water recovered amount for air self-sufficient in water are investigated theoretically and experimentally. It is shown that the condensed temperature for air self-sufficient in water is irrelevant with the working current of the stack. When the condenser outlet temperature was above the theoretical line, recovery water was not sufficient for the air humidification. On the contrary, it is sufficient while the temperature was below the theoretical line. It is also shown that when the moisture is sufficiently cooled, large amount water can be separated from the outlet gas, and it increased almost linearly with the time. With the introduction of the condenser, the recovered amount of water can easily satisfy the air self-sufficient in water by condensing the outlet gas to a proper temperature. - Highlights: ► We introduce a condenser to separate liquid water from the air outlet in the stack. ► The mechanism of air self-sufficient in water by condensing gas is presented. ► The condensed temperature and water recovered amount are investigated. ► An experiment is present to validate simplicity and feasibility of the criterion. ► The criterion for air humidification is used for choosing the condenser.

  13. Thermodynamic parameters for the protonation and the interaction of arsenate with Mg2+, Ca2+ and Sr2+: Application to natural waters.

    Science.gov (United States)

    Chillè, Donatella; Foti, Claudia; Giuffrè, Ottavia

    2018-01-01

    Thermodynamic parameters for the protonation of AsO 4 3- and for the interaction with Mg 2+ , Ca 2+ and Sr 2+ were reported, comprehensive also of their dependence on ionic strength, considering the 0.1 ≤ I ≤ 1 M range and using NaCl as background salt. The same speciation models were obtained for Mg 2+ , Ca 2+ and Sr 2+ systems, with the formation of three different species: ML, MLH and MLH 2 (L = AsO 4 3- ). Mono- and di-protonated species were very weak, with formation constant values (log K) ranging from 1.45 to 3.23. In order to have a complete picture of thermodynamic properties of the systems under study and to fill the shortage of thermodynamic data on arsenate complex systems, the ligand protonation and metal complex enthalpies were also determined by calorimetric titrations, at t = 25 °C and in NaCl at I = 0.7 M (for H + -AsO 4 3- species also at I = 0.1 M). On the light of the proposed speciation models, examples of As(V) distribution in some natural waters are reported. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Revisit the landscape of protonated water clusters H+(H2O)n with n = 10-17: An ab initio global search

    Science.gov (United States)

    Shi, Ruili; Li, Keyao; Su, Yan; Tang, Lingli; Huang, Xiaoming; Sai, Linwei; Zhao, Jijun

    2018-05-01

    Using a genetic algorithm incorporated with density functional theory, we explore the ground state structures of protonated water clusters H+(H2O)n with n = 10-17. Then we re-optimize the isomers at B97-D/aug-cc-pVDZ level of theory. The extra proton connects with a H2O molecule to form a H3O+ ion in all H+(H2O)10-17 clusters. The lowest-energy structures adopt a monocage form at n = 10-16 and core-shell structure at n = 17 based on the MP2/aug-cc-pVTZ//B97-D/aug-cc-pVDZ+ZPE single-point-energy calculation. Using second-order vibrational perturbation theory, we further calculate the infrared spectra with anharmonic correction for the ground state structures of H+(H2O)10-17 clusters at the PBE0/aug-cc-pVDZ level. The anharmonic correction to the spectra is crucial since it reproduces the experimental results quite well. The extra proton weakens the O-H bond strength in the H3O+ ion since the Wiberg bond order of the O-H bond in the H3O+ ion is smaller than that in H2O molecules, which causes a red shift of the O-H stretching mode in the H3O+ ion.

  15. Faster proton transfer dynamics of water on SnO2 compared to TiO2.

    Science.gov (United States)

    Kumar, Nitin; Kent, Paul R C; Bandura, Andrei V; Kubicki, James D; Wesolowski, David J; Cole, David R; Sofo, Jorge O

    2011-01-28

    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.

  16. A Ratio-Analysis Method to the Dynamics of Excited State Proton Transfer: Pyranine in Water and Micelles.

    Science.gov (United States)

    Sahu, Kalyanasis; Nandi, Nilanjana; Dolai, Suman; Bera, Avisek

    2018-06-05

    Emission spectrum of a fluorophore undergoing excited state proton transfer (ESPT) often exhibits two distinct bands each representing emissions from protonated and deprotonated forms. The relative contribution of the two bands, best represented by an emission intensity ratio (R) (intensity maximum of the protonated band / intensity maximum of the deprotonated band), is an important parameter which usually denotes feasibility or promptness of the ESPT process. However, the use of ratio is only limited to the interpretation of steady-state fluorescence spectra. Here, for the first time, we exploit the time-dependence of the ratio (R(t)), calculated from time-resolved emission spectra (TRES) at different times, to analyze ESPT dynamics. TRES at different times were fitted with a sum of two lognormal-functions representing each peaks and then, the peak intensity ratio, R(t) was calculated and further fitted with an analytical function. Recently, a time-resolved area-normalized emission spectra (TRANES)-based analysis was presented where the decay of protonated emission or the rise of deprotonated emission intensity conveniently accounts for the ESPT dynamics. We show that these two methods are equivalent but the new method provides more insights on the nature of the ESPT process.

  17. CFD analysis of the dynamic behaviour of a fuel rod subchannel in a supercritical water reactor with point kinetics

    International Nuclear Information System (INIS)

    Ampomah-Amoako, Emmanuel; Akaho, Edward H.K.; Nyarko, Benjamin J.B.; Ambrosini, Walter

    2013-01-01

    Highlights: • The analysis of flow stability of nuclear fuel subchannels with supercritical water is presented. • The results obtained by a CFD code are compared with those of a system code. • The model includes also heat conduction in the fuel rod and point neutron kinetics. - Abstract: The paper presents the analysis by a CFD code of coupled neutronic–thermal hydraulic instabilities in a subchannel slice belonging to a square lattice assembly. The work represents a further phase in the assessment of the suitability of CFD codes for studies of flow stability of supercritical fluids; the research started in previous work with the analysis of bare 2D circular pipes and already addressed 3D subchannel slices with no allowance for heat conduction or neutronic effects. In the present phase, a more realistic system is considered, dealing with a slice of a fuel assembly subchannel containing the regions of the pellet, the gap and the cladding and including also the effect of inlet and outlet throttling. The adopted neutronic model is a point kinetics one, including six delayed neutron groups with global Doppler and fluid density feedbacks. The response of the model to perturbations applied starting from a steady-state condition at the rated power is compared with that of a similar model developed for a 1D system code. Upward, horizontal and downward flow orientations are addressed making use of a uniform power profile and changing relevant parameters as the gap equivalent conductance and the density reactivity coefficient. A bottom-peaked power profile is also considered in the case of vertical upward flow. Though the adopted model can still be considered simple in comparison with actual details of fuel assemblies, the obtained results demonstrate the potential of the adopted methodology for more accurate analyses to be made with larger computational resources

  18. Isotherm and kinetic studies on adsorption of oil sands process-affected water organic compounds using granular activated carbon.

    Science.gov (United States)

    Islam, Md Shahinoor; McPhedran, Kerry N; Messele, Selamawit A; Liu, Yang; Gamal El-Din, Mohamed

    2018-07-01

    The production of oil from oil sands in northern Alberta has led to the generation of large volumes of oil sands process-affected water (OSPW) that was reported to be toxic to aquatic and other living organisms. The toxicity of OSPW has been attributed to the complex nature of OSPW matrix including the inorganic and organic compounds primarily naphthenic acids (NAs: C n H 2n+Z O x ). In the present study, granular activated carbon (GAC) adsorption was investigated for its potential use to treat raw and ozonated OSPW. The results indicated that NA species removal increased with carbon number (n) for a fixed Z number; however, the NA species removal decreased with Z number for a fixed carbon number. The maximum adsorption capacities obtained from Langmuir adsorption isotherm based on acid-extractable fraction (AEF) and NAs were 98.5 mg and 60.9 mg AEF/g GAC and 60 mg and 37 mg NA/g GAC for raw and ozonated OSPW, respectively. It was found that the Freundlich isotherm model best fits the AEF and NA equilibrium data (r 2  ≥ 0.88). The adsorption kinetics showed that the pseudo-second order and intraparticle diffusion models were both appropriate in modeling the adsorption kinetics of AEF and NAs to GAC (r 2  ≥ 0.97). Although pore diffusion was the rate limiting step, film diffusion was still significant for assessing the rate of diffusion of NAs. This study could be helpful to model, design and optimize the adsorption treatment technologies of OSPW and to assess the performance of other adsorbents. Copyright © 2018 Elsevier Ltd. All rights reserved.

  19. Nucleophilic addition to olefins. 5. Reaction of 1,1-dinitro-2,2-diphenylethylene with water and hydroxide ion in 50% Me2SO-50% water. Complete kinetic analysis of hydrolytic cleavage of the C=C double bond in acidic and basic solution

    International Nuclear Information System (INIS)

    Bernasconi, C.F.; Carre, D.J.; Kanavarioti, A.

    1981-01-01

    Hydrolysis of 1,1-dinitro-2,2-diphenylethylene (2) to form benzophenone and dinitromethane (or its anion) was studied in 50% Me 2 SO-50% H 2 O and also in 50% Me 2 SO-50% D 2 O at pHs of 1 to 16. Solvent isotope effects general acid and general base catalysis, and structure-reactivity relationships were used to study the kinetics. The conclusions are the following: (1) the equilibrium constants for OH - and water addition to 2 to form T/sub OH/ - are comparable to those for the corresponding reactions of benzylidene Meldrum's acid (1), but the rate constants are much lower for 2 than for 1; (2) carbon protonation of T/sub OH/ - follows an Eigen curve similar to that for 1,1-dinitroethane anion but which is displaced upward by nearly 1 log unit. This indicates a higher intrinsic protonation rate because of a smaller charge delocalization in T/sub OH/ - owing to an enhanced steric hindrance to coplanarity of the nitro groups in T/sub OH/ - ; (3) intramolecular proton transfer from the OH group to the carbanionic site in T/sub OH/ - is insignificant, which is in contrast to the behavior of the addition complex between 2 and morpholine; (4) the base-catalyzed breakdown of T/sub OH/ 0 into benzophenone and dinitromethane anion occurs by rate-limiting oxygen deprotonation, which implies that k 4 for CH(NO 2 ) 2 - departure from T/sub OH/ 0- is much greater than 2 x 10 9 s -1 , a remarkably high rate for a carbanionic leaving group. The water-catalyzed breakdown of T/sub OH/ 0 proceeds by a different mechanism, which is most likely concerted, with a transition state; (5) the acid-catalyzed breakdown of T/sub OH/ 2- occurs by rate-limiting carbon protonation (k 6 /sup BH/), but the water-catalyzed breakdown follows a different mechanism. Various possibilities are discussed, and a slight preference is given to a preassociation mechanism

  20. Electrochemical proton relay at the single-molecule level

    DEFF Research Database (Denmark)

    Kuznetsov, A. M.; Medvedev, I. G.; Ulstrup, Jens

    2009-01-01

    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....

  1. Kinetic features of cadmium electrodeposition in iodide water-acetone electrolytes

    International Nuclear Information System (INIS)

    Kuznetsov, V.V.; Skibina, L.M.; Khalikov, R.R.

    2006-01-01

    Based on the data of chronopotentiometric, galvanostatic, potentiodynamic, and impedance measurements, the composition of aqueous acetone electrolyte is studied for its effect on the rate of cadmium(II) electroreduction in iodide media. The adsorption of I - ions on the cadmium cathode surface is shown to depend on the interaction mechanism between the components of water-acetone mixtures. During a competitive adsorption of anions and organic solvent molecules, this affects the mechanism and the rate of electrodeposition and also the coating quality [ru

  2. Photocatalytic removal of perfluoroalkyl substances from water and wastewater: Mechanism, kinetics and controlling factors.

    Science.gov (United States)

    Xu, Bentuo; Ahmed, Mohammad Boshir; Zhou, John L; Altaee, Ali; Wu, Minghong; Xu, Gang

    2017-12-01

    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 In 2 O 3 as the catalyst, followed by Ga 2 O 3 and TiO 2 . Significantly, modifying the chemical composition or morphology of the catalyst can improve its efficacy for PFAS removal. In 2 O 3 porous nanoplates were found to have the best performance of 100% PFAS decomposition under UV light with rate constant (k t ) and half-time (τ 1/2 ) 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 Ga 2 O 3  > In 2 O 3  > TiO 2 . 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.

  3. Investigation of cloud condensation nuclei properties and droplet growth kinetics of the water-soluble aerosol fraction in Mexico City

    Science.gov (United States)

    Padró, Luz T.; Tkacik, Daniel; Lathem, Terry; Hennigan, Chris J.; Sullivan, Amy P.; Weber, Rodney J.; Huey, L. Greg; Nenes, Athanasios

    2010-05-01

    We present hygroscopic and cloud condensation nuclei (CCN) relevant properties of the water-soluble fraction of Mexico City aerosol collected upon filters during the 2006 Megacity Initiative: Local and Global Research Observations (MILAGRO) campaign. Application of κ-Köhler theory to the observed CCN activity gave a fairly constant hygroscopicity parameter (κ = 0.28 ± 0.06) regardless of location and organic fraction. Köhler theory analysis was used to understand this invariance by separating the molar volume and surfactant contributions to the CCN activity. Organics were found to depress surface tension (10-15%) from that of pure water. Daytime samples exhibited lower molar mass (˜200 amu) and surface tension depression than nighttime samples (˜400 amu); this is consistent with fresh hygroscopic secondary organic aerosol (SOA) condensing onto particles during peak photochemical hours, subsequently aging during nighttime periods of high relative humidity. Changes in surface tension partially compensate for shifts in average molar volume to give the constant hygroscopicity observed, which implies the amount (volume fraction) of soluble material in the parent aerosol is the key composition parameter required for CCN predictions. This finding, if applicable elsewhere, may explain why CCN predictions are often found to be insensitive to assumptions of chemical composition and provides a very simple way to parameterize organic hygroscopicity in atmospheric models (i.e., κorg = 0.28ɛWSOC). Special care should be given, however, to surface tension depression from organic surfactants, as its nonlinear dependence with organic fraction may introduce biases in observed (and predicted) hygroscopicity. Finally, threshold droplet growth analysis suggests the water-soluble organics do not affect activation kinetics.

  4. Multidimensional space-time kinetics of a heavy water moderated nuclear reactor

    International Nuclear Information System (INIS)

    Winn, W.G.; Baumann, N.P.; Jewell, C.E.

    1980-01-01

    Diffusion theory analysis of a series of multidimensional space-time experiments is appraised in terms of the final experiment of the series. In particular, TRIMHX diffusion calculations were examined for an experiment involving free-fall insertion of a 235 U-bearing rod into a heavy water moderated reactor with a large reflector. The experimental transient flux-tilts were accurately reproduced after cross section adjustments forced agreement between static diffusion calculations and static reactor measurements. The time-dependent features were particularly well modeled, and the bulk of the small discrepancies in space-dependent features should be removable by more refined cross-section adjustments. This experiment concludes a series of space-time experiments that span a wide range of delayed neutron holdback effects. TRIMHX calculations of these experiments demonstrate the accuracy of the modeling employed in the code

  5. 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.

    2015-06-01

    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

  6. Conceptual design of proton beam window

    International Nuclear Information System (INIS)

    Teraoku, Takuji; Kaminaga, Masanori; Terada, Atsuhiko; Ishikura, Syuichi; Kinoshita, Hidetaka; Hino, Ryutaro

    2001-01-01

    In a MW-scale neutron scattering facility coupled with a high-intensity proton accelerator, a proton beam window is installed as the boundary between a high vacuum region of the proton beam transport line and a helium environment around the target assembly working as a neutron source. The window is cooled by water so as to remove high volumetric heat generated by the proton beam. A concept of the flat-type proton beam window consisting of two plates of 3 mm thick was proposed, which was found to be feasible under the proton beam power of 5 MW through thermal-hydraulic and structural strength analyses. (authors)

  7. 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)

    2017-04-15

    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

  8. Adsorption kinetics of alkanethiol-capped gold nanoparticles at the hexane–water interface

    International Nuclear Information System (INIS)

    Ferdous, Sultana; Ioannidis, Marios A.; Henneke, Dale

    2011-01-01

    The pendant drop technique was used to characterize the adsorption behavior of n-dodecane-1-thiol and n-hexane-1-thiol-capped gold nanoparticles at the hexane–water interface. The adsorption process was studied by analyzing the dynamic interfacial tension versus nanoparticle concentration, both at early times and at later stages (i.e., immediately after the interface between the fluids is made and once equilibrium has been established). A series of gold colloids were made using nanoparticles ranging in size from 1.60 to 2.85 nm dissolved in hexane for the interfacial tension analysis. Following free diffusion of nanoparticles from the bulk hexane phase, adsorption leads to ordering and rearrangement of the nanoparticles at the interface and formation of a dense monolayer. With increasing interfacial coverage, the diffusion-controlled adsorption for the nanoparticles at the interface was found to change to an interaction-controlled assembly and the presence of an adsorption barrier was experimentally verified. At the same bulk concentration, different sizes of n-dodecane-1-thiol nanoparticles showed different absorption behavior at the interface, in agreement with the findings of Kutuzov et al. (Phys Chem Chem Phys 9:6351–6358, 2007). The experiments additionally demonstrated the important role played by the capping agent. At the same concentration, gold nanoparticles stabilized by n-hexane-1-thiol exhibited greater surface activity than gold nanoparticles of the same size stabilized by n-dodecane-1-thiol. These findings contribute to the design of useful supra-colloidal structures by the self-assembly of alkane-thiol-capped gold nanoparticles at liquid–liquid interfaces.

  9. Kinetics Extraction Modelling and Antiproliferative Activity of Clinacanthus nutans Water Extract

    Directory of Open Access Journals (Sweden)

    Farah Nadiah Mohd Fazil

    2016-01-01

    Full Text Available Clinacanthus nutans is widely grown in tropical Asia and locally known “belalai gajah” or Sabah snake grass. It has been used as a natural product to treat skin rashes, snake bites, lesion caused by herpes, diabetes, fever, and cancer. Therefore, the objectives of this research are to determine the maximum yield and time of exhaustive flavonoids extraction using Peleg’s model and to evaluate potential of antiproliferative activity on human lung cancer cell (A549. The extraction process was carried out on fresh and dried leaves at 28 to 30°C with liquid-to-solid ratio of 10 mL/g for 72 hrs. The extracts were collected intermittently analysed using mathematical Peleg’s model and RP-HPLC. The highest amount of flavonoids was used to evaluate the inhibitory concentration (IC50 via 2D cell culture of A549. Based on the results obtained, the predicted maximum extract density was observed at 29.20 ± 14.54 hrs of extraction (texhaustive. However, the exhaustive time of extraction to acquire maximum flavonoids content exhibited approximately 10 hrs earlier. Therefore, 18 hrs of extraction time was chosen to acquire high content of flavonoids. The best antiproliferative effect (IC50 on A549 cell line was observed at 138.82 ± 0.60 µg/mL. In conclusion, the flavonoids content in Clinacanthus nutans water extract possesses potential antiproliferative properties against A549, suggesting an alternative approach for cancer treatment.

  10. Drinking water treatment sludge as an effective additive for biogas production from food waste; kinetic evaluation and biomethane potential test.

    Science.gov (United States)

    Ebrahimi-Nik, Mohammadali; Heidari, Ava; Ramezani Azghandi, Shamim; Asadi Mohammadi, Fatemeh; Younesi, Habibollah

    2018-07-01

    The effect of drinking water treatment sludge (DWTS) as a mixture additive, on biogas and methane production from food waste was studied. Mesophilic anaerobic digestion of food waste with 5 concentrations of DWTS (0, 2, 6, 12, and 18 ppm) was carried out. It was found that DWTS can significantly enhance biogas and methane yield. The highest biogas (671 Nml/g VS) as well as methane yield (522 Nml/g VS) was observed when 6 mg/kg DWTS was added. This is equal to 65 and 58 percent increase in comparison with the control digester. The calculated lag time for methane was found to be in between 3.3 and 4.7 days. The DWTS also reduced the lag phase and retention time. The biogas experimental data was fitted with the modified Gompertz and the first-order kinetic models with R 2 higher than 0.994 and 0.949, respectively. The ratio of the experimental biogas production to the theoretical biogas production (ɛ) for control sample was 0.53 while for other samples containing additive were higher than 0.78. Copyright © 2018 Elsevier Ltd. All rights reserved.

  11. 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

    2013-01-01

    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.

  12. A kinetic model for impact/sliding wear of pressurized water reactor internal components: Application to rod cluster control assemblies

    International Nuclear Information System (INIS)

    Zbinden, M.

    1996-01-01

    Certain internal components of Pressurized Water Reactors are damaged by wear when subjected to vibration induced by flow. In order to enable predictive calculation of such wear, one must have a model which takes account reliably of real damages. The modelling of wear represents a final link in a succession of numerical calculations which begins by the determination of hydraulic excitations induced by the flow. One proceeds, then, in the dynamic response calculation of the structure to finish up with an estimation of volumetric wear and of the depth of wear scars. A new concept of industrial wear model adapted to components of nuclear plants is proposed. Its originality is to be supported, on one hand, by experimental results obtained via wear machines of relatively short operational times, and, on the other hand, by the information obtained from the operating feedback over real wear kinetics of the reactors components. The proposed model is illustrated by an example which correspond to a specific real situation. The determination of the coefficients permitting to cover all assembly of configurations and the validation of the model in these configurations have been the object of the most recent work

  13. Stomatal clustering in Begonia associates with the kinetics of leaf gaseous exchange and influences water use efficiency.

    Science.gov (United States)

    Papanatsiou, Maria; Amtmann, Anna; Blatt, Michael R

    2017-04-01

    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.

  14. Effect of water content and temperature on inactivation kinetics of myrosinase in broccoli (Brassica oleracea var. italica).

    Science.gov (United States)

    Oliviero, T; Verkerk, R; Van Boekel, M A J S; Dekker, M

    2014-11-15

    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.

  15. Removal of cationic pollutants from water by xanthated corn cob: optimization, kinetics, thermodynamics, and prediction of purification process.

    Science.gov (United States)

    Kostić, Miloš; Đorđević, Miloš; Mitrović, Jelena; Velinov, Nena; Bojić, Danijela; Antonijević, Milan; Bojić, Aleksandar

    2017-07-01

    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%.

  16. The EDDA experiment: proton-proton elastic scattering excitation functions at intermediate energies

    International Nuclear Information System (INIS)

    Hinterberher, F.

    1996-01-01

    The EDDA experiment is designed to provide a high precision measurement of proton-proton elastic scattering excitation functions ranging from 0.5 to 2.5 GeV of (lab) incident kinetic energy. It is an internal target experiment utilizing the proton beam of the cooler synchrotron COSY operated by KFA Juelich. The excitation functions are measured during the acceleration ramp of COSY. (author)

  17. New Parameterizations for Neutral and Ion-Induced Sulfuric Acid-Water Particle Formation in Nucleation and Kinetic Regimes

    Science.gov (United States)

    Määttänen, Anni; Merikanto, Joonas; Henschel, Henning; Duplissy, Jonathan; Makkonen, Risto; Ortega, Ismael K.; Vehkamäki, Hanna

    2018-01-01

    We have developed new parameterizations of electrically neutral homogeneous and ion-induced sulfuric acid-water particle formation for large ranges of environmental conditions, based on an improved model that has been validated against a particle formation rate data set produced by Cosmics Leaving OUtdoor Droplets (CLOUD) experiments at European Organization for Nuclear Research (CERN). The model uses a thermodynamically consistent version of the Classical Nucleation Theory normalized using quantum chemical data. Unlike the earlier parameterizations for H2SO4-H2O nucleation, the model is applicable to extreme dry conditions where the one-component sulfuric acid limit is approached. Parameterizations are presented for the critical cluster sulfuric acid mole fraction, the critical cluster radius, the total number of molecules in the critical cluster, and the particle formation rate. If the critical cluster contains only one sulfuric acid molecule, a simple formula for kinetic particle formation can be used: this threshold has also been parameterized. The parameterization for electrically neutral particle formation is valid for the following ranges: temperatures 165-400 K, sulfuric acid concentrations 104-1013 cm-3, and relative humidities 0.001-100%. The ion-induced particle formation parameterization is valid for temperatures 195-400 K, sulfuric acid concentrations 104-1016 cm-3, and relative humidities 10-5-100%. The new parameterizations are thus applicable for the full range of conditions in the Earth's atmosphere relevant for binary sulfuric acid-water particle formation, including both tropospheric and stratospheric conditions. They are also suitable for describing particle formation in the atmosphere of Venus.

  18. Computational consideration on advanced oxidation degradation of phenolic preservative, methylparaben, in water: mechanisms, kinetics, and toxicity assessments

    Energy Technology Data Exchange (ETDEWEB)

    Gao, Yanpeng [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Resources Utilization and Protection, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); An, Taicheng, E-mail: antc99@gig.ac.cn [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Resources Utilization and Protection, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Fang, Hansun [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Resources Utilization and Protection, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); University of Chinese Academy of Sciences, Beijing 100049 (China); Ji, Yuemeng; Li, Guiying [State Key Laboratory of Organic Geochemistry and Guangdong Key Laboratory of Environmental Resources Utilization and Protection, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China)

    2014-08-15

    Graphical abstract: - Highlights: • Computational approach is effective to reveal the transformation mechanism of MPB. • MPB degradation was more dependent on the [{sup •} OH] than temperature during AOPs. • O{sub 2} could enhance MPB degradation, but more harmful products were formed. • The risks of MPB products in natural waters should be considered seriously. • The risks of MPB products can be overlooked in AOPs due to short half-time. - Abstract: Hydroxyl radicals ({sup •} OH) are strong oxidants that can degrade organic pollutants in advanced oxidation processes (AOPs). The mechanisms, kinetics, and toxicity assessment of the {sup •} OH-initiated oxidative degradation of the phenolic preservative, methylparaben (MPB), were systematically investigated using a computational approach, as the supplementary information for experimental data. Results showed that MPB can be initially attacked by {sup •} OH via OH-addition and H-abstraction routes. Among these routes, the {sup •} OH addition to the C atom at the ortho-position of phenolic hydroxyl group was the most significant route. However, the methyl-H-abstraction route also cannot be neglected. Further, the formed transient intermediates, OH-adduct ({sup •} MPB-OH{sub 1}) and dehydrogenated radical ({sup •} MPB(-H)α), could be easily transformed to several stable degradation products in the presence of O{sub 2} and {sup •} OH. To better understand the potential toxicity of MPB and its products to aquatic organisms, both acute and chronic toxicities were assessed computationally at three trophic levels. Both MPB and its products, particularly the OH-addition products, are harmful to aquatic organisms. Therefore, the application of AOPs to remove MPB should be carefully performed for safe water treatment.

  19. 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)

    2013-03-15

    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

  20. Water droplet dynamic behavior during removal from a proton exchange membrane fuel cell gas diffusion layer by Lattice-Boltzmann method

    Energy Technology Data Exchange (ETDEWEB)

    Molaeimanesh, Golamreza; Akbari, Mohammad Hadi [Shiraz University, Shiraz (Iran, Islamic Republic of)

    2014-04-15

    A major challenge in the application of proton exchange membrane fuel cells (PEMFCs) is water management, with the flooding of electrodes as the main issue. The Lattice-Boltzmann method (LBM) is a relatively new technique that is superior in modeling the dynamic interface of multiphase fluid flow in complex microstructures such as non-homogeneous and anisotropic porous media of PEMFC electrodes. In this study, the dynamic behavior of a water droplet during removal from gas diffusion layer (GDL) of a PEMFC electrode with interdigitated flow field is simulated using LBM. The effects of GDL wettability and its spanwise and transverse gradients on the removal process are investigated. The results demonstrate great influence of wettability and its spanwise and transverse gradients on the dynamic behavior of droplets during the removal process. Although increasing the hydrophobicity of GDL results in better droplet removal, its increase beyond a critical value does not show a significant effect.

  1. Kinetics and Mechanisms of Phosphorus Adsorption in Soils from Diverse Ecological Zones in the Source Area of a Drinking-Water Reservoir.

    Science.gov (United States)

    Zhang, Liang; Loáiciga, Hugo A; Xu, Meng; Du, Chao; Du, Yun

    2015-11-10

    On-site soils are increasingly used in the treatment and restoration of ecosystems to harmonize with the local landscape and minimize costs. Eight natural soils from diverse ecological zones in the source area of a drinking-water reservoir in central China are used as adsorbents for the uptake of phosphorus from aqueous solutions. The X-ray fluorescence (XRF) spectrometric and BET (Brunauer-Emmett-Teller) tests and the Scanning Electron Microscopy (SEM) and Fourier Transform Infrared (FTIR) spectral analyses are carried out to investigate the soils' chemical properties and their potential changes with adsorbed phosphorous from aqueous solutions. The intra-particle diffusion, pseudo-first-order, and pseudo-second-order kinetic models describe the adsorption kinetic processes. Our results indicate that the adsorption processes of phosphorus in soils occurred in three stages and that the rate-controlling steps are not solely dependent on intra-particle diffusion. A quantitative comparison of two kinetics models based on their linear and non-linear representations, and using the chi-square (χ2) test and the coefficient of determination (r2), indicates that the adsorptive properties of the soils are best described by the non-linear pseudo-second-order kinetic model. The adsorption characteristics of aqueous phosphorous are determined along with the essential kinetic parameters.

  2. Kinetic analysis of cooking losses from beef and other animal muscles heated in a water bath--effect of sample dimensions and prior freezing and ageing.

    Science.gov (United States)

    Oillic, Samuel; Lemoine, Eric; Gros, Jean-Bernard; Kondjoyan, Alain

    2011-07-01

    Cooking loss kinetics were measured on cubes and parallelepipeds of beef Semimembranosus muscle ranging from 1 cm × 1 cm × 1 cm to 7 cm × 7 cm × 28 cm in size. The samples were water bath-heated at three different temperatures, i.e. 50°C, 70°C and 90°C, and for five different times. Temperatures were simulated to help interpret the results. Pre-freezing the sample, difference in ageing time, and in muscle fiber orientation had little influence on cooking losses. At longer treatment times, the effects of sample size disappeared and cooking losses depended only on the temperature. A selection of the tests was repeated on four other beef muscles and on veal, horse and lamb Semimembranosus muscle. Kinetics followed similar curves in all cases but resulted in different final water contents. The shape of the kinetics curves suggests first-order kinetics. Copyright © 2011 The American Meat Science Association. Published by Elsevier Ltd. All rights reserved.

  3. An investigation of proton conductivity of binary matrices sulfonated ...

    Indian Academy of Sciences (India)

    to their potential applications in proton exchange membrane fuel cells (PEMFCs) ... is highly sulfonated and has high water uptake property.11,12 The proton conductivity ... SPSU membranes have lower gas permeability and liquid. (water and ...

  4. Proton transfer dynamics in a polar nanodroplet: ESIPT of 4'-n,n-dimethylamino-3-hydroxyflavone in AOT/alkane/water reverse micelles

    Energy Technology Data Exchange (ETDEWEB)

    Ghosh, Deborin [Department of Chemistry, University College of Science & Technology, University of Calcutta, 92, A.P.C. Road, Kolkata 700 009 (India); Batuta, Shaikh; Begum, Naznin Ara [Bio-Organic Chemistry Lab, Department of Chemistry, Visva-Bharati University, Santiniketan 731 235 (India); Mandal, Debabrata, E-mail: dmandal.chemistry@gmail.com [Department of Chemistry, University College of Science & Technology, University of Calcutta, 92, A.P.C. Road, Kolkata 700 009 (India)

    2017-04-15

    The excited state intramolecular proton transfer (ESIPT) of the well-known fluorophore 4'-N,N-Dimethylamino-3-hydroxyflavone (DMA3HF) was studied in AOT/n-heptane/water reverse micelle solutions. For DMA3HF molecules located inside the AOT encapsulated polar nanodroplets, ESIPT from excited enol (E*) to tautomer (T*) forms was markedly inhibited, yielding time-constants of ≥100 ps, and followed the same trend as solvent relaxation when the ratio W= [H{sub 2}O]/[AOT] was varied. At W=0, the DMA3HF molecules were attached to the ionic AOT headgroups via strong intermolecular H-bonding, which hindered ESIPT. Addition of water changes the situation radically: water molecules form stronger H-bonds with AOT headgroups, displacing the DMA3HF, which are instead engaged in intermolecular H-bonded complexes of the type [DMA3HF···water]. ESIPT of these complex-bound fluorophores involves substantial rearrangement of H-bonding, and is coupled to solvation dynamics. With increasing W-value, solvation becomes faster, and so does ESIPT, reducing the yield of E* species. At the same time, the local environment within the nanodroplets become more more polar with gradual accumulation of water, which causes a monotonic red-shift of the E* emission peak.

  5. Quasi-three dimensional dynamic modeling of a proton exchange membrane fuel cell with consideration of two-phase water transport through a gas diffusion layer

    International Nuclear Information System (INIS)

    Kang, Sanggyu

    2015-01-01

    Water management is one of the challenging issues for low-temperature PEMFCs (proton exchange membrane fuel cells). When liquid water is formed at the GDL (gas diffusion layer), the pathway of reactant gas can be blocked, which inhibits the electrochemical reaction of PEMFC. Thus, liquid water transport through GDL is a critical factor determining the performance of a PEMFC. In present study, quasi-three dimensional dynamic modeling of PEMFC with consideration of two-phase water transport through GDL is developed. To investigate the distributions of PEMFC characteristics, including current density, species mole fraction, and membrane hydration, the PEMFC was discretized into twenty control volumes along the anode channel. To resolve the mass and energy conservation, the PEMFC is discretized into eleven and fifteen control volumes in the perpendicular direction, respectively. The dynamic variation of PEMFC characteristics of cell voltage, overvoltage of activation and ohmic, liquid water saturation through a GDL, and oxygen concentration were captured during transient behavior. - Highlights: • A quasi-three dimensional two-phase dynamic model of PEMFC is developed. • Presented model is validated by comparison with experimental data. • Two-phase model is compared with one-phase model at steady-states and transients.

  6. 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

    2017-01-01

    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...

  7. Redox Kinetics and Nonstoichiometry of Ce0.5Zr0.5O2−δ for Water Splitting and Hydrogen Production

    KAUST Repository

    Zhao, Zhenlong

    2017-04-25

    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

  8. 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

    2000-01-01

    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.

  9. Investigation of proton spin relaxation in water with dispersed silicon nanoparticles for potential magnetic resonance imaging applications

    Science.gov (United States)

    Kargina, Yu. V.; Gongalsky, M. B.; Perepukhov, A. M.; Gippius, A. A.; Minnekhanov, A. A.; Zvereva, E. A.; Maximychev, A. V.; Timoshenko, V. Yu.

    2018-03-01

    Porous and nonporous silicon (Si) nanoparticles (NPs) prepared by ball-milling of electrochemically etched porous Si layers and crystalline Si wafers were studied as potential agents for enhancement of the proton spin relaxation in aqueous media. While nonporous Si NPs did not significantly influence the spin relaxation, the porous ones resulted in strong shortening of the transverse relaxation times. In order to investigate an effect of the electron spin density in porous Si NPs on the proton spin relaxation, we use thermal annealing of the NPs in vacuum or in air. The transverse relaxation rate of about 0.5 l/(g s) was achieved for microporous Si NPs, which were thermally annealing in vacuum to obtain the electron spin density of the order of 1017 g-1. The transverse relaxation rate was found to be almost proportional to the concentration of porous Si NPs in the range from 0.1 to 20 g/l. The obtained results are discussed in view of possible biomedical applications of Si NPs as contrast agents for magnetic resonance imaging.

  10. Synthesis and characterization of water-dispersible core/shell Mn-doped magnetite/Au nanoparticles for proton radiotherapy

    International Nuclear Information System (INIS)

    Park, Jeong Chan

    2015-01-01

    The surface modification of the nanomaterials is required for the biomedical use to give physiological stability, surface reactivity and targeting properties. Among many approaches for the surface modification with materials, such as polymers, organic ligands and metals, one of the most attractive ways is to employ metals. The fabrication of metal-based, monolayer coated magnetic nanoparticles has been intensively studied. However, the synthesis of metal-capped magnetic nanoparticles with monodispersities and controllable sizes is still challenged. Recently, gold-capped magnetic nanoparticles have been reported to increase stability and to provide biocompatibility. Gold-coated magnetic nanoparticles are an attractive system, which can be stabilized in biological conditions and readily functionalized through well-established surface modification chemistry. In addition, the Au coating offers plasmonic properties to magnetic nanoparticles. This makes the magnetic/Au core/shell combinations interesting for magnetic and optical applications. The monodisperse Mn:Fe3O4/Au nanoparticles have been prepared in organic solvent first and then transferred from an organic phase to an aqueous solution. The resulting core/shell-structured nanoparticles may be an attractive system for biomedical applications, which are needed both magnetic resonance imaging and optical imaging. In addition, the resulting nanoparticles may be useful for proton radiotherapy due to the enhanced therapeutic effects of secondary radiation stemmed from gold and proton beam bombardment

  11. The freezing of water bonded in the wheat (Triticum aestivum L.) grain studied by means protons magnetic relaxation method

    International Nuclear Information System (INIS)

    Haranczyk, H.; Jasinski, G.; Strzalka, K.

    1994-01-01

    Some biological aspects of water freezing in the wheat grain have been studied using NMR methods. Measuring of the relaxation times for freezing and liquid water shown absence of T 2 ∼100 μs and T 2 ∼1 ms separated components what pointed for some different way of water bonding

  12. 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

    2017-06-01

    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.

  13. Photolysis of model emerging contaminants in ultra-pure water: kinetics, by-products formation and degradation pathways.

    Science.gov (United States)

    Benitez, F Javier; Acero, Juan L; Real, Francisco J; Roldan, Gloria; Rodriguez, Elena

    2013-02-01

    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. 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)

    2003-07-01

    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)

  15. Theory of kinetics and equilibrium of ion exchange-adsorption and mechanism of extracting uranium from sea-water with titanic gel

    International Nuclear Information System (INIS)

    Ai Hongtao

    1989-01-01

    An isothermal equation for ion exchange-adsorption is derived by mass action law. The equation can be used to sum up empirical and semiempirical formulas of the exchange adsorption, such as Gapon Equation, Sips Formula, Langmuir Equation and Freundlich Formula. In this paper, by adopting the ion exchange reaction to act as the determining step of the ion exchange adsorption kinetics, and exchange-adsorption kinetics equation is derived. It is verified by he results of a series of experiments in which uranium is extracted form enriched sea-water and natural sea-water with hydrous titanium oxide (titanic gel). This equation can be used to explain not only the results of test which have been applied to prove fast intraparticle diffusion of liquid film deffusion mechanism, but also test data which can be expalined by the co-controlling fast intraparticle and liquid film diffusion, and the kinetic data which can not be clarified by diffusion mechanism. It is proposed that the mechanism of the exchange adsorption of uranium from sea-water with titanic gel is a cationic exchange reaction. A method for calculating the quantity of exchange-adsorption at equilibrium is also given

  16. Numerical simulation of flood inundation using a well-balanced kinetic scheme for the shallow water equations with bulk recharge and discharge

    Science.gov (United States)

    Ersoy, Mehmet; Lakkis, Omar; Townsend, Philip

    2016-04-01

    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.

  17. 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.

    Science.gov (United States)

    Sun, Yan; Lu, Wenchao; Liu, Jianbo

    2017-02-09

    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 Δ g ) O 2 than the undamaged guanosine, and the lesions arising from the secondary oxidation of 8-oxodGuo are more mutagenic. Herein the 1 O 2 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 (E col ) on reaction cross sections over a center-of-mass E col 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] + ·W 0,1 (W = H 2 O) because insurmountable barriers block the addition of 1 O 2 to reactant ions. Neither was [8-oxoG - H] - reactive with 1 O 2 , 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 O 2 decreases with increasing E col 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] + ·W 0,1 and [8-oxoG - H] - ·W 0

  18. Detection of Amide and Aromatic Proton Resonances of Human Brain Metabolites Using Localized Correlated Spectroscopy Combined with Two Different Water Suppression Schemes

    Directory of Open Access Journals (Sweden)

    Rajakumar Nagarajan

    2010-01-01

    Full Text Available The purpose of the study was to demonstrate the J-coupling connectivity network between the amide, aliphatic, and aromatic proton resonances of metabolites in human brain using two-dimensional (2D localized correlated spectroscopy (L-COSY. Two different global water suppression techniques were combined with L-COSY, one before and another after localizing the volume of interest (VOI. Phantom solutions containing several cerebral metabolites at physiological concentrations were evaluated initially for sequence optimization. Nine healthy volunteers were scanned using a 3T whole body MRI scanner. The VOI for 2D L-COSY was placed in the right occipital white/gray matter region. The 2D cross and diagonal peak volumes were measured for several metabolites such as N-acetyl aspartate (NAA, creatine (Cr, free choline (Ch, glutamate/glutamine (Glx, aspartate (Asp, myo-inositol (mI, GABA, glutathione (GSH, phosphocholine (PCh, phosphoethanolamine (PE, tyrosine (Tyr, lactate (Lac, macromolecules (MM and homocarnosine (Car. Using the pre-water suppression technique with L-COSY, the above mentioned metabolites were clearly identifiable and the relative ratios of metabolites were calculated. In addition to detecting multitude of aliphatic resonances in the high field region, we have demonstrated that the amide and aromatic resonances can also be detected using 2D L-COSY by pre water suppression more reliably than the post-water suppression.

  19. Effects of clamping force on the water transport and performance of a PEM (proton electrolyte membrane) fuel cell with relative humidity and current density

    International Nuclear Information System (INIS)

    Cha, Dowon; Ahn, Jae Hwan; Kim, Hyung Soon; Kim, Yongchan

    2015-01-01

    The clamping force should be applied to a proton electrolyte membrane (PEM) fuel cell due to its structural characteristics. The clamping force affects the ohmic and mass transport resistances in the PEM fuel cell. In this study, the effects of the clamping force on the water transport and performance characteristics of a PEM fuel cell are experimentally investigated with variations in the relative humidity and current density. The water transport characteristics were analyzed by calculating the net drag coefficient. The ohmic resistance decreased with the increase in the clamping force due to the reduced contact resistance and more even membrane hydration. However, the mass transport resistance increased with the increase in the clamping force due to the gas diffusion layer compression. The net drag coefficient decreased with the increase in the clamping force due to high water back-diffusion. Additionally, the relationship between the total resistance and the net drag coefficient was investigated. - Highlights: • Effects of clamping force on the performance of a PEM fuel cell are investigated. • Water transport characteristics are analyzed using net drag coefficient. • Ohmic resistance decreased with clamping force, but mass transport resistance increased. • Net drag coefficient decreased with the increase in clamping force. • Total resistance was significantly degraded for a net drag coefficient below 0.2.

  20. Temperature sensitivity of extracellular enzyme kinetics in subtropical wetland soils under different nutrient and water level conditions

    Science.gov (United States)

    Goswami, S.; Inglett, K.; Inglett, P.

    2012-12-01

    Microbial extracellular enzymes play an important role in the initial steps of soil organic matter decomposition and are involved in regulating nutrient cycle processes. Moreover, with the recent concern of climate change, microbial extracellular enzymes may affect the functioning (C losses, C sequestration, greenhouse gas emissions, vegetation changes) of different ecosystems. Hence, it is imperative to understand the biogeochemical processes that may be climate change sensitive. Here, we have measured the Michaelis Menten Kinetics [maximal rate of velocity (Vmax) and half-saturation constant (Km)] of 6 enzymes involved in soil organic matter decomposition (phosphatase, phosphodiesterase, β-D-glucosidase, cellobiohydrolase, leucine aminopeptidase, N-Acetyl-β-D glucosaminidase) in different nutrient(P) concentration both aerobically and anaerobically in Everglade water conservation area 2A (F1, F4-slough and U3-slough). Temperature sensitivity of different enzymes is assessed within soil of different P concentrations. We hypothesized that the temperature sensitivity of the enzyme changes with the biogeochemical conditions including water level and nutrient condition. Furthermore, we have tested specific hypothesis that higher P concentration will initiate more C demand for microbes leading to higher Vmax value for carbon processing enzymes in high P site. We found temperature sensitivity of all enzymes for Vmax and Km under both aerobic and anaerobic condition ranges from 0.6 to 3.2 for Vmax and 0.5 to 2.5 for Km. Q10 values of Km for glucosidase indicate more temperature sensitivity under anaerobic condition. Under aerobic condition higher temperature showed significant effect on Vmax for bisphosphatase between high P and low P site. Decreasing P concentration from F1 site to U3-S site had showed significant effect in all temperature on carbon processing enzyme. This suggests that in high P site, microbes will use more carbon-processing enzyme to get more carbon

  1. Woody biomass: Niche position as a source of sustainable renewable chemicals and energy and kinetics of hot-water extraction/hydrolysis.

    Science.gov (United States)

    Liu, Shijie

    2010-01-01

    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

  2. Hydrogen-bond dynamics and proton transfer in nanoconfinement

    NARCIS (Netherlands)

    van der Loop, T.H.

    2015-01-01

    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

  3. Effects of the anion salt nature on the rate constants of the aqueous proton exchange reactions.

    Science.gov (United States)

    Paredes, Jose M; Garzon, Andres; Crovetto, Luis; Orte, Angel; Lopez, Sergio G; Alvarez-Pez, Jose M

    2012-04-28

    The proton-transfer ground-state rate constants of the xanthenic dye 9-[1-(2-methyl-4-methoxyphenyl)]-6-hydroxy-3H-xanthen-3-one (TG-II), recovered by Fluorescence Lifetime Correlation Spectroscopy (FLCS), have proven to be useful to quantitatively reflect specific cation effects in aqueous solutions (J. M. Paredes, L. Crovetto, A. Orte, J. M. Alvarez-Pez and E. M. Talavera, Phys. Chem. Chem. Phys., 2011, 13, 1685-1694). Since these phenomena are more sensitive to anions than to cations, in this paper we have accounted for the influence of salts with the sodium cation in common, and the anion classified according to the empirical Hofmeister series, on the proton transfer rate constants of TG-II. We demonstrate that the presence of ions accelerates the rate of the ground-state proton-exchange reaction in the same order than ions that affect ion solvation in water. The combination of FLCS with a fluorophore undergoing proton transfer reactions in the ground state, along with the desirable feature of a pseudo-dark state when the dye is protonated, allows one unique direct determination of kinetic rate constants of the proton exchange chemical reaction. This journal is © the Owner Societies 2012

  4. Radiative pion-proton scattering

    International Nuclear Information System (INIS)

    Ho-Kim, Q.; Lavine, J.P.

    1977-01-01

    The results are presented of a non-relativistic calculation of the π +- proton bremsstrahlung cross section at the pion kinetic energy of 298 MeV for backward photon angles. The pion-nucleon interaction is given by models that are based on the p-wave Chew-Low theory. An interaction current is included in an attempt to make the overall bremsstrahlung amplitude gauge-invariant. The predicted cross sections show little of the expected resonance, and are in fair agreement with the data. The authors have also calculated the cross sections at other kinetic energies, and have studied effects of the off-mass-shell electromagnetic vertex. (Auth.)

  5. Proton hopping mechanism in solid polymer electrolysis demonstrated by tritium enrichment and electro-osmotic drag measurement

    International Nuclear Information System (INIS)

    Saito, Masaaki; Imaizumi, Hiroshi; Kato, Norio; Ishii, Yoshiyuki; Saito, Keiichi

    2010-01-01

    Anomalies in tritium enrichment cannot be explained only by isotopic effects in water electrolysis. The temperature dependence of the enrichment factor had been reported as increasing with 1/T. However, the increase was difficult to explain on the basis of kinetics. In this study, electro-osmotic drag (EOD, number of water molecule accompanied by a proton) and tritium enrichment ratio were investigated using light water (H 2 O) and heavy water (D 2 O) by solid polymer electrolysis. The EOD decreased and tritium enrichment ratio increased at low temperature for H 2 O. Electrolysis showed no temperature dependence for D 2 O. It was revealed that proton hopping by a hydrogen bond network of water molecules (the Grotthuss mechanism) affects the temperature dependence of EOD and tritium enrichment in the case of H 2 O. (author)

  6. Energizing porters by proton-motive force.

    Science.gov (United States)

    Nelson, N

    1994-11-01

    It is generally accepted that the chemistry of water was the most crucial determinant in shaping life on earth. Among the more important chemical features of water is its dissociation into protons and hydroxyl ions. The presence of relatively high proton concentrations in the ambient solution resulted in the evolution of proton pumps during the dawn of life on earth. These proton pumps maintained neutral pH inside the cells and generated electrochemical gradients of protons (proton-motive force) across their membranes. The existence of proton-motive force enabled the evolution of porters driven by it that are most probably among the more primitive porters in the world. The directionality of the substrate transport by the porters could be to both sides of the membranes because they can serve as proton symporters or antiporters. One of the most important subjects of this meeting is the mechanism by which proton-motive and other ion-motive forces drive the transport processes through porters. Is there a common mechanism of action for all proton-driven porters? Is there some common partial reaction by which we can identify the way that porters are energized by proton-motive force? Is there a common coupling between proton movement and uptake or secretion of certain molecules? Even a partial answer to one of these questions would advance our knowledge... or confusion. As my mentor Efraim Racker used to say: 'If you are not totally confused you do not understand the issue'.

  7. The influence of the Coulomb-distortion effect on proton-proton observables

    International Nuclear Information System (INIS)

    Plessas, W.; Mathelitsch, L.

    1980-01-01

    The effect of the Coulomb distortion of the strong interaction is studied on the basis of nucleon-nucleon observables. In particular, cross sections, polarizations, spin-correlation parameters, and spin-transfer coefficients are considered for proton-proton as well as neutron-neutron scattering at laboratory kinetic energies Esub(Lab) = 10, 20, and 50 MeV. The calculations are performed for the meson-theoretical PARIS potential, the nonlocal separable GRAZ potential and also using the Arndt-Hackman-Roper parametrization of proton-proton scattering phase shifts. Important conclusions are drawn with respect to phenomenological phase-shift analyses. (Auth.)

  8. Biodegradation of hydrocarbon mixtures in surface waters at environmentally relevant levels - Effect of inoculum origin on kinetics and sequence of degradation.

    Science.gov (United States)

    Birch, Heidi; Hammershøj, Rikke; Comber, Mike; Mayer, Philipp

    2017-10-01

    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.

  9. Proton decay theory

    International Nuclear Information System (INIS)

    Marciano, W.J.

    1983-01-01

    Topics include minimal SU(5) predictions, gauge boson mediated proton decay, uncertainties in tau/sub p/, Higgs scalar effects, proton decay via Higgs scalars, supersymmetric SU(5), dimension 5 operators and proton decay, and Higgs scalars and proton decay

  10. 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

    1994-01-01

    Quantification in localized proton NMR spectroscopy has been achieved by various methods in recent years. A new method for absolute quantification is described in this paper. The method simultaneously rules out problems with B1 field inhomogeneity and coil loading, utilizing a relation between th......M and [NAA] = 9.15 +/- 0.74 nM. It is concluded that the quantification method is easily applied in vivo, and that the absolute concentrations obtained are similar to results in other studies except those relying on assumptions of the concentration of an internal reference. The advantage...

  11. Plasma kinetics and biodistribution of water-soluble CdTe quantum dots in mice: a comparison between Cd and Te

    International Nuclear Information System (INIS)

    Han Ying; Xie Guangyun; Sun Zhiwei; Mu Ying; Han Sihai; Xiao Yang; Liu Na; Wang Hui; Guo Caixia; Shi Zhixiong; Li Yanbo; Huang Peili

    2011-01-01

    Water-soluble quantum dots (QDs) have shown potential as tumor diagnostic agents. However, little is known about their biological behaviors in vivo. Male ICR mice were intravenously given a single dose (2.5 μmol kg −1 body weight) of water-soluble cadmium–telluride (CdTe) QDs (the QDs are approximately 4 nm in diameter and have maximal emission at 630 nm). Inductively coupled plasma mass spectrometry (ICP-MS) was used for measuring the kinetic action of 111 Cd and 125 Te for 7 days. The plasma kinetics of Cd and Te followed a two-compartment model, in which Cd exhibited greater apparent volume of distribution, greater clearance, faster distribution half-life, and significantly slower elimination half-life compared to Te. Contrary to its relatively transient fate in the plasma, high levels of Cd persisted in the liver and kidneys. Te accumulated primarily in the spleen. The different plasma kinetics and distribution patterns of Cd and Te imply that CdTe QDs have been part of the degradation or aggregation in vivo.

  12. Kinetics of carbonate mineral dissolution in CO2-acidified brines at storage reservoir conditions.

    Science.gov (United States)

    Peng, Cheng; Anabaraonye, Benaiah U; Crawshaw, John P; Maitland, Geoffrey C; Trusler, J P Martin

    2016-10-20

    We report experimental measurements of the dissolution rate of several carbonate minerals in CO 2 -saturated water or brine at temperatures between 323 K and 373 K and at pressures up to 15 MPa. The dissolution kinetics of pure calcite were studied in CO 2 -saturated NaCl brines with molalities of up to 5 mol kg -1 . The results of these experiments were found to depend only weakly on the brine molality and to conform reasonably well with a kinetic model involving two parallel first-order reactions: one involving reactions with protons and the other involving reaction with carbonic acid. The dissolution rates of dolomite and magnesite were studied in both aqueous HCl solution and in CO 2 -saturated water. For these minerals, the dissolution rates could be explained by a simpler kinetic model involving only direct reaction between protons and the mineral surface. Finally, the rates of dissolution of two carbonate-reservoir analogue minerals (Ketton limestone and North-Sea chalk) in CO 2 -saturated water were found to follow the same kinetics as found for pure calcite. Vertical scanning interferometry was used to study the surface morphology of unreacted and reacted samples. The results of the present study may find application in reactive-flow simulations of CO 2 -injection into carbonate-mineral saline aquifers.

  13. Proton therapy

    International Nuclear Information System (INIS)

    Jongen, Y.

    1995-01-01

    Ideal radiotherapy deposits a large amount of energy in the tumour volume, and none in the surrounding healthy tissues. Proton therapy comes closer to this goal because of a greater concentration of dose, well defined proton ranges and points of energy release which are precisely known - the Bragg peak1. In the past, the development of clinical proton therapy has been hampered by complexity, size, and cost. To be clinically effective, energies of several hundred MeV are required; these were previously unavailable for hospital installations, and pioneering institutions had to work with complex, inadequate equipment originally intended for nuclear physics research. Recently a number of specialist organizations and commercial companies have been working on dedicated systems for proton therapy. One, IBA of Belgium, has equipment for inhouse hospital operation which encompasses a complete therapy centre, delivered as a turnkey package and incorporating a compact, automated, higher energy cyclotron with isocentric gantries. Their system will be installed at Massachusetts General Hospital, Boston. The proton therapy system comprises: - a 235 MeV isochronous cyclotron to deliver beams of up to 1.5 microamps, but with a hardware limitation to restrict the maximum possible dose; - variable energy beam (235 to 70 MeV ) with energy spread and emittance verification; - a beam transport and switching system to connect the exit of the energy selection system to the entrances of a number of gantries and fixed beamlines. Along the beam transport system, the beam characteristics are monitored with non-interceptive multiwire ionization chambers for automatic tuning; - gantries fitted with nozzles and beamline elements for beam control; both beam scattering and beam wobbling techniques are available for shaping the beam;

  14. Combined Effects of Supersaturation Rates and Doses on the Kinetic-Solubility Profiles of Amorphous Solid Dispersions Based on Water-Insoluble Poly(2-hydroxyethyl methacrylate) Hydrogels.

    Science.gov (United States)

    Schver, Giovanna C R M; Lee, Ping I

    2018-05-07

    Under nonsink dissolution conditions, the kinetic-solubility profiles of amorphous solid dispersions (ASDs) based on soluble carriers typically exhibit so-called "spring-and-parachute" concentration-time behaviors. However, the kinetic-solubility profiles of ASDs based on insoluble carriers (including hydrogels) are known to show sustained supersaturation during nonsink dissolution through a matrix-regulated diffusion mechanism by which the supersaturation of the drug is built up gradually and sustained over an extended period without any dissolved polymers acting as crystallization inhibitors. Despite previous findings demonstrating the interplay between supersaturation rates and total doses on the kinetic-solubility profiles of soluble amorphous systems (including ASDs based on dissolution-regulated releases from soluble polymer carriers), the combined effects of supersaturation rates and doses on the kinetic-solubility profiles of ASDs based on diffusion-regulated releases from water-insoluble carriers have not been investigated previously. Thus, the objective of this study is to examine the impacts of total doses and supersaturation-generation rates on the resulting kinetic-solubility profiles of ASDs based on insoluble hydrogel carriers. We employed a previously established ASD-carrier system based on water-insoluble-cross-linked-poly(2-hydroxyethyl methacrylate) (PHEMA)-hydrogel beads and two poorly water soluble model drugs: the weakly acidic indomethacin (IND) and the weakly basic posaconazole (PCZ). Our results show clearly for the first time that by using the smallest-particle-size fraction and a high dose (i.e., above the critical dose), it is indeed possible to significantly shorten the duration of sustained supersaturation in the kinetic-solubility profile of an ASD based on a water-insoluble hydrogel carrier, such that it resembles the spring-and-parachute dissolution profiles normally associated with ASDs based on soluble carriers. This generates

  15. Kinetic studies of Chromobacterium viscosum lipase in AOT water in oil microemulsions and gelatin microemulsion-based organogels.

    Science.gov (United States)

    Jenta, T R; Batts, G; Rees, G D; Robinson, B H

    1997-06-05

    Kinetic studies have shown that octyl decanoate synthesis by Chromobacterium viscosum (CV) lipase in sodium bis-2-(ethylhexyl) sulfosuccinate (AOT) water in oil (w/o) microemulsions occurs via the nonsequential (ping-pong) bi bi mechanism. There was evidence of single substrate inhibition by decanoic acid at high concentrations. Initial rate data yielded estimates for acid and alcohol Michaelis constants of ca. 10(-1) mol dm(-3) and a maximum rate under saturation conditions of ca. 10(-3) mol dm(-3) s(-1) for a lipase concentration of 0.36 mg cm(-3). CV lipase immobilized in AOT microemulsion-based organogels (MBGs) was also found to catalyze the synthesis of octyl decanoate according to the ping-pong bi bi mechanism. Reaction rates were similar in the free and immobilized systems under comparable conditions. Initial rates at saturating (but noninhibiting) substrate concentrations were first order with respect to CV lipase concentration in both w/o microemulsions and the MBG/oil systems. Gradients yielded an apparent k(cat) = 4.4 x 10(-4) mol g(-1) s(-1) in the case of w/o microemulsions, and 6.1 x 10(-4) mol g(-1) s(-1) for CV lipase immobilized in the MBGs. A third system comprising w/o microemulsions containing substrates and gelatin at concentrations comparable to those employed in the MBG formulations, provided a useful link between the conventional liquid microemulsion medium and the solid organogels. The nongelation of these intermediate systems stems from the early inclusion of substrate during a modified preparative protocol. The presence of substrate appears to prevent the development of a percolated microstructure that is thought to be a prerequisite for MBG formation. FT-NMR was employed as a semicontinuous in situ assay procedure. The apparent activity expressed by CV lipase in compositionally equivalent liquid and solid phase gelatin-containing systems was similar. An apparent activation energy of 24 +/- 2 kJ mol(-1) was determined by (1)H-NMR for

  16. Free Radical Chemistry of Disinfection Byproducts 1: Kinetics of Hydrated Electron and Hydroxyl Radical Reactions with Halonitromethanes in Water

    International Nuclear Information System (INIS)

    B. J. Mincher; R. V. Fox; S. P. Mezyk; T. Helgeson; S. K. Cole; W. J. Cooper; P. R. Gardinali

    2006-01-01

    Halonitromethanes are disinfection-byproducts formed during ozonation and chlorine/chloramine treatment of waters that contain bromide ion and natural organic matter. In this study, the chemical kinetics of the free-radical-induced degradations of a series of halonitromethanes were determined. Absolute rate constants for hydroxyl radical, OH, and hydrated electron, e aq - , reaction with both chlorinated and brominated halonitromethanes were measured using the techniques of electron pulse radiolysis and transient absorption spectroscopy. The bimolecular rate constants obtained, k (M -1 s -1 ), for e aq - /OH, respectively, were the following: chloronitromethane (3.01 ± 0.40) x 10 10 /(1.94 ± 0.32) x 10 8 ; dichloronitromethane (3.21 ± 0.17) x 10 10 /(5.12 ± 0.77) x 10 8 ; bromonitromethane (3.13 ± 0.06) x 10 10 /(8.36 ± 0.57) x 107; dibromonitromethane (3.07 ± 0.40) x 10 10 /(4.75 ± 0.98) x 10 8 ; tribromonitromethane (2.29 ± 0.39) x 10 10 /(3.25 ± 0.67) x 10 8 ; bromochloronitromethane (2.93 ± 0.47) x 10 10 /(4.2 ± 1.1) x 10 8 ; bromodichloronitromethane (2.68 ± 0.13) x 10 10 /(1.02 ± 0.15) x 10 8 ; and dibromochloronitromethane (2.95 ± 0.43) x 10 10 /(1.80 ± 0.31) x 10 8 at room temperature and pH ∼7. Comparison data were also obtained for hydroxyl radical reaction with bromoform (1.50 ± 0.05) x 10 8 , bromodichloromethane (7.11 ± 0.26) x 10 7 , and chlorodibromomethane (8.31 ± 0.25) x 10 7 M -1 s -1 , respectively. These rate constants are compared to recently obtained data for trichloronitromethane and bromonitromethane, as well as to other established literature data for analogous compounds

  17. Serial water changes in human skeletal muscles on exercise studied with proton magnetic resonance spectroscopy and imaging

    International Nuclear Information System (INIS)

    Ogino, Toru; Ikehira, Hiroo; Arimizu, Noboru

    1994-01-01

    In vivo 1 H-magnetic resonance imaging (MRI) enabled us to study the distribution of water in living tissues and to document changes in human skeletal muscles during physical exercise. The purpose of the present study was to determine the total muscle water changes after exercise using water in 1 H-MR spectroscopy and to compare these changes to the signal intensity change on T 2 * -weighted images and/or to the T 2 value change. Seven young male volunteers were positioned in a 1.5 T Philips MR imaging system. They were then asked to dorsiflex their ankle joint against a 2 kg weight once every 2 seconds for 2 minutes. The peak height of water declined according to the clearance curve after exercise in all seven cases with the 1 H-MRS similar to the signal intensity. The increasing rate at peak height of total muscle water exceeded both the signal intensity and the T 2 value because the water peak height on the 1 H-MRS included the extracellular water. In addition, we measured the changes in signal intensity in both calf muscles after walking race exercise. The time intensity curves were used to draw a clearance curve for each muscle group after exercise. It was possible to discern which muscle was used most from the T 2 * -weighted image that was obtained once after exercise. (author)

  18. Restrained Proton Indicator in Combined Quantum-Mechanics/Molecular-Mechanics Dynamics Simulations of Proton Transfer through a Carbon Nanotube.

    Science.gov (United States)

    Duster, Adam W; Lin, Hai

    2017-09-14

    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.

  19. APEX (Aqueous Photochemistry of Environmentally occurring Xenobiotics): a free software tool to predict the kinetics of photochemical processes in surface waters.

    Science.gov (United States)

    Bodrato, Marco; Vione, Davide

    2014-04-01

    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.

  20. Kinetic Typography

    DEFF Research Database (Denmark)

    van Leeuwen, Theo; Djonov, Emilia

    2014-01-01

    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.......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....