Spent fuel dissolution mechanisms

International Nuclear Information System (INIS)

Ollila, K.

1993-11-01

This study is a literature survey on the dissolution mechanisms of spent fuel under disposal conditions. First, the effects of radiolysis products on the oxidative dissolution mechanisms and rates of UO 2 are discussed. These effects have mainly been investigated by using electrochemical methods. Then the release mechanisms of soluble radionuclides and the dissolution of the UO 2 matrix including the actinides, are treated. Experimental methods have been developed for measuring the grain-boundary inventories of radionuclides. The behaviour of cesium, strontium and technetium in leaching tests shows different trends. Comparison of spent fuel leaching data strongly suggests that the release of 90 Sr into the leachant can be used as a measure of the oxidation/dissolution of the fuel matrix. Approaches to the modelling UO 2 , dissolution are briefly discussed in the next chapter. Lastly, the use of natural material, uraninite, in the evaluation of the long-term performance of spent fuel is discussed. (orig.). (81 ref., 37 figs., 8 tabs.)

Accurate rates of the complex mechanisms for growth and dissolution of minerals using a combination of rare event theories

International Nuclear Information System (INIS)

Stack, Andrew G.; Raiten, Paolo; Gale, Julian D.

2012-01-01

Mineral growth and dissolution are often treated as occurring via a single, reversible process that governs the rate of reaction. We show that multiple, distinct intermediate states can occur during both growth and dissolution. Specifically, we have used metadynamics, a method to efficiently explore the free energy landscape of a system, coupled to umbrella sampling and reactive flux calculations, to examine the mechanism and rates of attachment and detachment of a barium ion onto a stepped, barite (BaSO4) surface. The activation energies calculated for the rate limiting reactions, which are different for attachment and detachment, precisely match those measured experimentally during both growth and dissolution. These results can potentially explain anomalous, non-steady state mineral reaction rates observed experimentally, and will enable the design of more efficient growth inhibitors and facilitate an understanding of the effect of impurities.

A Study on the Anodic Dissolution of Aluminum(II)

International Nuclear Information System (INIS)

Nam, C. W.; Park, C. S.; Park, C. S.

1978-01-01

In many cases oxide films formed on metals in atmosphere or aqueous solution are chemically inactive, especially it is the case with aluminum. In this study, anodic dissolution of aluminum was done using various electrolyte and cathode, mechanism of which was examined. As a consequence, oxide film on aluminum surface was dissolved together with the dissolution reaction of metal by the anodic current. It was shown that the dissolution reaction due to the contact between electrolyte and metal happened in the same time

Dissolution mechanisms of CO2 hydrate droplets in deep seawaters

International Nuclear Information System (INIS)

Gabitto, Jorge; Tsouris, Costas

2006-01-01

Carbon dioxide dissolution at intermediate ocean depths was studied using physical and mass transfer models. Particle density and hydrate layer thickness were determined using existing field data. Pseudo-homogeneous and heterogeneous mass transfer models were proposed to study the dissolution process. Pseudo-homogeneous models do not seem to represent the dissolution process well. Although heterogeneous models interpret the physical behavior better, unresolved issues related to hydrate dissolution still remain. For example, solid hydrate forms on one side of the hydrate film while it dissolves on the other. Dissolution is a complex process that comprises at least two sequential steps. The global process is controlled by mass transfer inside the hydrate layer or by a dissolution reaction at the hydrate-water interface

Dissolution mechanism of aluminum hydroxides in acid media

Science.gov (United States)

Lainer, Yu. A.; Gorichev, I. G.; Tuzhilin, A. S.; Gololobova, E. G.

2008-08-01

The effects of the concentration, temperature, and potential at the hydroxide/electrolyte interface on the aluminum hydroxide dissolution in sulfuric, hydrochloric, and perchloric acids are studied. The limiting stage of the aluminum hydroxide dissolution in the acids is found to be the transition of the complexes that form on the aluminum hydroxide surface from the solid phase into the solution. The results of the calculation of the acid-base equilibrium constants at the oxide (hydroxide)/solution interface using the experimental data on the potentiometric titration of Al2O3 and AlOOH suspensions are analyzed. A mechanism is proposed for the dissolution of aluminum hydroxides in acid media.

Importance of surface structure on dissolution of fluorite

DEFF Research Database (Denmark)

Godinho, Jose; Piazolo, Sandra; Balic Zunic, Tonci

2014-01-01

forming the initial surface and its inclination to the closest stable planes, which are specific for each surface orientation. During an initial dissolution regime dissolution rates decrease significantly, even though the total surface area increases. During a second dissolution regime, some surfaces...... by the relative stability of the planes and type of edges that constitute a surface needs to be considered. Significant differences between dissolution rates calculated based on surface area alone, and based on surface reactivity are expected for materials with the fluorite structure....

Haw-glass dissolution and radionuclide release: mechanism - modelling - source term

Energy Technology Data Exchange (ETDEWEB)

Grambow, B [Forschungszentrum Karlsruhe, Institut fur Nukleare, Karlsruhe (Germany)

1997-07-01

Important release controlling processes are: 1) kinetics of glass matrix dissolution (leaching), 2) formation of secondary alteration products (controlling thermodynamic solubility), 3) sorption on surfaces in the engineered barrier system and 4) formation of mobile species. Quantification of these processes requires assessment of the energetics and dynamics of the various reversible and irreversible processes within an overall open non-equilibrium system. Corrosion/dissolution of the waste matrices is not necessarily associated with a proportional release of radionuclides. The formation of new secondary phases, such as silicates, molybdates, uranates, carbonates... establishes a new geochemical barrier for re-immobilization of radionuclides dissolved from the waste matrices. The presence of iron (corroding canisters during glass alteration) reduces the solution concentration of redox sensitive radionuclides. Consequently, the container, after being corroded, constitutes an important geochemical barrier for radionuclide re-immobilization. Geochemical modelling of the long-term behaviour of glasses must be performed in an integrated way, considering simultaneous reactions of the glass, of container corrosion, of repository rock and of backfill material. Until now, only few attempts were made for integral systems modelling. (A.C.)

Reaction of hydrogen peroxide with uranium zirconium oxide solid solution - Zirconium hinders oxidative uranium dissolution

Science.gov (United States)

Kumagai, Yuta; Takano, Masahide; Watanabe, Masayuki

2017-12-01

We studied oxidative dissolution of uranium and zirconium oxide [(U,Zr)O2] in aqueous H2O2 solution to estimate (U,Zr)O2 stability to interfacial reactions with H2O2. Studies on the interfacial reactions are essential for anticipating how a (U,Zr)O2-based molten fuel may chemically degrade after a severe accident. The fuel's high radioactivity induces water radiolysis and continuous H2O2 generation. Subsequent reaction of the fuel with H2O2 may oxidize the fuel surface and facilitate U dissolution. We conducted our experiments with (U,Zr)O2 powder (comprising Zr:U mole ratios of 25:75, 40:60, and 50:50) and quantitated the H2O2 reaction via dissolved U and H2O2 concentrations. Although (U,Zr)O2 reacted more quickly than UO2, the dissolution yield relative to H2O2 consumption was far less for (U,Zr)O2 compared to that of UO2. The reaction kinetics indicates that most of the H2O2 catalytically decomposed to O2 at the surface of (U,Zr)O2. We confirmed the H2O2 catalytic decomposition via O2 production (quantitative stoichiometric agreement). In addition, post-reaction Raman scattering spectra of the undissolved (U,Zr)O2 showed no additional peaks (indicating a lack of secondary phase formation). The (U,Zr)O2 matrix is much more stable than UO2 against H2O2-induced oxidative dissolution. Our findings will improve understanding on the molten fuels and provide an insight into decommissioning activities after a severe accident.

Surface studies of feldspar dissolution using surface replication combined with electron microscopic and spectroscopic techniques

Energy Technology Data Exchange (ETDEWEB)

Fung, P C [Petro-Canada, Calgary, Alberta; Sanipelli, G G

1982-04-01

The replica of a microcline cleavage surface was examined before and at various stages of interaction with water and acid solutions at 70/sup 0/C, as part of basic geochemical research for the Canadian Nuclear Fuel Waste Management Program to investigate the feasibility of disposal of these wastes in repositories mined in crystalline rocks. The objective of the report presented was to investigate the mechanism for Al and Si removal during incongruent dissolution of feldspars and its effect on dissolution rate. It was found that phase transformation, like dissolution occured preferentially along crystal defects on the surfaces of the feldspars. Secondary minerals always occured as discrete particles occupying only a very small fraction of the total parent surface, and hence, their presence would not affect the bulk composition or, in this regard, the overall dissolution rate of the feldspars by the formation of diffusion barriers.

Microscopic Mechanisms of Dissolution-Precipitation at the Water-Manganese Mineral Interfaces

Science.gov (United States)

Jun, Y.; Martin, S. T.

2006-12-01

The fate and transport of metal contaminants in water are often affected by the manganese redox cycling and the accompanying dissolution and precipitation reactions. Direct microscopic observations of such dynamic reactions, however, are sparse. In this work, microscopic mechanisms of simultaneous dissolution and precipitation of manganese minerals is studied by atomic force microscope (AFM) at circumneutral pH. The effects of the substrate surface morphology, the substrate atomic structure, and the aqueous concentration of Mn2+ on the formation of Mn oxide islands are investigated. Under oxic conditions, Mn2+(aq) dissolved from MnCO3 surface is reacted with O2(aq) at circumneutral pH to form Mn oxide islands on the (10-14) surface of MnCO3. The Mn oxide islands grow heteroepitaxially. On terraces, rhombohedral islands form with 90° rotation relative to crystallographic axis of the underlying substrate, and with z-directional self-limitation. Comparison studies done with MgCO3 and CaCO3 show that the former also promotes heteroepitaxial growth whereas the latter does not. This difference is explained by the relative bond length mismatch between the structures of the carbonate substrates and the atomic structures of Mn oxide islands. A free energy model is also employed to explain why the heights of the Mn oxide islands self limit. Our results provide an improved understanding for the development of predictive models both of exchange across the sediment-water interfaces and the fate and transport of contaminants in aqueous environments.

A dissolution-diffusion sliding model for soft rock grains with hydro-mechanical effect

Directory of Open Access Journals (Sweden)

Z. Liu

2018-06-01

Full Text Available The deformation and failure of soft rock affected by hydro-mechanical (HM effect are one of the most concerns in geotechnical engineering, which are basically attributed to the grain sliding of soft rock. This study tried to develop a dissolution-diffusion sliding model for the typical red bed soft rock in South China. Based on hydration film, mineral dissolution and diffusion theory, and geochemical thermodynamics, a dissolution-diffusion sliding model with the HM effect was established to account for the sliding rate. Combined with the digital image processing technology, the relationship between the grain size of soft rock and the amplitude of sliding surface was presented. An equation for the strain rate of soft rocks under steady state was also derived. The reliability of the dissolution-diffusion sliding model was verified by triaxial creep tests on the soft rock with the HM coupling effect and by the relationship between the inversion average disjoining pressure and the average thickness of the hydration film. The results showed that the sliding rate of the soft rock grains was affected significantly by the waviness of sliding surface, the shear stress, and the average thickness of hydration film. The average grain size is essential for controlling the steady-state creep rate of soft rock. This study provides a new idea for investigating the deformation and failure of soft rock with the HM effect. Keywords: Soft rock, Hydro-mechanical (HM effect, Mineral dissolution-diffusion, Grain sliding model

Understanding the mechanisms of solid-water reactions through analysis of surface topography.

Science.gov (United States)

Bandstra, Joel Z; Brantley, Susan L

2015-12-01

The topography of a reactive surface contains information about the reactions that form or modify the surface and, therefore, it should be possible to characterize reactivity using topography parameters such as surface area, roughness, or fractal dimension. As a test of this idea, we consider a two-dimensional (2D) lattice model for crystal dissolution and examine a suite of topography parameters to determine which may be useful for predicting rates and mechanisms of dissolution. The model is based on the assumption that the reactivity of a surface site decreases with the number of nearest neighbors. We show that the steady-state surface topography in our model system is a function of, at most, two variables: the ratio of the rate of loss of sites with two neighbors versus three neighbors (d(2)/d(3)) and the ratio of the rate of loss of sites with one neighbor versus three neighbors (d(1)/d(3)). This means that relative rates can be determined from two parameters characterizing the topography of a surface provided that the two parameters are independent of one another. It also means that absolute rates cannot be determined from measurements of surface topography alone. To identify independent sets of topography parameters, we simulated surfaces from a broad range of d(1)/d(3) and d(2)/d(3) and computed a suite of common topography parameters for each surface. Our results indicate that the fractal dimension D and the average spacing between steps, E[s], can serve to uniquely determine d(1)/d(3) and d(2)/d(3) provided that sufficiently strong correlations exist between the steps. Sufficiently strong correlations exist in our model system when D>1.5 (which corresponds to D>2.5 for real 3D reactive surfaces). When steps are uncorrelated, surface topography becomes independent of step retreat rate and D is equal to 1.5. Under these conditions, measures of surface topography are not independent and any single topography parameter contains all of the available mechanistic

Dissolution of organic solvents from painted surfaces into water

International Nuclear Information System (INIS)

Wren, J.C.; Jobe, D.J.; Sanipelli, G.G.; Ball, J.M.

2000-01-01

The presence of volatile iodine in containment buildings is one of the major safety concerns in the potential event of nuclear reactor accidents. Organic impurities in containment water, originating from various painted structural surfaces and organic materials, could have a significant impact on iodine volatility following an accident. To determine the source and magnitude of organic impurities and their effects on time-dependent iodine volatility, the dissolution for organic constituents from paints used in reactor buildings has been studied under postulated accident conditions. The studies of the organic dissolution from carbon steel coupons coated with zinc-primed vinyl, epoxy-primed polyurethane or epoxy paints over the temperature range 25-90 deg C are reported. Relatively large activation energies were measured for the release of the principal organic compounds from painted surfaces, suggesting it is the release of the solvents from the paint matrix rather than their diffusion through the solution that is the rate determining step for the dissolution mechanism. The similarities in the values of activation energies for the dissolution of different organic compounds from the paints suggest the release rate is independent of the nature of the painted surface or the type of organic being released from the surface. These two observations indicate that it may be possible to write a generalized rate expression for the release of organic compounds from painted surfaces in containment following an accident. The possible implications of these results for predicting iodine volatility in containment are also discussed. (author)

The effect of Ti and Nb on nitrogen dissolution reaction in stainless steel melt

International Nuclear Information System (INIS)

Jang, Min Whan; Hong, In Kook; Pak, Jong Jin; Song, Hyo Seok; Lee, Yong Deuk

2002-01-01

A kinetic study of nitrogen dissolution in STS304 stainless steel melt containing Ti and Nb has been carried out at 1500 degree C using an induction furnace and a levitation melting furnace. At low O and S levels, the nitrogen dissolution rate showed the first-order kinetics being controlled by the mass transfer of nitrogen in the melt. Ti addition to STS304 stainless melt significantly retarded the nitrogen dissolution rate by the formation of solid Ti oxide layer adhered on the melt surface. Nb did not affect the rate of nitrogen dissolution. In the levitation melting experiment where the oxide layer was removed from the melt surface, Ti did not retard the nitrogen dissolution rate. Simultaneous addition of Ti and Al increased the dissolution rate by the formation of non-wetting Al 2 O 3 on the melt surface. A small addition of CaO-Al 2 O 3 synthetic flux to Ti containing melt was very effective to remove the oxide layer, hence to increase the nitrogen dissolution rate

The effect of Ti and Nb on nitrogen dissolution reaction in stainless steel melt

Energy Technology Data Exchange (ETDEWEB)

Jang, Min Whan; Hong, In Kook; Pak, Jong Jin [Hanyang Univ., Ansan (Korea, Republic of); Song, Hyo Seok; Lee, Yong Deuk [POSCO, Pohang (Korea, Republic of)

2002-03-01

A kinetic study of nitrogen dissolution in STS304 stainless steel melt containing Ti and Nb has been carried out at 1500 degree C using an induction furnace and a levitation melting furnace. At low O and S levels, the nitrogen dissolution rate showed the first-order kinetics being controlled by the mass transfer of nitrogen in the melt. Ti addition to STS304 stainless melt significantly retarded the nitrogen dissolution rate by the formation of solid Ti oxide layer adhered on the melt surface. Nb did not affect the rate of nitrogen dissolution. In the levitation melting experiment where the oxide layer was removed from the melt surface, Ti did not retard the nitrogen dissolution rate. Simultaneous addition of Ti and Al increased the dissolution rate by the formation of non-wetting Al{sub 2}O{sub 3} on the melt surface. A small addition of CaO-Al{sub 2}O{sub 3} synthetic flux to Ti containing melt was very effective to remove the oxide layer, hence to increase the nitrogen dissolution rate.

Surface-Activated Coupling Reactions Confined on a Surface.

Science.gov (United States)

Dong, Lei; Liu, Pei Nian; Lin, Nian

2015-10-20

-functional theory (DFT) transition-state calculations have been used to shed light on reaction mechanisms and to unravel the trends of different surface materials. In this Account, we discuss recent progress made in two widely studied surface-confined coupling reactions, aryl-aryl (Ullmann-type) coupling and alkyne-alkyne (Glaser-type) coupling, and focus on surface activation effects. Combined experimental and theoretical studies on the same reactions taking place on different metal surfaces have clearly demonstrated that different surfaces not only reduce the reaction barrier differently and render different reaction pathways but also control the morphology of the reaction products and, to some degree, select the reaction products. We end the Account with a list of questions to be addressed in the future. Satisfactorily answering these questions may lead to using the surface-confined coupling reactions to synthesize predefined products with high yield.

Dissolution kinetics of heulandite at pH 2--12 and 25 degrees C

International Nuclear Information System (INIS)

Ragnarsdottir, K.V.

1993-01-01

Because of their favourable cation exchange reactions, heulandite and clinoptilolite have been suggested as being capable of immobilizing radionuclides and therefore could possibly act as an important barrier for nuclear waste. Recent studies of laboratory-reacted minerals indicate, however, that hydrated surface layers tend to accumulate highly hydrolyzable heavy elements. These hydrated layers may therefore be the most important retardants for radionuclides. The dissolution rate of heulandite depends strongly on pH. Based on silica release, the logarithm of the steady-state dissolution rate at pH 2 is -13.1 mol cm -2 s -1 . The logarithm of the rate decreases to -15.8 mol cm -2 s -1 at pH 7.2 and increases again to -14.6 mol cm -2 s -1 at pH 12.2. At low pH, Al is released preferentially to silica; but at intermediate and high pH, the release of silica appears to be congruent relative to Al. The change in dissolution rate with pH indicates that at low pH, the dissolution mechanism is controlled by the detachment of a positively charged Al species, >Al-OH 2 + . Below pH 5, however, a silica-rich surface layer is formed requiring diffusion through the layer. At intermediate and high pH, it is likely that the dissolution rate is controlled by the detachment of a negatively charged silica species, >Si - O - . The reaction order of the hydrogen ion under low pH conditions is 0.7, and the reaction order of the OH - ion is 0.3 at high pH. The measured dissolution rates indicate that a 1 mm heulandite crystal would dissolve in 300,000 yrs if the solution composition is maintained undersaturated. 75 refs., 11 figs., 3 tabs

Dissolution kinetics of magnesium hydroxide for CO{sub 2} separation from coal-fired power plants

Energy Technology Data Exchange (ETDEWEB)

Bharadwaj, Hari Krishna [Chemical Engineering Program, School of Energy, Environmental, Biological, and Medical Engineering, University of Cincinnati, Cincinnati, OH 45221-0012 (United States); Lee, Joo-Youp, E-mail: joo.lee@uc.edu [Chemical Engineering Program, School of Energy, Environmental, Biological, and Medical Engineering, University of Cincinnati, Cincinnati, OH 45221-0012 (United States); Li, Xin; Liu, Zhouyang [Chemical Engineering Program, School of Energy, Environmental, Biological, and Medical Engineering, University of Cincinnati, Cincinnati, OH 45221-0012 (United States); Keener, Tim C. [Environmental Engineering Program, School of Energy, Environmental, Biological, and Medical Engineering, University of Cincinnati, Cincinnati, OH 45221-0012 (United States)

2013-04-15

Highlights: ► Magnesium hydroxide dissolution was found to be controlled by chemical reaction. ► The intrinsic kinetics has a fractional order between 0.20 and 0.31. ► The true activation energy value was found to have 76 ± 11 kJ/gmol. ► A shrinking-core model predicted experimental data with good accuracy. -- Abstract: The dissolution of magnesium hydroxide in water for the release of magnesium and hydroxyl ions into the solution to maintain suitable alkalinity is a crucial step in the Mg(OH){sub 2}-based CO{sub 2} absorption process. In this study, the rate of dissolution of Mg(OH){sub 2} was investigated under different operating conditions using a pH stat apparatus. The dissolution process was modeled using a shrinking core model and the overall Mg(OH){sub 2} dissolution process was found to be controlled by the surface chemical reaction of Mg(OH){sub 2} with H{sup +} ions. Under the chemical reaction control regime, the dissolution of Mg(OH){sub 2} in alkaline conditions was found not to follow a first-order reaction, and the fractional order of reaction was estimated to lie between 0.20 and 0.31. This suggests that the dissolution reaction is a non-elementary reaction, consisting of a sequence of elementary reactions, via most likely forming a surface magnesium complex. The true activation energy value of 76 ± 11 kJ/gmol was found to be almost twice as much as the observed activation energy value of 42 ± 6 kJ/gmol determined at pH 8.6, and was comparable with the previously reported values. The particle sizes predicted from the intrinsic kinetics determined from the model were in good agreement with the experimentally measured particle sizes during the dissolution process.

Kinetics of UO2(s) dissolution under reducing conditions: Numerical modelling

International Nuclear Information System (INIS)

Puigdomenech, I.; Casas, I.; Bruno, J.

1990-05-01

A numerical model is presented that describes the dissolution and precipitation of UO 2 (s) under reducing conditions. For aqueous solutions with pH>4, main reaction is: UO 2 (s)+2H 2 O↔U(OH) 4 (aq). The rate constant for the precipitation reaction is found to be log(k p )=-1.2±0.2 h -1 m -2 , while the value for the rate constant of the dissolution reaction is log(k d )=-9.0±0.2 mol/(1 h m 2 ). Most of the experiments reported in the literature show a fast initial dissolution of a surface film of hexavalent uranium oxide. Making the assumption that the chemical composition of the surface coating is U 3 O 7 (s), we have derived a mechanism for this process, and its rate constants have been obtained. The influence of HCO 3 - and CO 3 2- on the mechanism of dissolution and precipitation of UO 2 (s) is still unclear. From the solubility measurements reported, one may conclude that the identity of the aqueous complexes in solution is not well known. Therefore it is not possible to make a mechanistic interpretation of the kinetic data in carbonate medium. (orig.)

Bond-selective control of a gas-surface reaction

Science.gov (United States)

Killelea, Daniel R.

The prospect of using light to selectively control chemical reactions has tantalized chemists since the development of the laser. Unfortunately, the realization of laser-directed chemistry is frequently thwarted by the randomization of energy within the molecule through intramolecular vibrational energy distribution (IVR). However, recent results showing vibrational mode-specific reactivity on metal surfaces suggest that IVR may not always be complete for gas-surface reactions. Here, we combine molecular beam techniques and direct laser excitation to characterize the bond-specific reactivity of trideuteromethane on a Ni(111) surface. Our results reveal important details about how vibrational energy is distributed in the reactive molecule. We use a molecular beam to direct state-selected trideuteromethane (CHD 3) molecules onto a nickel single crystal sample and use the results we obtain to describe the flow of vibrational energy in the methane-surface reaction complex. We show that CHD3 molecules initially excited to v=1, J=2, K=0 of the v 1 symmetric C-H stretching mode will dissociate exclusively via C-H cleavage on Ni(111). This result highlights the localization of vibrational energy in the reaction complex, despite the presence of many energy exchange channels with the high state-density surface. We demonstrate, for the first time, highly parallel bond-selective control of a heterogeneously catalyzed reaction. We place our results in the context of recent experiments investigating IVR for molecules in both the gas phase and liquid solutions. If IVR is fast on the reaction timescale, vibrational energy would be randomly distributed throughout the nascent methane-surface reaction complex and vibrational mode-specific behavior would not occur. The short timescale of a direct gas-surface collision may explain how the exchange of energy via IVR is limited to only a small subset of the energetic configurations available to the reaction complex. This framework

Controlled Dissolution of Surface Layers for Elemental Analysis by Inductively Coupled Plasma-Mass Spectrometry

Energy Technology Data Exchange (ETDEWEB)

Lorge, Susan Elizabeth [Iowa State Univ., Ames, IA (United States)

2007-01-01

Determining the composition of thin layers is increasingly important for a variety of industrial materials such as adhesives, coatings and microelectronics. Secondary ion mass spectrometry (SIMS), Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy (XPS), glow discharge optical emission spectroscopy (GDOES), glow discharge mass spectrometry (GDMS), and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) are some of the techniques that are currently employed for the direct analysis of the sample surface. Although these techniques do not suffer from the contamination problems that often plague sample dissolution studies, they do require matrix matched standards for quantification. Often, these standards are not readily available. Despite the costs of clean hoods, Teflon pipette tips and bottles, and pure acids, partial sample dissolution is the primary method used in the semiconductor industry to quantify surface impurities. Specifically, vapor phase decomposition (VPD) coupled to ICP-MS or total reflection x-ray fluorescence (TXRF) provides elemental information from the top most surface layers at detection sensitivities in the 10⁷-10¹⁰atoms/cm² range. The ability to quantify with standard solutions is a main advantage of these techniques. Li and Houk applied a VPD-like technique to steel. The signal ratio of trace element to matrix element was used for quantification. Although controlled dissolution concentrations determined for some of the dissolved elements agreed with the certified values, concentrations determined for refractory elements (Ti, Nb and Ta) were too low. LA-ICP-MS and scanning electron microscopy (SEM) measurements indicated that carbide grains distributed throughout the matrix were high in these refractory elements. These elements dissolved at a slower rate than the matrix element, Fe. If the analyte element is not removed at a rate similar to the matrix element a true

Assessing the effect of dissolved organic ligands on mineral dissolution rates: An example from calcite dissolution

International Nuclear Information System (INIS)

DeMaio, T.; Grandstaff, D.E.

1997-01-01

Experiments suggest that dissolved organic ligands may primarily modify mineral dissolution rates by three mechanisms: (1) metal-ligand (M-L) complex formation in solution, which increases the degree of undersaturation, (2) formation of surface M-L complexes that attack the surface, and (3) formation of surface complexes which passivate or protect the surface. Mechanisms (1) and (2) increase the dissolution rate and the third decreases it compared with organic-free solutions. The types and importance of these mechanisms may be assessed from plots of dissolution rate versus degree of undersaturation. To illustrate this technique, calcite, a common repository cementing and vein-filling mineral, was dissolved at pH 7.8 and 22 C in Na-Ca-HCO 3 -Cl solutions with low concentrations of three organic ligands. Low citrate concentrations (50 microM) increased the dissolution rate consistent with mechanism (1). Oxalate decreased the rate, consistent with mechanism (3). Low phthalate concentration (<50 microM) decreased calcite dissolution rates; however, higher concentrations increased the dissolution rates, which became faster than in inorganic solutions. Thus, phthalate exhibits both mechanisms (2) and (3) at different concentrations. In such cases linear extrapolations of dissolution rates from high organic ligand concentrations may not be valid

Mechanisms of oxide dissolution by acid chelating agents

International Nuclear Information System (INIS)

Blesa, M.A.; Maroto, A.J.G.

1982-01-01

In this paper, the different possible rate controlling processes in the dissolution of metallic oxides are examined. In particular, the following situations are assessed: mass-transfer control; coupling of mass-transfer and reactions at the interface; interface equilibration with the solution; various interface disruption and reconstruction phenomena. For each of the above mentioned cases, the influence of variables such as reagent concentration, temperature, pH, fluid hydrodynamics and general and specific catalysts is discussed. Depending upon the particular situation it is found that a more rational basis for the development of reagent is given by these considerations. The influence of chelating agents on both the thermodynamics and kinetics of the process is discussed, and the results of experimental studies in batch on magnetite and various ferrites are presented and discussed. For this purpose, several reagents were studied, including some very effective ones like thioglycolic acid, and others commonly used in actual decontamination, like ethylenediaminetetraacetic acid and oxalic acid. The relation to other (reductive) chemical decontamination procedures is discussed. The relevance of these studies to decontamination of metallic surfaces is discussed

Determination of the dissolution slowness surface by study of etched shapes I. Morphology of the dissolution slowness surface and theoretical etched shapes

Science.gov (United States)

Leblois, T.; Tellier, C. R.

1992-07-01

We propose a theoretical model for the anisotropic etching of crystals, in order to be applied in the micromachining. The originality of the model is due to the introduction of dissolution tensors to express the representative surface of the dissolution slowness. The knowledge of the equation of the slowness surface allows us to determine the trajectories of all the elements which compose the starting surface. It is then possible to construct the final etched shape by numerical simulation. Several examples are given in this paper which show that the final etched shapes are correlated to the extrema of the dissolution slowness. Since the slowness surface must be determined from experiments, emphasis is placed on difficulties encountered when we correlate theory to experiments. Nous avons modélisé le processus de dissolution anisotrope des cristaux en vue d'une application à la simulation des formes obtenues par photolithogravure chimique. La principale originalité de ce modèle tient à l'introduction de tenseurs de dissolution pour exprimer la surface représentative de la lenteur de dissolution. La connaissance de l'équation de la lenteur de dissolution permet de calculer les trajectoires des différents éléments constituant la surface de départ puis de reconstituer par simulation la forme dissoute. Les simulations démontrent que les formes limites des cristaux dissous sont corrélées aux extrema de la lenteur de dissolution. La détermination de la surface de la lenteur se faisant à partir de mesures expérimetales, nous nous sommes efforcés de montrer toutes les difficultés attachées à cette analyse.

Modeling surface area to volume effects on borosilicate glass dissolution

International Nuclear Information System (INIS)

Bourcier, W.L.; Ebert, W.L.; Feng, X.

1992-11-01

We simulated the reaction of SRL-131 glass with equilibrated J-13 water in order to investigate the effects of surface area to volume ratio (SA/V) on glass dissolution. We show that glass-fluid ion exchange causes solution pH to rise to progressively higher values as SA/V increases. Because the ion exchange is rapid relative to the duration of the glass dissolution experiment, the pH effect does not scale with (SA/V)*time. Experiments compared at the same (SA/V)*time value therefore have different pHs, with higher pHs at higher SA/V ratios. Both experimental data and our simulation results show similar trends of increasing reaction rate as a function of SA/V ratio when scaled to (SA/V)*time. Glasses which react in systems of differing SA/V ratio therefore follow different reaction paths and high SA/V ratios cannot be used to generate data which accurately scales to long time periods unless the ion exchange effect is taken into account. We suggest some simple test designs which enable more reliable high. SA/V accelerated tests

Affinity functions for modeling glass dissolution rates

Energy Technology Data Exchange (ETDEWEB)

Bourcier, W.L. [Lawrence Livermore National Lab., CA (United States)

1997-07-01

Glass dissolution rates decrease dramatically as glass approach ''saturation'' with respect to the leachate solution. Most repository sites are chosen where water fluxes are minimal, and therefore the waste glass is most likely to dissolve under conditions close to ''saturation''. The key term in the rate expression used to predict glass dissolution rates close to ''saturation'' is the affinity term, which accounts for saturation effects on dissolution rates. Interpretations of recent experimental data on the dissolution behaviour of silicate glasses and silicate minerals indicate the following: 1) simple affinity control does not explain the observed dissolution rate for silicate minerals or glasses; 2) dissolution rates can be significantly modified by dissolved cations even under conditions far from saturation where the affinity term is near unity; 3) the effects of dissolved species such as Al and Si on the dissolution rate vary with pH, temperature, and saturation state; and 4) as temperature is increased, the effect of both pH and temperature on glass and mineral dissolution rates decrease, which strongly suggests a switch in rate control from surface reaction-based to diffusion control. Borosilicate glass dissolution models need to be upgraded to account for these recent experimental observations. (A.C.)

Aqueous dissolution of silver iodide and associated iodine release under reducing conditions with FeCl2 solution

International Nuclear Information System (INIS)

Inagaki, Yaohiro; Imamura, Toshitaka; Idemitsu, Kazuya; Arima, Tatsumi; Kato, Osamu; Nishimura, Tsutomu; Asano, Hidekazu

2008-01-01

An empirical and analytical study was performed on the aqueous dissolution of silver iodide (AgI) to release iodine under reducing conditions with Fe 2+ in order to understand the fundamental chemical and/or physical behavior of potential radioactive iodine waste forms under geological disposal conditions. Aqueous dissolution tests of AgI powder in FeCl 2 solutions (10 -6 M to 10 -3 M) were performed in a glove box purged with a gas mixture (Ar + 5% H 2 ). The test results showed that AgI dissolves to release iodine at extremely slow rates, being controlled by a diffusion process in any FeCl 2 solution. The comparison with thermodynamic calculations based on redox equilibria suggested that the AgI dissolution proceeds by redox reaction between Ag + and Fe 2+ ; however, it was far from the thermodynamic equilibrium. These results suggested that the form of AgI itself has a potential to immobilize iodine for a long time even under the disposal conditions. Solid-phase analysis for the reacted AgI by using SEM/EDS showed a certain amount of silver (maybe metallic silver) precipitated at the surface. On the basis of these results and discussion, a potential mechanism for the actual AgI dissolution was proposed as follows. The AgI dissolution proceeds by redox reaction between Ag + and Fe 2+ to release I - , which results in the precipitation of metallic silver as a reduction product of Ag + at the AgI surface to form a thin layer covering the AgI surface. The silver layer evolves to be protective against the transport of reactant species, by which the further dissolution to reach the equilibrium is suppressed. Consequently, the dissolution proceeds at extremely slow rates, being controlled by a diffusion process. (author)

Turbulent solutal convection and surface patterning in solid dissolution

International Nuclear Information System (INIS)

Sullivan, T.S.; Liu, Y.; Ecke, R.E.

1996-01-01

We describe experiments in which crystals of NaCl, KBr, and KCl are dissolved from below by aqueous solutions containing concentrations of the respective salts from zero concentration to near saturation. The solution near the solid-liquid interface is gravitationally unstable, producing turbulent hydrodynamic motion similar to thermal convection from a single surface cooled from above. The coupling of the fluid flow with the solid dissolution produces irregular patterns at the solid-liquid interface with a distribution of horizontal length scales. The dissolution mass flux and the pattern length scales are compared with a turbulent boundary layer model. Remarkable agreement is found, showing that the fluid motion controls both the dissolution rate and the interface patterning. copyright 1996 The American Physical Society

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

Physical heterogeneity control on effective mineral dissolution rates

Science.gov (United States)

Jung, Heewon; Navarre-Sitchler, Alexis

2018-04-01

Hydrologic heterogeneity may be an important factor contributing to the discrepancy in laboratory and field measured dissolution rates, but the governing factors influencing mineral dissolution rates among various representations of physical heterogeneity remain poorly understood. Here, we present multiple reactive transport simulations of anorthite dissolution in 2D latticed random permeability fields and link the information from local grid scale (1 cm or 4 m) dissolution rates to domain-scale (1m or 400 m) effective dissolution rates measured by the flux-weighted average of an ensemble of flow paths. We compare results of homogeneous models to heterogeneous models with different structure and layered permeability distributions within the model domain. Chemistry is simplified to a single dissolving primary mineral (anorthite) distributed homogeneously throughout the domain and a single secondary mineral (kaolinite) that is allowed to dissolve or precipitate. Results show that increasing size in correlation structure (i.e. long integral scales) and high variance in permeability distribution are two important factors inducing a reduction in effective mineral dissolution rates compared to homogeneous permeability domains. Larger correlation structures produce larger zones of low permeability where diffusion is an important transport mechanism. Due to the increased residence time under slow diffusive transport, the saturation state of a solute with respect to a reacting mineral approaches equilibrium and reduces the reaction rate. High variance in permeability distribution favorably develops large low permeability zones that intensifies the reduction in mixing and effective dissolution rate. However, the degree of reduction in effective dissolution rate observed in 1 m × 1 m domains is too small (equilibrium conditions reduce the effective dissolution rate by increasing the saturation state. However, in large domains where less- or non-reactive zones develop, higher

Non-equilibrium Thermodynamic Dissolution Theory for Multi-Component Solid/Liquid Surfaces Involving Surface Adsorption and Radiolysis Kinetics

International Nuclear Information System (INIS)

Stout, R B

2001-01-01

A theoretical expression is developed for the dissolution rate response for multi-component radioactive materials that have surface adsorption kinetics and radiolysis kinetics when wetted by a multi-component aqueous solution. An application for this type of dissolution response is the performance evaluation of multi-component spent nuclear fuels (SNFs) for long term interim storage and for geological disposition. Typically, SNF compositions depend on initial composition, uranium oxide and metal alloys being most common, and on reactor burnup which results in a wide range of fission product and actinide concentrations that decay by alpha, beta, and gamma radiation. These compositional/burnup ranges of SNFs, whether placed in interim storage or emplaced in a geologic repository, will potentially be wetted by multi-component aqueous solutions, and these solutions may be further altered by radiolytic aqueous species due to three radiation fields. The solid states of the SNFs are not thermodynamically stable when wetted and will dissolve, with or without radiolysis. The following development of a dissolution theory is based on a non-equilibrium thermodynamic analysis of energy reactions and energy transport across a solid-liquid phase change discontinuity that propagates at a quasi-steady, dissolution velocity. The integral form of the energy balance equation is used for this spatial surface discontinuity analysis. The integral formulation contains internal energy functional of classical thermodynamics for both the SNFs' solid state and surface adsorption species, and the adjacent liquid state, which includes radiolytic chemical species. The steady-state concentrations of radiolytic chemical species are expressed by an approximate analysis of the decay radiation transport equation. For purposes of illustration a modified Temkin adsorption isotherm was assumed for the surface adsorption kinetics on an arbitrary, finite area of the solid-liquid dissolution interface. For

Modelling of the UO2 dissolution mechanisms in synthetic groundwater. Experiments carried out under anaerobic and reducing conditions

International Nuclear Information System (INIS)

Cera, E.; Grive, M.; Bruno, J.; Ollila, K.

2000-07-01

The experimental data generated under anaerobic and reducing conditions within the EU R and D programme 1996-1998 entitled 'Source term for performance assessment of spent fuel as a waste form' and published as a POSIVA report (Ollila, 1999) have been modelled in the present work. The dissolution data available, mainly U in the aqueous phase as a function of time and redox potentials have been used to elucidate the redox pairs controlling the redox potential of the systems studied. Dissolution experiments carried out under anaerobic conditions have shown the important role of the uranium system on buffering the redox capacity of these systems. In the presence of carbonates in the system, the redox control has been given by the UO 2 (c)/U(VI) aqueous redox couple while in absence of carbonates in the system, the redox control has been governed by the UO 2 (c)/UO 2+x transition. In addition dissolution rates have been satisfactorily modelled by assuming an oxidative dissolution mechanism consisting in an initial oxidation of the surface of the uranium dioxide, binding of the HCO 3 or H+ at the U(VI) sites of the oxidised surface layer and detachment of these surface complexes. The redox controls in the experiments carried out under reducing conditions have been exerted by the different reducing agents added in the systems. Therefore, the addition of Fe 2+ lead to a redox control exerted by the Fe 2+ /Fe(OH) 3 (s) redox pair, while the addition of sulphide lead to a different redox control governed by the HS/SO 3 2- redox pair. (orig.)

Interactions between magnetite and humic substances: redox reactions and dissolution processes.

Science.gov (United States)

Sundman, Anneli; Byrne, James M; Bauer, Iris; Menguy, Nicolas; Kappler, Andreas

2017-10-19

Humic substances (HS) are redox-active compounds that are ubiquitous in the environment and can serve as electron shuttles during microbial Fe(III) reduction thus reducing a variety of Fe(III) minerals. However, not much is known about redox reactions between HS and the mixed-valent mineral magnetite (Fe 3 O 4 ) that can potentially lead to changes in Fe(II)/Fe(III) stoichiometry and even dissolve the magnetite. To address this knowledge gap, we incubated non-reduced (native) and reduced HS with four types of magnetite that varied in particle size and solid-phase Fe(II)/Fe(III) stoichiometry. We followed dissolved and solid-phase Fe(II) and Fe(III) concentrations over time to quantify redox reactions between HS and magnetite. Magnetite redox reactions and dissolution processes with HS varied depending on the initial magnetite and HS properties. The interaction between biogenic magnetite and reduced HS resulted in dissolution of the solid magnetite mineral, as well as an overall reduction of the magnetite. In contrast, a slight oxidation and no dissolution was observed when native and reduced HS interacted with 500 nm magnetite. This variability in the solubility and electron accepting and donating capacity of the different types of magnetite is likely an effect of differences in their reduction potential that is correlated to the magnetite Fe(II)/Fe(III) stoichiometry, particle size, and crystallinity. Our study suggests that redox-active HS play an important role for Fe redox speciation within minerals such as magnetite and thereby influence the reactivity of these Fe minerals and their role in biogeochemical Fe cycling. Furthermore, such processes are also likely to have an effect on the fate of other elements bound to the surface of Fe minerals.

Dissolution mechanism of UO2 at various parametric conditions

International Nuclear Information System (INIS)

Ollila, K.

1988-04-01

The aim of this experimental study is to investigate the solubility and dissolution mechanism of uranium dioxide under simulated disposal conditions of spent fuel. Unirradiated UO 2 is used as a surrogate for spent fuel. Two types of synthetic groundwaters were used in these experiments, on simulating the natural conditions deep in granitic bedrock (synthetic groundwater I) and the other simulating the effects of bentonite on groundwater (synthetic groundwater II). The effect of carbonate concentration was investigated by following dissolution in sodium bicarbonate solution as a function of bicarbonate concentration. Deionized wate was used as a reference water. All the experiments were carried out under both air-saturated, oxidizing and anoxic, reducing conditions. A separate test series under anoxic conditions was initiated in order to study the oxidation state of uranium. The experimental uranium solubilities are compared with the solubilities obtained from theoetical calculations by applying the geochemical code PHREEQ. The theoretical solubility values of uranium under oxidizing conditions calculated by PHREEQE are higher when compared to the corresponding experimental solubility values. The reason for the lower solubility values may be the mechanism of dissolution leading for example either to a situation where low dissolution rate is a limiting factor or to formation of some solid phase of uranium with lower solubility. Formation of a surface layer was observed on the pellet after dissolution in synthetic groundwater II. The theoretical solubility values under educing conditions calculated for uranium by PHREEQE appear to be in good agreement with the experimental solubility values

Microbially mediated barite dissolution in anoxic brines

International Nuclear Information System (INIS)

Ouyang, Bingjie; Akob, Denise M.; Dunlap, Darren; Renock, Devon

2017-01-01

Fluids injected into shale formations during hydraulic fracturing of black shale return with extraordinarily high total-dissolved-solids (TDS) and high concentrations of barium (Ba) and radium (Ra). Barite, BaSO_4, has been implicated as a possible source of Ba as well as a problematic mineral scale that forms on internal well surfaces, often in close association with radiobarite, (Ba,Ra)SO_4. The dissolution of barite by abiotic processes is well quantified. However, the identification of microbial communities in flowback and produced water necessitates the need to understand barite dissolution in the presence of bacteria. Therefore, we evaluated the rates and mechanisms of abiotic and microbially-mediated barite dissolution under anoxic and hypersaline conditions in the laboratory. Barite dissolution experiments were conducted with bacterial enrichment cultures established from produced water from Marcellus Shale wells located in northcentral Pennsylvania. These cultures were dominated by anaerobic halophilic bacteria from the genus Halanaerobium. Dissolved Ba was determined by ICP-OES and barite surfaces were investigated by SEM and AFM. Our results reveal that: 1) higher amounts of barium (up to ∼5 × ) are released from barite in the presence of Halanaerobium cultures compared to brine controls after 30 days of reaction, 2) etch pits that develop on the barite (001) surface in the presence of Halanaerobium exhibit a morphology that is distinct from those that form during control experiments without bacteria, 3) etch pits that develop in the presence of Halanaerobium exhibit a morphology that is similar to the morphology of etch pits formed in the presence of strong organic chelators, EDTA and DTPA, and 4) experiments using dialysis membranes to separate barite from bacteria suggest that direct contact between the two is not required in order to promote dissolution. These results suggest that Halanaerobium increase the rate of barite dissolution in anoxic

A cellular automata approach to chemical reactions : 1 reaction controlled systems

NARCIS (Netherlands)

Korte, de A.C.J.; Brouwers, H.J.H.

2013-01-01

A direct link between the chemical reaction controlled (shrinking core) model and cellular automata, to study the dissolution of particles, is derived in this paper. Previous research on first and second order reactions is based on the concentration of the reactant. The present paper describes the

Modelling of the UO{sub 2} dissolution mechanisms in synthetic groundwater. Experiments carried out under anaerobic and reducing conditions

Energy Technology Data Exchange (ETDEWEB)

Cera, E.; Grive, M.; Bruno, J. [EnvirosQuantiSci (Spain); Ollila, K. [VTT Chemical Technology, Espoo (Finland)

2000-07-01

The experimental data generated under anaerobic and reducing conditions within the EU R and D programme 1996-1998 entitled 'Source term for performance assessment of spent fuel as a waste form' and published as a POSIVA report (Ollila, 1999) have been modelled in the present work. The dissolution data available, mainly U in the aqueous phase as a function of time and redox potentials have been used to elucidate the redox pairs controlling the redox potential of the systems studied. Dissolution experiments carried out under anaerobic conditions have shown the important role of the uranium system on buffering the redox capacity of these systems. In the presence of carbonates in the system, the redox control has been given by the UO{sub 2}(c)/U(VI) aqueous redox couple while in absence of carbonates in the system, the redox control has been governed by the UO{sub 2}(c)/UO{sub 2+x} transition. In addition dissolution rates have been satisfactorily modelled by assuming an oxidative dissolution mechanism consisting in an initial oxidation of the surface of the uranium dioxide, binding of the HCO{sub 3} or H+ at the U(VI) sites of the oxidised surface layer and detachment of these surface complexes. The redox controls in the experiments carried out under reducing conditions have been exerted by the different reducing agents added in the systems. Therefore, the addition of Fe{sup 2+} lead to a redox control exerted by the Fe{sup 2+}/Fe(OH){sub 3}(s) redox pair, while the addition of sulphide lead to a different redox control governed by the HS/SO{sub 3}{sup 2-} redox pair. (orig.)

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

International Nuclear Information System (INIS)

Karraker, D.G.

1985-01-01

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

Direct Measurement of Surface Dissolution Rates in Potential Nuclear Waste Forms: The Example of Pyrochlore.

Science.gov (United States)

Fischer, Cornelius; Finkeldei, Sarah; Brandt, Felix; Bosbach, Dirk; Luttge, Andreas

2015-08-19

The long-term stability of ceramic materials that are considered as potential nuclear waste forms is governed by heterogeneous surface reactivity. Thus, instead of a mean rate, the identification of one or more dominant contributors to the overall dissolution rate is the key to predict the stability of waste forms quantitatively. Direct surface measurements by vertical scanning interferometry (VSI) and their analysis via material flux maps and resulting dissolution rate spectra provide data about dominant rate contributors and their variability over time. Using pyrochlore (Nd2Zr2O7) pellet dissolution under acidic conditions as an example, we demonstrate the identification and quantification of dissolution rate contributors, based on VSI data and rate spectrum analysis. Heterogeneous surface alteration of pyrochlore varies by a factor of about 5 and additional material loss by chemo-mechanical grain pull-out within the uppermost grain layer. We identified four different rate contributors that are responsible for the observed dissolution rate range of single grains. Our new concept offers the opportunity to increase our mechanistic understanding and to predict quantitatively the alteration of ceramic waste forms.

Control of Maillard Reactions in Foods: Strategies and Chemical Mechanisms.

Science.gov (United States)

Lund, Marianne N; Ray, Colin A

2017-06-14

Maillard reactions lead to changes in food color, organoleptic properties, protein functionality, and protein digestibility. Numerous different strategies for controlling Maillard reactions in foods have been attempted during the past decades. In this paper, recent advances in strategies for controlling the Maillard reaction and subsequent downstream reaction products in food systems are critically reviewed. The underlying mechanisms at play are presented, strengths and weaknesses of each strategy are discussed, and reasonable reaction mechanisms are proposed to reinforce the evaluations. The review includes strategies involving addition of functional ingredients, such as plant polyphenols and vitamins, as well as enzymes. The resulting trapping or modification of Maillard targets, reactive intermediates, and advanced glycation endproducts (AGEs) are presented with their potential unwanted side effects. Finally, recent advances in processing for control of Maillard reactions are discussed.

Insights into the Surface Transformation and Electrochemical Dissolution Process of Bornite in Bioleaching

Directory of Open Access Journals (Sweden)

Hongbo Zhao

2018-04-01

Full Text Available In this work, density functional theory (DFT calculations, X-ray photoelectron spectroscopy (XPS and electrochemistry analysis were combined to analyze the electrochemical dissolution process of bornite during bioleaching. DFT calculations showed that bornite was a conductor with metallic conductivity. The formula of bornite may be (Cu+5Fe3+(S2−4 and the surface reconstruction of (111-S surface was discussed. Electrochemistry and XPS analysis showed that bornite tended to be directly oxidized with high conductivity when the potential was higher than 0.3 V vs. Ag/AgCl. Elemental sulfur (S0, FeOOH and CuS were the main intermediate species on the bornite surface during the oxidation process. The production of S0 and FeOOH on bornite surface can be significantly accelerated with increased redox potential, but no insoluble sulfate (SO42− formed on bornite surface in 0.3–0.65 V vs. Ag/AgCl. The oxidative dissolution of bornite was significantly accelerated with increasing redox potential, which was one important reason why mixed culture was more effective than single strains of A. caldus and L. ferriphilum in bornite bioleaching. The insoluble SO42− was formed mainly through the chemical reactions in solution and then covered the bornite surface in bioleaching. Based on the obtained results, a model for interpreting the dissolution process of bornite in bioleaching was proposed.

Dissolution of basaltic glass in seawater: Mechanism and rate

International Nuclear Information System (INIS)

Crovisier, J.L.; Honnorez, J.; Eberhart, J.P.

1987-01-01

Basaltic glasses are considered as natural analogues for nuclear waste glasses. Thermodynamic computer codes used to evaluate long term behavior of both nuclear waste and basaltic glasses require the knowledge of the dissolution mechanism of the glass network. The paper presents the results of a series of experiments designed to study the structure and chemical composition of alteration layers formed on the surface of artificial tholeiitic glass altered in artificial seawater. Experiments were performed at 60 degree C, 1 bar and 350 bars in non-renewed conditions. A natural sample from Palagonia (Sicily) has been studied by electron microscopy and comparison between natural and experimental palagonitic layers is made. The behavior of dissolved silica during experiments, and both the structure and the chemical composition of the palagonitic layers, indicate that they form by precipitation of secondary minerals from solution after a total breakdown of the glassy network, i.e., congruent dissolution of the glass. Hence the dissolution equation necessary for thermodynamic modelling of basaltic glass dissolution in seawater at low temperature must be written as a simple stoichiometric process. These experiments indicate that the transformation of glass to palagonitic material is not isovolumetric. Hence it is preferable to use Fe or Ti as conservative elements for chemical budget calculations

Formalization of the kinetics for autocatalytic dissolutions. Focus on the dissolution of uranium dioxide in nitric medium

International Nuclear Information System (INIS)

Charlier, F.; Canion, D.; Gravinese, A.; Magnaldo, A.; Lalleman, S.; Borda, G.; Schaer, E.

2017-01-01

Uranium dioxide dissolution in nitric acid is a complex reaction. On the one hand, the dissolution produces nitrous oxides (NOX), which makes it a triphasic reaction. On the other hand, one of the products accelerates the kinetic rate; the reaction is hence called autocatalytic.The kinetics for these kinds of reactions need to be formalized in order to optimize and design innovative dissolution reactors. In this work, the kinetics rates have been measured by optical microscopy using a single particle approach. The advantages of this analytical technique are an easier management of species transport in solution and a precise following of the dissolution rate. The global rate is well described by a mechanism considering two steps: a non-catalyzed reaction, where the catalyst concentration has no influence on the dissolution rate, and a catalyzed reaction. The mass transfer rate of the catalyst was quantified in order to discriminate when the reaction was influenced by catalyst accumulated in the boundary layer or uncatalyzed. This first approximation described well the sigmoid dissolution curve profile. Moreover, experiments showed that solutions filled with catalyst proved to lose reactivity over time. Results pointed out that the higher the liquid-gas exchanges, the faster the kinetic rate decreases with time. Thus, it was demonstrated, for the first time, that there is a link between catalyst and nitrous oxides. The outcome of this study leads to new ways for improving the design of dissolvers. Gas-liquid exchanges are indeed a lever to impact dissolution rates. Temperature and catalyst concentration can be optimized to reduce residence times in dissolvers. (authors)

Controlled precipitation for enhanced dissolution rate of flurbiprofen: development of rapidly disintegrating tablets.

Science.gov (United States)

Essa, Ebtessam A; Elmarakby, Amira O; Donia, Ahmed M A; El Maghraby, Gamal M

2017-09-01

The aim of this work was to investigate the potential of controlled precipitation of flurbiprofen on solid surface, in the presence or absence of hydrophilic polymers, as a tool for enhanced dissolution rate of the drug. The work was extended to develop rapidly disintegrated tablets. This strategy provides simple technique for dissolution enhancement of slowly dissolving drugs with high scaling up potential. Aerosil was dispersed in ethanolic solution of flurbiprofen in the presence and absence of hydrophilic polymers. Acidified water was added as antisolvent to produce controlled precipitation. The resultant particles were centrifuged and dried at ambient temperature before monitoring the dissolution pattern. The particles were also subjected to FTIR spectroscopic, X-ray diffraction and thermal analyses. The FTIR spectroscopy excluded any interaction between flurbiprofen and excipients. The thermal analysis reflected possible change in the crystalline structure and or crystal size of the drug after controlled precipitation in the presence of hydrophilic polymers. This was further confirmed by X-ray diffraction. The modulation in the crystalline structure and size was associated with a significant enhancement in the dissolution rate of flurbiprofen. Optimum formulations were successfully formulated as rapidly disintegrating tablet with subsequent fast dissolution. Precipitation on a large solid surface area is a promising strategy for enhanced dissolution rate with the presence of hydrophilic polymers during precipitation process improving the efficiency.

Mathematical model to analyze the dissolution behavior of metastable crystals or amorphous drug accompanied with a solid-liquid interface reaction.

Science.gov (United States)

Hirai, Daiki; Iwao, Yasunori; Kimura, Shin-Ichiro; Noguchi, Shuji; Itai, Shigeru

2017-04-30

Metastable crystals and the amorphous state of poorly water-soluble drugs in solid dispersions (SDs), are subject to a solid-liquid interface reaction upon exposure to a solvent. The dissolution behavior during the solid-liquid interface reaction often shows that the concentration of drugs is supersaturated, with a high initial drug concentration compared with the solubility of stable crystals but finally approaching the latter solubility with time. However, a method for measuring the precipitation rate of stable crystals and/or the potential solubility of metastable crystals or amorphous drugs has not been established. In this study, a novel mathematical model that can represent the dissolution behavior of the solid-liquid interface reaction for metastable crystals or amorphous drug was developed and its validity was evaluated. The theory for this model was based on the Noyes-Whitney equation and assumes that the precipitation of stable crystals at the solid-liquid interface occurs through a first-order reaction. Moreover, two models were developed, one assuming that the surface area of the drug remains constant because of the presence of excess drug in the bulk and the other that the surface area changes in time-dependency because of agglomeration of the drug. SDs of Ibuprofen (IB)/polyvinylpyrrolidone (PVP) were prepared and their dissolution behaviors under non-sink conditions were fitted by the models to evaluate improvements in solubility. The model assuming time-dependent surface area showed good agreement with experimental values. Furthermore, by applying the model to the dissolution profile, parameters such as the precipitation rate and the potential solubility of the amorphous drug were successfully calculated. In addition, it was shown that the improvement in solubility with supersaturation was able to be evaluated quantitatively using this model. Therefore, this mathematical model would be a useful tool to quantitatively determine the supersaturation

Experimental hydrothermal dissolution of forsterite, enstatite, diopside, and labradorite

Energy Technology Data Exchange (ETDEWEB)

Ponader, H.B.

1989-01-01

Natural hydrothermal water/rock interactions such as those which occur during mineral dissolution and serpentinization were experimentally duplicated using a flow-through apparatus. Labradorite, forsterite, enstatite, diopside, and lherzolite powders were reached with flowing aqueous fluids ({approximately} 10 ml/day) at 300 C and 300 bars for up to 58 days in order to quantify mineral stabilities and dissolution rates, and to characterize dissolution textures and mechanisms. The principal methods for characterization of the solids included surface sensitive spectroscopies (SAM and SPS), SEM, and XRD; reacted fluids were analyzed for major element chemistry and pH. Chapters 1 and 2 investigate labradorite dissolution by deionized water. The labradorite powder dissolved extensively while boehmite and halloysite precipitated. The SAM results show that, in general, the reacted surfaces are enriched in Al and depleted in Si, Na, and Ca. Chapter 3 describes the experiments that reacted deionized water with diopside, enstatite, forsterite, and lherzolite, from which lizardite {plus minus} chrysotile {plus minus} Fe-oxides precipitated. The reacted diopside and enstatite surfaces appeared highly corroded; their crystal structures, in part, control the mechanisms by which they dissolve. The stabilities of the minerals decrease in the order: lherzolite > diopside > enstatite > forsterite. At near neutral pH, the degree to which total surface areas influence dissolution rates appears greater that the effect of mineral composition and interaction of the primary minerals within the lherzolite.

Comparative solubilisation of potassium carbonate, sodium bicarbonate and sodium carbonate in hot dimethylformamide: application of cylindrical particle surface-controlled dissolution theory.

Science.gov (United States)

Forryan, Claire L; Compton, Richard G; Klymenko, Oleksiy V; Brennan, Colin M; Taylor, Catherine L; Lennon, Martin

2006-02-07

A surface-controlled dissolution of cylindrical solid particles model is applied to potassium carbonate, sodium bicarbonate and sodium carbonate in dimethylformamide at elevated temperatures. Previously published data for the dissolution of potassium carbonate is interpreted assuming a cylindrical rather than a spherical shape of the particles, the former representing a closer approximation to the true shape of the particles as revealed by scanning electron microscopy. The dissolution kinetics of sodium carbonate and sodium bicarbonate in dimethylformamide at 100 degrees C were investigated via monitoring of the deprotonation of 2-cyanophenol with dissolved solid to form the 2-cyanophenolate anion that was detected with UV-visible spectroscopy. From fitting of experimental results to theory, the dissolution rate constant, k, for the dissolutions of potassium carbonate, sodium bicarbonate and sodium carbonate in dimethylformamide at 100 degrees C were found to have the values of (1.0 +/- 0.1) x 10(-7) mol cm(-2) s(-1), (5.5 +/- 0.3) x 10(-9) mol cm(-2) s(-1) and (9.7 +/- 0.8) x 10(-9) mol cm(-2) s(-1), respectively.

Effects of Chlorine Ions on the Dissolution Mechanism of Cu Thin Film in Phosphoric Acid Based Solution.

Science.gov (United States)

Seo, Bo-Hyun; Kim, Byoung O; Seo, Jong Hyun

2015-10-01

The dissolution mechanisms of Cu thin film were studied with a focus on the effect of chlorine ion concentrations in mixture solutions of phosphoric and nitric acid. The dissolution behaviors of Cu thin film were investigated by using potentio-dynamic curves and impedance spectroscopy with varying chlorine ion concentrations. The copper dissolution rate decreased and as a result of this change, CuCl, salt films formed on the Cu surface in the presence of chlorine ions in the mixture solution. Such behavior was interpreted as being competitive adsorption between chlorine and nitrate ions on the copper surface. The passive oxide film on the Cu surface was further investigated in detail using X-ray photoelectron spectroscopy in both the absence and presence of differing chlorine ion concentrations.

Investigation of dissolution kinetics of a Nigerian columbite in ...

African Journals Online (AJOL)

Investigation of dissolution kinetics of a Nigerian columbite in hydrofluoric acid using the shrinking core model. ... Experimental results indicate that the dissolution rate is chemical reaction controlled, with reaction order of 0.57. Dissolution of over 90 % of the columbite was achieved in 5 h, using 20 M HF at 90 oC with 100 ...

A multiphase interfacial model for the dissolution of spent nuclear fuel

Energy Technology Data Exchange (ETDEWEB)

Jerden, James L., E-mail: jerden@anl.gov [Argonne National Laboratory, 9700 South Cass Ave., Argonne, IL 60439 (United States); Frey, Kurt [University of Notre Dame, Notre Dame, IN 46556 (United States); Ebert, William [Argonne National Laboratory, 9700 South Cass Ave., Argonne, IL 60439 (United States)

2015-07-15

Highlights: • This model accounts for chemistry, temperature, radiolysis, U(VI) minerals, and hydrogen effect. • The hydrogen effect dominates processes determining spent fuel dissolution rate. • The hydrogen effect protects uranium oxide spent fuel from oxidative dissolution. - Abstract: The Fuel Matrix Dissolution Model (FMDM) is an electrochemical reaction/diffusion model for the dissolution of spent uranium oxide fuel. The model was developed to provide radionuclide source terms for use in performance assessment calculations for various types of geologic repositories. It is based on mixed potential theory and consists of a two-phase fuel surface made up of UO{sub 2} and a noble metal bearing fission product phase in contact with groundwater. The corrosion potential at the surface of the dissolving fuel is calculated by balancing cathodic and anodic reactions occurring at the solution interfaces with UO{sub 2} and NMP surfaces. Dissolved oxygen and hydrogen peroxide generated by radiolysis of the groundwater are the major oxidizing agents that promote fuel dissolution. Several reactions occurring on noble metal alloy surfaces are electrically coupled to the UO{sub 2} and can catalyze or inhibit oxidative dissolution of the fuel. The most important of these is the oxidation of hydrogen, which counteracts the effects of oxidants (primarily H{sub 2}O{sub 2} and O{sub 2}). Inclusion of this reaction greatly decreases the oxidation of U(IV) and slows fuel dissolution significantly. In addition to radiolytic hydrogen, large quantities of hydrogen can be produced by the anoxic corrosion of steel structures within and near the fuel waste package. The model accurately predicts key experimental trends seen in literature data, the most important being the dramatic depression of the fuel dissolution rate by the presence of dissolved hydrogen at even relatively low concentrations (e.g., less than 1 mM). This hydrogen effect counteracts oxidation reactions and can limit

A multiphase interfacial model for the dissolution of spent nuclear fuel

Science.gov (United States)

Jerden, James L.; Frey, Kurt; Ebert, William

2015-07-01

The Fuel Matrix Dissolution Model (FMDM) is an electrochemical reaction/diffusion model for the dissolution of spent uranium oxide fuel. The model was developed to provide radionuclide source terms for use in performance assessment calculations for various types of geologic repositories. It is based on mixed potential theory and consists of a two-phase fuel surface made up of UO2 and a noble metal bearing fission product phase in contact with groundwater. The corrosion potential at the surface of the dissolving fuel is calculated by balancing cathodic and anodic reactions occurring at the solution interfaces with UO2 and NMP surfaces. Dissolved oxygen and hydrogen peroxide generated by radiolysis of the groundwater are the major oxidizing agents that promote fuel dissolution. Several reactions occurring on noble metal alloy surfaces are electrically coupled to the UO2 and can catalyze or inhibit oxidative dissolution of the fuel. The most important of these is the oxidation of hydrogen, which counteracts the effects of oxidants (primarily H2O2 and O2). Inclusion of this reaction greatly decreases the oxidation of U(IV) and slows fuel dissolution significantly. In addition to radiolytic hydrogen, large quantities of hydrogen can be produced by the anoxic corrosion of steel structures within and near the fuel waste package. The model accurately predicts key experimental trends seen in literature data, the most important being the dramatic depression of the fuel dissolution rate by the presence of dissolved hydrogen at even relatively low concentrations (e.g., less than 1 mM). This hydrogen effect counteracts oxidation reactions and can limit fuel degradation to chemical dissolution, which results in radionuclide source term values that are four or five orders of magnitude lower than when oxidative dissolution processes are operative. This paper presents the scientific basis of the model, the approach for modeling used fuel in a disposal system, and preliminary

Reaction Mechanisms on Multiwell Potential Energy Surfaces in Combustion (and Atmospheric) Chemistry

International Nuclear Information System (INIS)

Osborn, David L.

2017-01-01

Chemical reactions occurring on a potential energy surface with multiple wells are ubiquitous in low temperature combustion and the oxidation of volatile organic compounds in earth’s atmosphere. The rich variety of structural isomerizations that compete with collisional stabilization make characterizing such complex-forming reactions challenging. This review describes recent experimental and theoretical advances that deliver increasingly complete views of their reaction mechanisms. New methods for creating reactive intermediates coupled with multiplexed measurements provide many experimental observables simultaneously. Automated methods to explore potential energy surfaces can uncover hidden reactive pathways, while master equation methods enable a holistic treatment of both sequential and well-skipping pathways. Our ability to probe and understand nonequilibrium effects and reaction sequences is increasing. These advances provide the fundamental science base for predictive models of combustion and the atmosphere that are crucial to address global challenges.

Reaction Mechanisms on Multiwell Potential Energy Surfaces in Combustion (and Atmospheric) Chemistry

Science.gov (United States)

Osborn, David L.

2017-05-01

Chemical reactions occurring on a potential energy surface with multiple wells are ubiquitous in low-temperature combustion and in the oxidation of volatile organic compounds in Earth's atmosphere. The rich variety of structural isomerizations that compete with collisional stabilization makes characterizing such complex-forming reactions challenging. This review describes recent experimental and theoretical advances that deliver increasingly complete views of their reaction mechanisms. New methods for creating reactive intermediates coupled with multiplexed measurements provide many experimental observables simultaneously. Automated methods to explore potential energy surfaces can uncover hidden reactive pathways, and master equation methods enable a holistic treatment of both sequential and well-skipping pathways. Our ability to probe and understand nonequilibrium effects and reaction sequences is increasing. These advances provide the fundamental science base for predictive models of combustion and the atmosphere that are crucial to address global challenges.

Understanding the mechanism of base development of HSQ

Energy Technology Data Exchange (ETDEWEB)

Kim, Jihoon; Chao, Weilun; Griedel, Brian; Liang, Xiaogan; Lewis, Mark; Hilken, Dawn; Olynick, Deirdre

2009-06-16

We study the dissolution mechanism of HSQ (hydrogen silsesquioxane) in base solutions with the addition of chloride salts to elucidate the development mechanism. Reaction mechanisms are proposed based on the dissolution mechanism of quartz. Development kinetics points to two dose-dependent development mechanisms. Considering ion sizes, both hydrated and non-hydrated, and ion exchange, we propose that a combination of a surface dominated reaction at higher doses and a matrix dominated reaction at lower doses accounts for the high development contrast with a NaOH base/NaCl salt mixture. The interplay between the hydrated and non-hydrated ion size leads to higher contrast developers, such as tetramethyl ammonium hydroxide (TMAH) with NaCl.

The anodic dissolution of SIMFUEL (UO2) in slightly alkaline sodium carbonate/bicarbonate solutions

International Nuclear Information System (INIS)

Keech, P.G.; Goldik, J.S.; Qin, Z.; Shoesmith, D.W.

2011-01-01

The corrosion of nuclear fuel under waste disposal conditions is likely to be influenced by the bicarbonate/carbonate content of the groundwater since it increases the solubility of the U VI corrosion product, [UO 2 ] 2+ . As one of the half reactions involved in the corrosion process, the anodic dissolution of SIMFUEL (UO 2 ) has been studied in bicarbonate/carbonate solutions (pH 9.8) using voltammetric and potentiostatic techniques and electrochemical impedance spectroscopy. The reaction proceeds by two consecutive one electron transfer reactions (U IV → U V → U VI ). At low potentials (≤250 mV (vs. SCE) the rate of the first electron transfer reaction is rate determining irrespective of the total carbonate concentration. At potentials >250 mV (vs. SCE) the formation of a U VI O 2 CO 3 surface layer begins to inhibit the dissolution rate and the current becomes independent of potential indicating rate control by the chemical dissolution of this layer.

Etching of semiconductor cubic crystals: Determination of the dissolution slowness surfaces

Science.gov (United States)

Tellier, C. R.

1990-03-01

Equations of the representative surface of dissolution slowness for cubic crystals are determined in the framework of a tensorial approach of the orientation-dependent etching process. The independent dissolution constants are deduced from symmetry considerations. Using previous data on the chemical etching of germanium and gallium arsenide crystals, some possible polar diagrams of the dissolution slowness are proposed. A numerical and graphical simulation method is used to obtain the derived dissolution shapes. The influence of extrema in the dissolution slowness on the successive dissolution shapes is also examined. A graphical construction of limiting shapes of etched crystals appears possible using the tensorial representation of the dissolution slowness.

Predicting dissolution patterns in variable aperture fractures: 1. Development and evaluation of an enhanced depth-averaged computational model

Energy Technology Data Exchange (ETDEWEB)

Detwiler, R L; Rajaram, H

2006-04-21

Water-rock interactions within variable-aperture fractures can lead to dissolution of fracture surfaces and local alteration of fracture apertures, potentially transforming the transport properties of the fracture over time. Because fractures often provide dominant pathways for subsurface flow and transport, developing models that effectively quantify the role of dissolution on changing transport properties over a range of scales is critical to understanding potential impacts of natural and anthropogenic processes. Dissolution of fracture surfaces is controlled by surface-reaction kinetics and transport of reactants and products to and from the fracture surfaces. We present development and evaluation of a depth-averaged model of fracture flow and reactive transport that explicitly calculates local dissolution-induced alterations in fracture apertures. The model incorporates an effective mass transfer relationship that implicitly represents the transition from reaction-limited dissolution to transport-limited dissolution. We evaluate the model through direct comparison to previously reported physical experiments in transparent analog fractures fabricated by mating an inert, transparent rough surface with a smooth single crystal of potassium dihydrogen phosphate (KDP), which allowed direct measurement of fracture aperture during dissolution experiments using well-established light transmission techniques [Detwiler, et al., 2003]. Comparison of experiments and simulations at different flow rates demonstrate the relative impact of the dimensionless Peclet and Damkohler numbers on fracture dissolution and the ability of the computational model to simulate dissolution. Despite some discrepancies in the small-scale details of dissolution patterns, the simulations predict the evolution of large-scale features quite well for the different experimental conditions. This suggests that our depth-averaged approach to simulating fracture dissolution provides a useful approach for

Calcite Dissolution Kinetics

Science.gov (United States)

Berelson, W.; Subhas, A.; Dong, S.; Naviaux, J.; Adkins, J. F.

2016-12-01

A geological buffer for high atmospheric CO2 concentrations is neutralization via reaction with CaCO3. We have been studying the dissolution kinetics of carbonate minerals using labeled 13C calcite and Picarro-based measurements of 13C enrichments in solution DIC. This methodology has greatly facilitated our investigation of dissolution kinetics as a function of water carbonate chemistry, temperature and pressure. One can adjust the saturation state Omega by changing the ion activity product (e.g. adjusting carbonate ion concentration), or by changing the solubility product (e.g. adjusting temperature or pressure). The canonical formulation of dissolution rate vs. omega has been refined (Subhas et al. 2015) and shows distinct non-linear behavior near equilibrium and rates in sea water of 1-3 e-6 g/cm2day at omega = 0.8. Carbonic anhydrase (CA), an enzyme that catalyzes the hydration of dissolved CO2 to carbonic acid, was shown (in concentrations 500x. This result points to the importance of carbonic acid in enhancing dissolution at low degrees of undersaturation. CA activity and abundance in nature must be considered regarding the role it plays in catalyzing dissolution. We also have been investigating the role of temperature on dissolution kinetics. An increase of 16C yields an order of magnitude increase in dissolution rate. Temperature (and P) also change Omega critical, the saturation state where dissolution rates change substantially. Increasing pressure (achieved in a pressure reaction chamber we built) also shifts Omega critical closer to equilibrium and small pressure increases have large impact on dissolution kinetics. Dissolution rates are enhanced by an order of magnitude for a change in pressure of 1500 psi relative to the dissolution rate achieved by water chemistry effects alone for an omega of 0.8. We've shown that the thermodynamic determination of saturation state does not adequately describe the kinetics of dissolution. The interplay of mineral

Bayesian inversion analysis of nonlinear dynamics in surface heterogeneous reactions.

Science.gov (United States)

Omori, Toshiaki; Kuwatani, Tatsu; Okamoto, Atsushi; Hukushima, Koji

2016-09-01

It is essential to extract nonlinear dynamics from time-series data as an inverse problem in natural sciences. We propose a Bayesian statistical framework for extracting nonlinear dynamics of surface heterogeneous reactions from sparse and noisy observable data. Surface heterogeneous reactions are chemical reactions with conjugation of multiple phases, and they have the intrinsic nonlinearity of their dynamics caused by the effect of surface-area between different phases. We adapt a belief propagation method and an expectation-maximization (EM) algorithm to partial observation problem, in order to simultaneously estimate the time course of hidden variables and the kinetic parameters underlying dynamics. The proposed belief propagation method is performed by using sequential Monte Carlo algorithm in order to estimate nonlinear dynamical system. Using our proposed method, we show that the rate constants of dissolution and precipitation reactions, which are typical examples of surface heterogeneous reactions, as well as the temporal changes of solid reactants and products, were successfully estimated only from the observable temporal changes in the concentration of the dissolved intermediate product.

Mechanisms Of The Dissolution Inhibition Effect And Their Application To Designing Novel Deep-UV Resists

Science.gov (United States)

Murata, Makoto; Koshiba, Mitsunobu; Harita, Yoshiyuki

1989-08-01

The dissolution inhibition effect and alkaline solubility were investigated for naphthoquinone diazides like 1,2-naphthoquinone diazide (NQD), its 5-sulfonylchloride (NQD-C) and 5-sulfonyloxybenzene (DAM), and for other compounds like sulfonylchlorides, sulfonyl esters, sulfones and a ketone which do not contain a naphthoquinone diazide moiety. As a result, it has turned out that the dissolution inhibition effect does not depend on the specific structure; namely, the naphthoquinone diazide moiety itself, but largely on the alkaline solubility of the compounds added to a novolak resin. An XPS study for the films consisting of a novolak resin and a dissolution inhibitor indicates a formation of an inhibitor-rich protective thin layer on the film surface after immersion of the film in an alkaline developer. In this paper is proposed a new third dissolution inhibition mechanism in addition to the previously reported chemical crosslinking and dipolar interaction; i.e., the alkaline insoluble protective layer inhibits the dissolution of novolak resin at the interface between the film and the developer. A new three-component type deep-UV resist has been also developed as an application of the new mechanism. The resist consists of a novolak resin, 5-diazo Meldrum's acid and a new dissolution inhibitors like phenyltosylate and p-phenylene ditosylate, which successfully improve the residual resist thickness.

A reaction limited in vivo dissolution model for the study of drug absorption: Towards a new paradigm for the biopharmaceutic classification of drugs.

Science.gov (United States)

Macheras, Panos; Iliadis, Athanassios; Melagraki, Georgia

2018-05-30

The aim of this work is to develop a gastrointestinal (GI) drug absorption model based on a reaction limited model of dissolution and consider its impact on the biopharmaceutic classification of drugs. Estimates for the fraction of dose absorbed as a function of dose, solubility, reaction/dissolution rate constant and the stoichiometry of drug-GI fluids reaction/dissolution were derived by numerical solution of the model equations. The undissolved drug dose and the reaction/dissolution rate constant drive the dissolution rate and determine the extent of absorption when high-constant drug permeability throughout the gastrointestinal tract is assumed. Dose is an important element of drug-GI fluids reaction/dissolution while solubility exclusively acts as an upper limit for drug concentrations in the lumen. The 3D plots of fraction of dose absorbed as a function of dose and reaction/dissolution rate constant for highly soluble and low soluble drugs for different "stoichiometries" (0.7, 1.0, 2.0) of the drug-reaction/dissolution with the GI fluids revealed that high extent of absorption was found assuming high drug- reaction/dissolution rate constant and high drug solubility. The model equations were used to simulate in vivo supersaturation and precipitation phenomena. The model developed provides the theoretical basis for the interpretation of the extent of drug's absorption on the basis of the parameters associated with the drug-GI fluids reaction/dissolution. A new paradigm emerges for the biopharmaceutic classification of drugs, namely, a model independent biopharmaceutic classification scheme of four drug categories based on either the fulfillment or not of the current dissolution criteria and the high or low % drug metabolism. Copyright © 2018. Published by Elsevier B.V.

Electrochemical studies of the effect of H2 on UO2 dissolution

International Nuclear Information System (INIS)

King, F.; Shoesmith, D.W.

2004-09-01

This report summarises evidence for the effect of H 2 on the oxidation and dissolution of UO 2 derived from electrochemical studies. In the presence of γ-radiation or with SIMFUEL electrodes containing ε-particles, the corrosion potential (E CORR ) of UO 2 is observed to be suppressed in the presence of H 2 by up to several hundred milli volts. This effect has been observed at room temperature with 5 MPa H 2 (in the case of γ-irradiated solutions) and at 60 deg C with a H 2 partial pressure of only 0.002-0.014 MPa H 2 with the SIMFUEL electrode. The suppression of E CORR in the presence of H 2 indicates that the degree of surface oxidation and the rate of dissolution of UO 2 is lower in the presence of H 2 .The precise mechanism of the effect of H 2 is unclear at this time. The mechanism appears to involve a surface heterogeneous process, rather than a homogeneous solution process. Under some circumstances the value of E CORR approaches the equilibrium potential for the H 2 /H + couple, suggesting galvanic coupling between sites on which this electrochemical process is catalysed and the rest of the UO 2 surface. It is also possible that H* radical species, either produced radiolytically from H 2 O or by dissociation of H 2 on ε-particles or surface-active UO 2+x sites, reduce oxidised U(V)/U(VI) surface states to U(IV). The effect of H 2 on reducing the degree of surface oxidation is only partially reversible, since surfaces reduced in H 2 atmospheres (re-)oxidise more slowly and to a lesser degree than surfaces not previously exposed to H 2 . Homogeneous reactions between dissolved H 2 and either oxidants or dissolved U(VI) cannot explain the observed effects.Regardless of the precise mechanism, the suppression of the degree of surface oxidation results in lower UO 2 dissolution rates in the presence of H 2 . Application of an electro-chemical dissolution model to the observed E CORR values suggests that the fractional dissolution rate of used fuel in the

In situ spectroscopic and solution analyses of the reductive dissolution of Mn02 by Fe(II)

Science.gov (United States)

Villinski, John E.; O'Day, Peggy A.; Corley, Timothy L.; Conklin, Martha H.

2001-01-01

The reductive dissolution of MnO2 by Fe(II) under conditions simulating acid mine drainage (pH 3, 100 mM SO42-) was investigated by utilizing a flow-through reaction cell and synchrotron X-ray absorption spectroscopy. This configuration allows collection of in situ, real-time X-ray absorption near-edge structure (XANES) spectra and bulk solution samples. Analysis of the solution chemistry suggests that the reaction mechanism changed (decreased reaction rate) as MnO2 was reduced and Fe(III) precipitated, primarily as ferrihydrite. Simultaneously, we observed an additional phase, with the local structure of jacobsite (MnFe2O4), in the Mn XANES spectra of reactants and products. The X-ray absorbance of this intermediate phase increased during the experiment, implying an increase in concentration. The presence of this phase, which probably formed as a surface coating, helps to explain the reduced rate of dissolution of manganese(IV) oxide. In natural environments affected by acid mine drainage, the formation of complex intermediate solid phases on mineral surfaces undergoing reductive dissolution may likewise influence the rate of release of metals to solution.

Dissolution process of atmospheric aerosol particles into cloud droplets; Processus de dissolution des aerosols atmospheriques au sein des gouttes d'eau nuageuses

Energy Technology Data Exchange (ETDEWEB)

Desboeufs, K

2001-01-15

Clouds affect both climate via the role they play in the Earth's radiation balance and tropospheric chemistry since they are efficient reaction media for chemical transformation of soluble species. Cloud droplets are formed in the atmosphere by condensation of water vapour onto aerosol particles, the cloud condensation nuclei (CCN). The water soluble fraction of these CCN governs the cloud micro-physics, which is the paramount factor playing on the radiative properties of clouds. Moreover, this soluble fraction is the source of species imply in the oxidation/reduction reactions in the aqueous phase. Thus, it is of particular importance to understand the process controlling the solubilization of aerosols in the cloud droplets. The main purpose of this work is to investigate experimentally and theoretically the dissolution of particles incorporated in the aqueous phase. From the studies conducted up to now, we have identify several factors playing on the dissolution reaction of aerosols. However, the quantification of the effects of these factors is difficult since the current means of study are not adapted to the complexity of cloud systems. First, this work consisted to perform a experimental system, compound by an open flow reactor, enabling to follow the kinetic of dissolution in conditions representative of cloud. This experimental device is used to a systematic characterisation of the known factors playing on the dissolution, i.e. pH, aerosol nature, aerosol weathering... and also for the identification and the quantification of the effects of other factors: ionic strength, acid nature, clouds processes. These experiments gave quantitative results, which are used to elaborate a simple model of aerosol dissolution in the aqueous phase. This model considers the main factors playing on the dissolution and results in a general mechanism of aerosol dissolution extrapolated to the cloud droplets. (author)

Peroxide formation and kinetics of sodium dissolution in alcohols

International Nuclear Information System (INIS)

Muralidaran, P.; Chandran, K.; Ganesan, V.; Periaswami, G.

1997-01-01

Suitable techniques for sodium removal and decontamination of sodium wetted components of Liquid Metal Fast Reactors (LMFRs) are necessary both for repair, reuse and decommissioning of such components. Among the methods followed for sodium removal, alcohol dissolution is usually employed for small components like bellow sealed valves, gripping tools to handle core components and sodium sampling devices (primary and secondary). One of the concerns in the alcohol dissolution method is the possible role of peroxide formation in the ethoxy group during storage and handling leading to explosion. This paper describes the study of peroxide formation in ethyl carbitol and butyl cellosolve as well as some of the results of dissolution kinetic studies carried out in our laboratory using different alcohols. The peroxide formation of ethyl carbitol and butyl cellosolve were studied by iodometric technique. It has been found that the peroxide formation is less in sodium containing alcohol than in pure one. Ethyl carbitol, butyl cellosolve and Jaysol-SS (mixture of ethyl alcohol, methyl alcohol, isopropyl alcohol and methyl isobutyl ketone) were used in dissolution kinetics studies. The effects due to area and orientation of the fresh sodium surface have also been investigated. The reaction rates were studied in the temperature range of 303-343 K. The rate of dissolution was estimated by measuring the sodium content of alcohol at periodic intervals. It is found that the reaction rate varies in the order of ethyl alcohol-water mixture > Jaysol-SS > butyl cellosolve > ethyl carbitol. While cleaning sodium using alcohol, the concentration of alcohol is held essentially constant throughout the process. The rate of reaction depends only on the amount of sodium and follows pseudo-first order kinetics. Increase in surface area has a marked impact on the dissolution rate at lower temperatures while at higher temperatures, the temperature factor overrides the effect due to surface area

Surface/subsurface observation and removal mechanisms of ground reaction bonded silicon carbide

Science.gov (United States)

Yao, Wang; Zhang, Yu-Min; Han, Jie-cai; Zhang, Yun-long; Zhang, Jian-han; Zhou, Yu-feng; Han, Yuan-yuan

2006-01-01

Reaction Bonded Silicon Carbide (RBSiC) has long been recognized as a promising material for optical applications because of its unique combination of favorable properties and low-cost fabrication. Grinding of silicon carbide is difficult because of its high hardness and brittleness. Grinding often induces surface and subsurface damage, residual stress and other types of damage, which have great influence on the ceramic components for optical application. In this paper, surface integrity, subsurface damage and material removal mechanisms of RBSiC ground using diamond grinding wheel on creep-feed surface grinding machine are investigated. The surface and subsurface are studied with scanning electron microscopy (SEM) and optical microscopy. The effects of grinding conditions on surface and subsurface damage are discussed. This research links the surface roughness, surface and subsurface cracks to grinding parameters and provides valuable insights into the material removal mechanism and the dependence of grind induced damage on grinding conditions.

Dissolution process of atmospheric aerosol particles into cloud droplets; Processus de dissolution des aerosols atmospheriques au sein des gouttes d'eau nuageuses

Energy Technology Data Exchange (ETDEWEB)

Desboeufs, K.

2001-01-15

Clouds affect both climate via the role they play in the Earth's radiation balance and tropospheric chemistry since they are efficient reaction media for chemical transformation of soluble species. Cloud droplets are formed in the atmosphere by condensation of water vapour onto aerosol particles, the cloud condensation nuclei (CCN). The water soluble fraction of these CCN governs the cloud micro-physics, which is the paramount factor playing on the radiative properties of clouds. Moreover, this soluble fraction is the source of species imply in the oxidation/reduction reactions in the aqueous phase. Thus, it is of particular importance to understand the process controlling the solubilization of aerosols in the cloud droplets. The main purpose of this work is to investigate experimentally and theoretically the dissolution of particles incorporated in the aqueous phase. From the studies conducted up to now, we have identify several factors playing on the dissolution reaction of aerosols. However, the quantification of the effects of these factors is difficult since the current means of study are not adapted to the complexity of cloud systems. First, this work consisted to perform a experimental system, compound by an open flow reactor, enabling to follow the kinetic of dissolution in conditions representative of cloud. This experimental device is used to a systematic characterisation of the known factors playing on the dissolution, i.e. pH, aerosol nature, aerosol weathering... and also for the identification and the quantification of the effects of other factors: ionic strength, acid nature, clouds processes. These experiments gave quantitative results, which are used to elaborate a simple model of aerosol dissolution in the aqueous phase. This model considers the main factors playing on the dissolution and results in a general mechanism of aerosol dissolution extrapolated to the cloud droplets. (author)

Electrochemical dissolution of surface alloys in acids: Thermodynamic trends from first-principles calculations

DEFF Research Database (Denmark)

Greeley, Jeffrey Philip; Nørskov, Jens Kehlet

2007-01-01

A simple procedure is introduced to use periodic Density Functional Theory calculations to estimate trends in the thermodynamics of surface alloy dissolution in acidic media. With this approach, the dissolution potentials for solute metal atoms embedded in the surface layer of various host metals...

The anodic dissolution of SIMFUEL (UO{sub 2}) in slightly alkaline sodium carbonate/bicarbonate solutions

Energy Technology Data Exchange (ETDEWEB)

Keech, P.G.; Goldik, J.S.; Qin, Z. [Department of Chemistry, University of Western Ontario, 1151 Richmond St, London ON, N6A 5B7 (Canada); Shoesmith, D.W., E-mail: dwshoesm@uwo.ca [Department of Chemistry, University of Western Ontario, 1151 Richmond St, London ON, N6A 5B7 (Canada)

2011-09-30

The corrosion of nuclear fuel under waste disposal conditions is likely to be influenced by the bicarbonate/carbonate content of the groundwater since it increases the solubility of the U{sup VI} corrosion product, [UO{sub 2}]{sup 2+}. As one of the half reactions involved in the corrosion process, the anodic dissolution of SIMFUEL (UO{sub 2}) has been studied in bicarbonate/carbonate solutions (pH 9.8) using voltammetric and potentiostatic techniques and electrochemical impedance spectroscopy. The reaction proceeds by two consecutive one electron transfer reactions (U{sup IV} {yields} U{sup V} {yields} U{sup VI}). At low potentials ({<=}250 mV (vs. SCE) the rate of the first electron transfer reaction is rate determining irrespective of the total carbonate concentration. At potentials >250 mV (vs. SCE) the formation of a U{sup VI}O{sub 2}CO{sub 3} surface layer begins to inhibit the dissolution rate and the current becomes independent of potential indicating rate control by the chemical dissolution of this layer.

Structure and reactivity of oxalate surface complexes on lepidocrocite derived from infrared spectroscopy, DFT-calculations, adsorption, dissolution and photochemical experiments

Science.gov (United States)

Borowski, Susan C.; Biswakarma, Jagannath; Kang, Kyounglim; Schenkeveld, Walter D. C.; Hering, Janet G.; Kubicki, James D.; Kraemer, Stephan M.; Hug, Stephan J.

2018-04-01

Oxalate, together with other ligands, plays an important role in the dissolution of iron(hdyr)oxides and the bio-availability of iron. The formation and properties of oxalate surface complexes on lepidocrocite were studied with a combination of infrared spectroscopy (IR), density functional theory (DFT) calculations, dissolution, and photochemical experiments. IR spectra measured as a function of time, concentration, and pH (50-200 μM oxalate, pH 3-7) showed that several surface complexes are formed at different rates and in different proportions. Measured spectra could be separated into three contributions described by Gaussian line shapes, with frequencies that agreed well with the theoretical frequencies of three different surface complexes: an outer-sphere complex (OS), an inner-sphere monodentate mononuclear complex (MM), and a bidentate mononuclear complex (BM) involving one O atom from each carboxylate group. At pH 6, OS was formed at the highest rate. The contribution of BM increased with decreasing pH. In dissolution experiments, lepidocrocite was dissolved at rates proportional to the surface concentration of BM, rather than to the total adsorbed concentration. Under UV-light (365 nm), BM was photolyzed at a higher rate than MM and OS. Although the comparison of measured spectra with calculated frequencies cannot exclude additional possible structures, the combined results allowed the assignment of three main structures with different reactivities consistent with experiments. The results illustrate the importance of the surface speciation of adsorbed ligands in dissolution and photochemical reactions.

Prediction of Tetraoxygen Reaction Mechanism with Sulfur Atom on the Singlet Potential Energy Surface

Directory of Open Access Journals (Sweden)

Ashraf Khademzadeh

2014-01-01

Full Text Available The mechanism of S+O4 (D2h reaction has been investigated at the B3LYP/6-311+G(3df and CCSD levels on the singlet potential energy surface. One stable complex has been found for the S+O4 (D2h reaction, IN1, on the singlet potential energy surface. For the title reaction, we obtained four kinds of products at the B3LYP level, which have enough thermodynamic stability. The results reveal that the product P3 is spontaneous and exothermic with −188.042 and −179.147 kcal/mol in Gibbs free energy and enthalpy of reaction, respectively. Because P1 adduct is produced after passing two low energy level transition states, kinetically, it is the most favorable adduct in the 1S+1O4 (D2h atmospheric reactions.

Morphological evolution of dissolving feldspar particles with anisotropic surface kinetics and implications for dissolution rate normalization and grain size dependence: A kinetic modeling study

Science.gov (United States)

Zhang, Li; Lüttge, Andreas

2009-11-01

With previous two-dimensional (2D) simulations based on surface-specific feldspar dissolution succeeding in relating the macroscopic feldspar kinetics to the molecular-scale surface reactions of Si and Al atoms ( Zhang and Lüttge, 2008, 2009), we extended our modeling effort to three-dimensional (3D) feldspar particle dissolution simulations. Bearing on the same theoretical basis, the 3D feldspar particle dissolution simulations have verified the anisotropic surface kinetics observed in the 2D surface-specific simulations. The combined effect of saturation state, pH, and temperature on the surface kinetics anisotropy has been subsequently evaluated, found offering diverse options for morphological evolution of dissolving feldspar nanoparticles with varying grain sizes and starting shapes. Among the three primary faces on the simulated feldspar surface, the (1 0 0) face has the biggest dissolution rate across an extensively wide saturation state range and thus acquires a higher percentage of the surface area upon dissolution. The slowest dissolution occurs to either (0 0 1) or (0 1 0) faces depending on the bond energies of Si-(O)-Si ( ΦSi-O-Si/ kT) and Al-(O)-Si ( ΦAl-O-Si/ kT). When the ratio of ΦSi-O-Si/ kT to ΦAl-O-Si/ kT changes from 6:3 to 7:5, the dissolution rates of three primary faces change from the trend of (1 0 0) > (0 1 0) > (0 0 1) to the trend of (1 0 0) > (0 0 1) > (0 1 0). The rate difference between faces becomes more distinct and accordingly edge rounding becomes more significant. Feldspar nanoparticles also experience an increasing degree of edge rounding from far-from-equilibrium to close-to-equilibrium. Furthermore, we assessed the connection between the continuous morphological modification and the variation in the bulk dissolution rate during the dissolution of a single feldspar particle. Different normalization treatments equivalent to the commonly used mass, cube assumption, sphere assumption, geometric surface area, and reactive

Mechanism of the rapid dissolution of Pu02 under oxidizing conditions and applications

International Nuclear Information System (INIS)

Madic, C.; Lecomte, M.; Bourges, J.; Koehly, G.

1991-01-01

Until the recent years, plutonium dioxide was known to be among the metallic oxides the most difficult to dissolve. From thermodynamic calculations it can be predicted that PuO 2 will dissolve under oxidizing conditions. This can be achieved using Ag(II) species possibly regenerated by electrochemical means. The mechanism of such a process has been elucidated using carbon paste electrochemistry and 18 O labelling. These studies demonstrate that the chemical reaction limiting the overall proces is located on the surface of the solid PuO 2 , and that the first step consists in the oxidation of the plutonium into Pu(V) species. Applications of the dissolution process of PuO 2 by electrogenerated Ag(II) were growing in the recent years in FRANCE. These applications developed often in collaboration with SGN and COGEMA, concern the treatment of: out of specifications PuO 2 , incineration ashes, wastes produced during MOX fuel fabrication, and during the dismantling of old nuclear facilities. A general overview of these different applications is given

Kinetics of carbonate dissolution in CO2-saturated aqueous system at reservoir conditions

Science.gov (United States)

Peng, Cheng; Crawshaw, John P.; Maitland, Geoffrey; Trusler, J. P. Martin

2014-05-01

results of the study indicate that the rotating disc technique can allow accurate measurement of the carbonate dissolution rate under surface-reaction-controlled conditions, and that the carbonate dissolution rate typically increases with the increase of temperature, CO2 partial pressure and solution acidity. The study shows that the dissolution of carbonate in CO2-free acidic solutions can be described as a first order heterogeneous reaction; however, this model is not sufficient to describe the reaction kinetics of carbonate minerals in the (CO2 + H2O) system, particularly for high reactivity carbonates, such as calcite, at reservoir conditions. For these systems, both pH and the activity of CO2(aq) influence the dissolution rate. Based on the experimental results, kinetic models have been developed and parameterised to describe the dissolution of different carbonate minerals. The results of this study should facilitate more rigorous modelling of mineral dissolution in deep saline aquifers used for CO2 storage. We gratefully acknowledge the funding of QCCSRC provided jointly by Qatar Petroleum, Shell, and the Qatar Science & Technology Park. Keywords: Carbon Dioxide, Carbonate, High Pressure, High Temperature, Reaction Kinetics.

Hydro-chemo-mechanical coupling in sediments: Localized mineral dissolution

KAUST Repository

Cha, Minsu; Santamarina, Carlos

2016-01-01

Mineral dissolution is inherently a chemo-hydro-mechanical coupled process. Field evidence and laboratory results show that dissolution may localize and form open conduits in cohesive media such as carbonate rocks. This study focuses on the evolution of localized dissolution in soils (i.e., frictional and non-cohesive granular materials) under effective confining stresses. Experimental results show the development of localized dissolution (“pipe”) when a carbonate-quartz sand is subjected to reactive fluid flow: only loosely packed quartz grains remain within pipes, and the number of pipes decreases away from the inlet port. Concurrent shear wave velocity measurements show a decrease in stiffness during dissolution due to stress and fabric changes, and more complex signal codas anticipate the development of internal heterogeneity. The discrete element method is used to simulate localized vertical dissolution features in granular materials, under constant vertical stress and zero lateral strain far-field boundaries. As porosity increases along dissolution pipes, vertical load is transferred to the surrounding soils and marked force chains develop. In terms of equivalent stress, principal stress rotation takes place within pipes and the sediment reaches the Coulomb failure condition inside pipes and in the surrounding medium. Dissolution pipes alter the geo-plumbing of the subsurface, enhance fluid transport but limit the long term performance of storage systems, alter the fluid pressure and effective stress fields, soften the sediment and may trigger shear failures.

Hydro-chemo-mechanical coupling in sediments: Localized mineral dissolution

KAUST Repository

Cha, Minsu

2016-06-11

Mineral dissolution is inherently a chemo-hydro-mechanical coupled process. Field evidence and laboratory results show that dissolution may localize and form open conduits in cohesive media such as carbonate rocks. This study focuses on the evolution of localized dissolution in soils (i.e., frictional and non-cohesive granular materials) under effective confining stresses. Experimental results show the development of localized dissolution (“pipe”) when a carbonate-quartz sand is subjected to reactive fluid flow: only loosely packed quartz grains remain within pipes, and the number of pipes decreases away from the inlet port. Concurrent shear wave velocity measurements show a decrease in stiffness during dissolution due to stress and fabric changes, and more complex signal codas anticipate the development of internal heterogeneity. The discrete element method is used to simulate localized vertical dissolution features in granular materials, under constant vertical stress and zero lateral strain far-field boundaries. As porosity increases along dissolution pipes, vertical load is transferred to the surrounding soils and marked force chains develop. In terms of equivalent stress, principal stress rotation takes place within pipes and the sediment reaches the Coulomb failure condition inside pipes and in the surrounding medium. Dissolution pipes alter the geo-plumbing of the subsurface, enhance fluid transport but limit the long term performance of storage systems, alter the fluid pressure and effective stress fields, soften the sediment and may trigger shear failures.

Montmorillonite dissolution kinetics: Experimental and reactive transport modeling interpretation

Science.gov (United States)

Cappelli, Chiara; Yokoyama, Shingo; Cama, Jordi; Huertas, F. Javier

2018-04-01

The dissolution kinetics of K-montmorillonite was studied at 25 °C, acidic pH (2-4) and 0.01 M ionic strength by means of well-mixed flow-through experiments. The variations of Si, Al and Mg over time resulted in high releases of Si and Mg and Al deficit, which yielded long periods of incongruent dissolution before reaching stoichiometric steady state. This behavior was caused by simultaneous dissolution of nanoparticles and cation exchange between the interlayer K and released Ca, Mg and Al and H. Since Si was only involved in the dissolution reaction, it was used to calculate steady-state dissolution rates, RSi, over a wide solution saturation state (ΔGr ranged from -5 to -40 kcal mol-1). The effects of pH and the degree of undersaturation (ΔGr) on the K-montmorillonite dissolution rate were determined using RSi. Employing dissolution rates farthest from equilibrium, the catalytic pH effect on the K-montmorillonite dissolution rate was expressed as Rdiss = k·aH0.56±0.05 whereas using all dissolution rates, the ΔGr effect was expressed as a non-linear f(ΔGr) function Rdiss = k · [1 - exp(-3.8 × 10-4 · (|ΔGr|/RT)2.13)] The functionality of this expression is similar to the equations reported for dissolution of Na-montmorillonite at pH 3 and 50 °C (Metz, 2001) and Na-K-Ca-montmorillonite at pH 9 and 80 °C (Cama et al., 2000; Marty et al., 2011), which lends support to the use of a single f(ΔGr) term to calculate the rate over the pH range 0-14. Thus, we propose a rate law that also accounts for the effect of pOH and temperature by using the pOH-rate dependence and the apparent activation energy proposed by Rozalén et al. (2008) and Amram and Ganor (2005), respectively, and normalizing the dissolution rate constant with the edge surface area of the K-montmorillonite. 1D reactive transport simulations of the experimental data were performed using the Crunchflow code (Steefel et al., 2015) to quantitatively interpret the evolution of the released cations

Jarosite dissolution rates in perchlorate brine

Science.gov (United States)

Legett, Carey; Pritchett, Brittany N.; Elwood Madden, Andrew S.; Phillips-Lander, Charity M.; Elwood Madden, Megan E.

2018-02-01

Perchlorate salts and the ferric sulfate mineral jarosite have been detected at multiple locations on Mars by both landed instruments and orbiting spectrometers. Many perchlorate brines have eutectic temperatures bearing rocks and sediments may have been altered by perchlorate brines. Here we measured jarosite dissolution rates in 2 M sodium perchlorate brine as well as dilute water at 298 K to determine the effects of perchlorate anions on jarosite dissolution rates and potential reaction products. We developed a simple method for determining aqueous iron concentrations in high salinity perchlorate solutions using ultraviolet-visible spectrophotometry that eliminates the risk of rapid oxidation reactions during analyses. Jarosite dissolution rates in 2 M perchlorate brine determined by iron release rate (2.87 × 10-12 ±0.85 × 10-12 mol m-2 s-1) were slightly slower than the jarosite dissolution rate measured in ultrapure (18.2 MΩ cm-1) water (5.06 × 10-12 mol m-2 s-1) using identical methods. No additional secondary phases were observed in XRD analyses of the reaction products. The observed decrease in dissolution rate may be due to lower activity of water (ɑH2O = 0.9) in the 2 M NaClO4 brine compared with ultrapure water (ɑH2O = 1). This suggests that the perchlorate anion does not facilitate iron release, unlike chloride anions which accelerated Fe release rates in previously reported jarosite and hematite dissolution experiments. Since dissolution rates are slower in perchlorate-rich solutions, jarosite is expected to persist longer in perchlorate brines than in dilute waters or chloride-rich brines. Therefore, if perchlorate brines dominate aqueous fluids on the surface of Mars, jarosite may remain preserved over extended periods of time, despite active aqueous processes.

Surface reaction of SnII on goethite (α-FeOOH): surface complexation, redox reaction, reductive dissolution, and phase transformation.

Science.gov (United States)

Dulnee, Siriwan; Scheinost, Andreas C

2014-08-19

To elucidate the potential risk of (126)Sn migration from nuclear waste repositories, we investigated the surface reactions of Sn(II) on goethite as a function of pH and Sn(II) loading under anoxic condition with O2 level redox state and surface structure were investigated by Sn K edge X-ray absorption spectroscopy (XAS), goethite phase transformations were investigated by high-resolution transmission electron microscopy and selected area electron diffraction. The results demonstrate the rapid and complete oxidation of Sn(II) by goethite and formation of Sn(IV) (1)E and (2)C surface complexes. The contribution of (2)C complexes increases with Sn loading. The Sn(II) oxidation leads to a quantitative release of Fe(II) from goethite at low pH, and to the precipitation of magnetite at higher pH. To predict Sn sorption, we applied surface complexation modeling using the charge distribution multisite complexation approach and the XAS-derived surface complexes. Log K values of 15.5 ± 1.4 for the (1)E complex and 19.2 ± 0.6 for the (2)C complex consistently predict Sn sorption across pH 2-12 and for two different Sn loadings and confirm the strong retention of Sn(II) even under anoxic conditions.

Anomalous dissolution of metals and chemical corrosion

Directory of Open Access Journals (Sweden)

DRAGUTIN M. DRAZIC

2005-03-01

Full Text Available An overview is given of the anomalous behavior of some metals, in particular Fe and Cr, in acidic aqueous solutions during anodic dissolution. The anomaly is recognizable by the fact that during anodic dissolutionmore material dissolves than would be expected from the Faraday law with the use of the expected valence of the formed ions. Mechanical disintegration, gas bubble blocking, hydrogen embrittlement, passive layer cracking and other possible reasons for such behavior have been discussed. It was shown, as suggested by Kolotyrkin and coworkers, that the reason can be, also, the chemical reaction in which H2O molecules with the metal form metal ions and gaseous H2 in a potential independent process. It occurs simultaneously with the electrochemical corrosion process, but the electrochemical process controls the corrosion potential. On the example of Cr in acid solution itwas shown that the reason for the anomalous behavior is dominantly chemical dissolution, which is considerably faster than the electrochemical corrosion, and that the increasing temperature favors chemical reaction, while the other possible reasons for the anomalous behavior are of negligible effect. This effect is much smaller in the case of Fe, but exists. The possible role of the chemical dissolution reacton and hydrogen evolution during pitting of steels and Al and stress corrosion cracking or corrosion fatigue are discussed.

Anodic dissolution and corrosion of alloy Cu30Ni in chloride solutions

International Nuclear Information System (INIS)

Zolotarev, E.I.

1989-01-01

The anodic and corrosion behavior of alloy Cu30Ni is studied in a solution of 3 N NaCl + 0.01 N HCl by a radiometric method using gamma isotopes of 58 Co (as a marker for Ni) and 64 Cu in combination with electrochemical measurements. It was established that under stationary conditions there was uniform dissolution of the alloy both during free corrosion and anodic polarization. The authors obtained partial anodic dissolution curves for the components of the alloy. It was shown that the dissolution kinetics differed from the mechanisms controlling dissolution of the corresponding pure metals. During corrosion of the alloy in an oxygen atmosphere a back precipitation of copper on the surface of the alloy was not observed. The characteristics observed in the corrosion-electrochemical behavior of the alloy in concentrated chloride solutions can be explained by the presence of Ni on the surface of the dissolving alloy

Evaporation rates and surface profiles on heterogeneous surfaces with mass transfer and surface reaction

Energy Technology Data Exchange (ETDEWEB)

Flytzani-Stephanopoulos, M; Schmidt, L D

1979-01-01

Simple models incorporating surface reaction and diffusion of volatile products through a boundary layer are developed to calculate effective rates of evaporation and local surface profiles on surfaces having active and inactive regions. The coupling between surface heterogeneities with respect to a particular reaction and external mass transfer may provide a mechanism for the surface rearrangement and metal loss encountered in several catalytic systems of practical interest. Calculated transport rates for the volatilization of platinum in oxidizing environments and the rearrangement of this metal during the ammonia oxidation reaction agree well with published experimental data.

Quantum Mechanics/Molecular Mechanics Study of the Sialyltransferase Reaction Mechanism.

Science.gov (United States)

Hamada, Yojiro; Kanematsu, Yusuke; Tachikawa, Masanori

2016-10-11

The sialyltransferase is an enzyme that transfers the sialic acid moiety from cytidine 5'-monophospho-N-acetyl-neuraminic acid (CMP-NeuAc) to the terminal position of glycans. To elucidate the catalytic mechanism of sialyltransferase, we explored the potential energy surface along the sialic acid transfer reaction coordinates by the hybrid quantum mechanics/molecular mechanics method on the basis of the crystal structure of sialyltransferase CstII. Our calculation demonstrated that CstII employed an S N 1-like reaction mechanism via the formation of a short-lived oxocarbenium ion intermediate. The computational barrier height was 19.5 kcal/mol, which reasonably corresponded with the experimental reaction rate. We also found that two tyrosine residues (Tyr156 and Tyr162) played a vital role in stabilizing the intermediate and the transition states by quantum mechanical interaction with CMP.

Chemical alteration of cement hydrates by dissolution

International Nuclear Information System (INIS)

Sugiyama, Daisuke; Fujita, Tomonari; Nakanishi, Kiyoshi

2000-01-01

Cementitious material is a potential waste packaging and backfilling material for the radioactive waste disposal, and is expected to provide both physical and chemical containment. In particular, the sorption of radionuclides onto cementitious material and the ability to provide a high pH condition are very important parameters when considering the release of radionuclides from radioactive wastes. For the long term, in the geological disposal environment, cement hydrates will be altered by, for example, dissolution, chemical reaction with ions in the groundwater, and hydrothermal reaction. Once the composition or crystallinity of the constituent minerals of a cement hydrate is changed by these processes, the pH of the repository buffered by cementitious material and its sorption ability might be affected. However, the mechanism of cement alteration is not yet fully understood. In this study, leaching experiments of some candidate cements for radioactive waste disposal were carried out. Hydrated Ordinary Portland Cement (OPC), Blast Furnace Slag blended cement (OPC/BFS) and Highly containing Flyash and Silicafume Cement (HFSC) samples were contacted with distilled water at liquid:solid ratios of 10:1, 100:1 and 1000:1 at room temperature for 200 days. In the case of OPC, Ca(OH) 2 dissolved at high liquid:solid ratios. The specific surface area of all cement samples increased by leaching process. This might be caused by further hydration and change of composition of constituent minerals. A model is presented which predicts the leaching of cement hydrates and the mineral composition in the hydrated cement solid phase, including the incongruent dissolution of CSH gel phases and congruent dissolution of Ca(OH) 2 , Ettringite and Hydrotalcite. Experimental results of dissolution of Ca-O-H and Ca-Si-O-H phases were well predicted by this model. (author)

Study of the dissolution of (U,P)O2 mixed oxides with a high plutonium content

International Nuclear Information System (INIS)

Fournier, S.

2001-01-01

Plutonium from nuclear reactors is partially integrated in the fuel cycle as Mixed OXide (U,Pu)O 2 (MOX). Their dissolution in nitric acid is needed to reprocess them in present reprocessing plants. The main difficulty of this study is that dissolution is a phenomenon depending on solution characteristics as well as the structural properties of the pellets, which depend themselves on the material fabrication process. After showing kinetic and thermodynamic dissolution data of mixed oxides in nitric media, an inventory of the parameters which affect the dissolution process has been made. A separable variable concept was introduced in order to describe the process by studying separately the role of chemical parameters of the solution and geometric parameters of the material. The first part of the study estimates the effect of nitric solution chemical parameters (concentrations, acidity, temperature) on the dissolution and underlines the role of the oxide surface protonation step. The second part of this work deals with the study of surface area evolution for materials with controlled plutonium rich heterogeneities. Experimental results show that the pellet surface undergoes erosion and is progressively weakened by the formation of fault lines in the bulk of the material followed by the dispersion of sub-millimeter fragments in the solution. An heterogeneous kinetic model derived from study of solid-gas interface systems has been applied to fuel pellets dissolution, allowing a mechanism to be proposed, based on surface dissolution of the oxide as well as fault creation in the volume. The dissolution kinetics are therefore dependant on the microstructure and mechanical strength and cohesion of the pellets. (author)

A copper-catalyzed bioleaching process for enhancement of cobalt dissolution from spent lithium-ion batteries

International Nuclear Information System (INIS)

Zeng, Guisheng; Deng, Xiaorong; Luo, Shenglian; Luo, Xubiao; Zou, Jianping

2012-01-01

Highlights: ► Catalytic ion was first applied to the bioleaching process of spent lithium-ion batteries. ► The bioleaching efficiency was great improved from 43.1% to 99.9% in the presence of copper ion. ► A new reaction model was proposed to explain the catalytic mechanism. - Abstract: A copper-catalyzed bioleaching process was developed to recycle cobalt from spent lithium-ion batteries (mainly LiCoO 2 ) in this paper. The influence of copper ions on bioleaching of LiCoO 2 by Acidithiobacillus ferrooxidans (A.f) was investigated. It was shown that almost all cobalt (99.9%) went into solution after being bioleached for 6 days in the presence of 0.75 g/L copper ions, while only 43.1% of cobalt dissolution was obtained after 10 days without copper ions. EDX, XRD and SEM analyses additionally confirmed that the cobalt dissolution from spent lithium-ion batteries could be improved in the presence of copper ions. The catalytic mechanism was investigated to explain the enhancement of cobalt dissolution by copper ions, in which LiCoO 2 underwent a cationic interchange reaction with copper ions to form CuCo 2 O 4 on the surface of the sample, which could be easily dissolved by Fe 3+ .

Accelerated dissolution testing for controlled release microspheres using the flow-through dissolution apparatus.

Science.gov (United States)

Collier, Jarrod W; Thakare, Mohan; Garner, Solomon T; Israel, Bridg'ette; Ahmed, Hisham; Granade, Saundra; Strong, Deborah L; Price, James C; Capomacchia, A C

2009-01-01

Theophylline controlled release capsules (THEO-24 CR) were used as a model system to evaluate accelerated dissolution tests for process and quality control and formulation development of controlled release formulations. Dissolution test acceleration was provided by increasing temperature, pH, flow rate, or adding surfactant. Electron microscope studies on the theophylline microspheres subsequent to each experiment showed that at pH values of 6.6 and 7.6 the microspheres remained intact, but at pH 8.6 they showed deterioration. As temperature was increased from 37-57 degrees C, no change in microsphere integrity was noted. Increased flow rate also showed no detrimental effect on integrity. The effect of increased temperature was determined to be the statistically significant variable.

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.

A literature survey on the dissolution mechanism of spent fuel under disposal conditions

International Nuclear Information System (INIS)

Ollila, Kaija

1989-06-01

In Finland spent nuclear fuel is planned to be disposed of at large depths in crystalline bedrock. As part of the YJT (Nuclear Waste Commission of Finnish Power Companies) - program, the solubiliy and dissolution mechanisms of unirradiated UO 2 are experimentally investigated as a function of groundwater conditions. This study is a literature survey on the leaching and dissolution studies carried out with spent fuel. It consists first a review on characterization studies of spent fuel. Then the solubilities and release mechanisms of the radionuclides from spent fuel in granitic or related groundwaters are discussed, including the dissolution of UO 2 matrix, and the leaching of fission products and actinides. Lastly approaches to modelling the dissolution of spent fuel are shortly discussed

Dissolution, agglomerate morphology, and stability limits of protein-coated silver nanoparticles.

Science.gov (United States)

Martin, Matthew N; Allen, Andrew J; MacCuspie, Robert I; Hackley, Vincent A

2014-09-30

Little is understood regarding the impact that molecular coatings have on nanoparticle dissolution kinetics and agglomerate formation in a dilute nanoparticle dispersion. Dissolution and agglomeration processes compete in removing isolated nanoparticles from the dispersion, making quantitative time-dependent measurements of the mechanisms of nanoparticle loss particularly challenging. In this article, we present in situ ultra-small-angle X-ray scattering (USAXS) results, simultaneously quantifying dissolution, agglomeration, and stability limits of silver nanoparticles (AgNPs) coated with bovine serum albumin (BSA) protein. When the BSA corona is disrupted, we find that the loss of silver from the nanoparticle core is well matched by a second-order kinetic rate reaction, arising from the oxidative dissolution of silver. Dissolution and agglomeration are quantified, and morphological transitions throughout the process are qualified. By probing the BSA-AgNP suspension around its stability limits, we provide insight into the destabilization mechanism by which individual particles rapidly dissolve as a whole rather than undergo slow dissolution from the aqueous interface inward, once the BSA layer is breached. Because USAXS rapidly measures over the entire nanometer to micrometer size range during the dissolution process, many insights are also gained into the stabilization of NPs by protein and its ability to protect the labile metal core from the solution environment by prohibiting the diffusion of reactive species. This approach can be extended to a wide variety of coating molecules and reactive metal nanoparticle systems to carefully survey their stability limits, revealing the likely mechanisms of coating breakdown and ensuing reactions.

Uranothorite solid solutions: From synthesis to dissolution

International Nuclear Information System (INIS)

Costin, Dan-Tiberiu

2012-01-01

USiO 4 coffinite appears as one of the potential phases formed in the back-end of the alteration of spent fuel, in reducing storage conditions. A study aiming to assess the thermodynamic data associated with coffinite through an approach based on the preparation of Th 1-x U x SiO 4 uranothorite solid solutions was then developed during this work. First, the preparation of uranothorite samples was successfully undertaken in hydrothermal conditions. However, the poly-phased samples systematically formed for x ≥ 0,2 underlined the kinetic hindering linked with the preparation of uranium-enriched samples, including coffinite end-member. Nevertheless, the characterization of the various samples led to confirm the formation of an ideal solid solution and allowed the constitution of a spectroscopic database. The purification of the samples was then performed by the means of different protocols based on physical (dispersion-centrifugation) or chemical (selective dissolution of secondary phases) methods. This latter led to a complete of the impurities (Th 1-y U y O 2 mixed oxide and amorphous silica) through successive washing steps in acid then basic media. Finally, dissolution experiments were undertaken on uranothorite samples (0 ≤ xexp. ≤ 0,5) and allowed pointing out the influence of composition, pH and temperature on the normalized dissolution rate of the compounds. Also, the associated thermodynamic data, such as activation energy, indicate that the reaction is controlled by surface reactions. Once the equilibrium is reached, the analogous solubility constants were determined for each composition studied, then allowing the extrapolation to coffinite value. It was then finally possible to conclude on the inversion of coffinitisation reaction with temperature. (author) [fr

Effect of alteration phase formation on the glass dissolution rate

International Nuclear Information System (INIS)

Ebert, W.L.

1997-01-01

The dissolution rates of many glasses have been observed to increase upon the formation of certain alteration phases. While simulations have predicted the accelerating effect of formation of certain phases, the phases predicted to form in computer simulations are usually different than those observed to form in experiments. This is because kinetically favored phases form first in experiments, while simulations predict the thermodynamically favored phases. Static dissolution tests with crushed glass have been used to measure the glass dissolution rate after alteration phases form. Because glass dissolution rates are calculated on a per area basis, an important effect in tests conducted with crushed glass is the decrease in the surface area of glass that is available for reaction as the glass dissolves. This loss of surface area must be taken into account when calculating the dissolution rate. The phases that form and their effect on the dissolution rate are probably related to the glass composition. The impact of phase formation on the glass dissolution rate also varies according to the solubility products of the alteration phases and how the orthocilicic acid activity is affected. Insight into the relationship between the glass dissolution rate, solution chemistry and alteration phase formation is provided by the results of accelerated dissolution tests

Effect of alteration phase formation on the glass dissolution rate

Energy Technology Data Exchange (ETDEWEB)

Ebert, W L [Argonne National Laboratory, Chemical Technology Div. (United States)

1997-07-01

The dissolution rates of many glasses have been observed to increase upon the formation of certain alteration phases. While simulations have predicted the accelerating effect of formation of certain phases, the phases predicted to form in computer simulations are usually different than those observed to form in experiments. This is because kinetically favored phases form first in experiments, while simulations predict the thermodynamically favored phases. Static dissolution tests with crushed glass have been used to measure the glass dissolution rate after alteration phases form. Because glass dissolution rates are calculated on a per area basis, an important effect in tests conducted with crushed glass is the decrease in the surface area of glass that is available for reaction as the glass dissolves. This loss of surface area must be taken into account when calculating the dissolution rate. The phases that form and their effect on the dissolution rate are probably related to the glass composition. The impact of phase formation on the glass dissolution rate also varies according to the solubility products of the alteration phases and how the orthocilicic acid activity is affected. Insight into the relationship between the glass dissolution rate, solution chemistry and alteration phase formation is provided by the results of accelerated dissolution tests.

Theoretical Study of Sodium-Water Surface Reaction Mechanism

Science.gov (United States)

Kikuchi, Shin; Kurihara, Akikazu; Ohshima, Hiroyuki; Hashimoto, Kenro

Computational study of the sodium-water reaction at the gas (water) - liquid (sodium) interface has been carried out using the ab initio (first-principle) method. A possible reaction channel has been identified for the stepwise OH bond dissociations of a single water molecule. The energetics including the binding energy of a water molecule on the sodium surface, the activation energies of the bond cleavages, and the reaction energies, have been evaluated, and the rate constants of the first and second OH bond-breakings have been compared. It was found that the estimated rate constant of the former was much larger than the latter. The results are the basis for constructing the chemical reaction model used in a multi-dimensional sodium-water reaction code, SERAPHIM, being developed by Japan Atomic Energy Agency (JAEA) toward the safety assessment of the steam generator (SG) in a sodium-cooled fast reactor (SFR).

Theoretical study of sodium-water surface reaction mechanism

International Nuclear Information System (INIS)

Kikuchi, Shin; Kurihara, Akikazu; Ohshima, Hiroyuki; Hashimoto, Kenro

2012-01-01

Computational study of the sodium-water reaction at the gas (water) - liquid (sodium) interface has been carried out using the ab initio (first-principle) method. A possible reaction channel has been identified for the stepwise OH bond dissociations of a single water molecule. The energetics including the binding energy of a water molecule on the sodium surface, the activation energies of the bond cleavages, and the reaction energies, have been evaluated, and the rate constants of the first and second OH bond-breakings have been compared. It was found that the estimated rate constant of the former was much larger than the latter. The results are the basis for constructing the chemical reaction model used in a multi-dimensional sodium-water reaction code, SERAPHIM, being developed by Japan Atomic Energy Agency (JAEA) toward the safety assessment of the steam generator (SG) in a sodium-cooled fast reactor (SFR). (author)

SurfKin: an ab initio kinetic code for modeling surface reactions.

Science.gov (United States)

Le, Thong Nguyen-Minh; Liu, Bin; Huynh, Lam K

2014-10-05

In this article, we describe a C/C++ program called SurfKin (Surface Kinetics) to construct microkinetic mechanisms for modeling gas-surface reactions. Thermodynamic properties of reaction species are estimated based on density functional theory calculations and statistical mechanics. Rate constants for elementary steps (including adsorption, desorption, and chemical reactions on surfaces) are calculated using the classical collision theory and transition state theory. Methane decomposition and water-gas shift reaction on Ni(111) surface were chosen as test cases to validate the code implementations. The good agreement with literature data suggests this is a powerful tool to facilitate the analysis of complex reactions on surfaces, and thus it helps to effectively construct detailed microkinetic mechanisms for such surface reactions. SurfKin also opens a possibility for designing nanoscale model catalysts. Copyright © 2014 Wiley Periodicals, Inc.

Oxidation and dissolution of UO{sub 2} in bicarbonate media: Implications for the spent nuclear fuel oxidative dissolution mechanism

Energy Technology Data Exchange (ETDEWEB)

Gimenez, J. [Department of Chemical Engineering, Universitat Politecnica de Catalunya, Diagonal 647, 08028 Barcelona (Spain)]. E-mail: francisco.javier.gimenez@upc.edu; Clarens, F. [Department of Chemical Engineering, Universitat Politecnica de Catalunya, Diagonal 647, 08028 Barcelona (Spain); Casas, I. [Department of Chemical Engineering, Universitat Politecnica de Catalunya, Diagonal 647, 08028 Barcelona (Spain); Rovira, M. [CTM Centre Tecnologic, Avda. Bases de Manresa 1. 08240 Manresa (Spain); Pablo, J. de [Department of Chemical Engineering, Universitat Politecnica de Catalunya, Diagonal 647, 08028 Barcelona (Spain); Bruno, J. [Enresa-Enviros Environmental Science and Waste Management Chair, UPC, Jordi Girona 1-3 B2, 08034 Barcelona (Spain)

2005-10-15

The objective of this work is to study the UO{sub 2} oxidation by O{sub 2} and dissolution in bicarbonate media and to extrapolate the results obtained to improve the knowledge of the oxidative dissolution of spent nuclear fuel. The results obtained show that in the studied range the oxygen consumption rate is independent on the bicarbonate concentration while the UO{sub 2} dissolution rate does depend on. Besides, at 10{sup -4} mol dm{sup -3} bicarbonate concentration, the oxygen consumption rate is almost two orders of magnitude higher than the UO{sub 2} dissolution rate. These results suggest that at low bicarbonate concentration (<10{sup -2} mol dm{sup -3}) the alteration of the spent nuclear fuel cannot be directly derived from the measured uranium concentrations in solution. On the other hand, the study at low bicarbonate concentrations of the evolution of the UO{sub 2} surface at nanometric scale by means of the SFM technique shows that the difference between oxidation and dissolution rates is not due to the precipitation of a secondary solid phase on UO{sub 2}.

A full understanding of oxygen reduction reaction mechanism on Au(1 1 1) surface

Science.gov (United States)

Yang, Yang; Dai, Changqing; Fisher, Adrian; Shen, Yanchun; Cheng, Daojian

2017-09-01

Oxygen reduction and hydrogen peroxide reduction are technologically important reactions in energy-conversion devices. In this work, a full understanding of oxygen reduction reaction (ORR) mechanism on Au(1 1 1) surface is investigated by density functional theory (DFT) calculations, including the reaction mechanisms of O2 dissociation, OOH dissociation, and H2O2 dissociation. Among these ORR mechanisms on Au(1 1 1), the activation energy of \\text{O}2* hydrogenation reaction is much lower than that of \\text{O}2* dissociation, indicating that \\text{O}2* hydrogenation reaction is more appropriate at the first step than \\text{O}2* dissociation. In the following, H2O2 can be formed with the lower activation energy compared with the OOH dissociation reaction, and finally H2O2 could be generated as a detectable product due to the high activation energy of H2O2 dissociation reaction. Furthermore, the potential dependent free energy study suggests that the H2O2 formation is thermodynamically favorable up to 0.4 V on Au(1 1 1), reducing the overpotential for 2e - ORR process. And the elementary step of first H2O formation becomes non-spontaneous at 0.4 V, indicating the difficulty of 4e - reduction pathway. Our DFT calculations show that H2O2 can be generated on Au(1 1 1) and the first electron transfer is the rate determining step. Our results show that gold surface could be used as a good catalyst for small-scale manufacture and on-site production of H2O2.

Carbonate mineral dissolution kinetics in high pressure experiments

Science.gov (United States)

Dethlefsen, F.; Dörr, C.; Schäfer, D.; Ebert, M.

2012-04-01

The potential CO2 reservoirs in the North German Basin are overlain by a series of Mesozoic barrier rocks and aquifers and finally mostly by Tertiary and Quaternary close-to-surface aquifers. The unexpected rise of stored CO2 from its reservoir into close-to-surface aquifer systems, perhaps through a broken well casing, may pose a threat to groundwater quality because of the acidifying effect of CO2 dissolution in water. The consequences may be further worsening of the groundwater quality due to the mobilization of heavy metals. Buffer mechanisms counteracting the acidification are for instance the dissolution of carbonates. Carbonate dissolution kinetics is comparably fast and carbonates can be abundant in close-to-surface aquifers. The disadvantages of batch experiments compared to column experiments in order to determine rate constants are well known and have for instance been described by v. GRINSVEN and RIEMSDIJK (1992). Therefore, we have designed, developed, tested, and used a high-pressure laboratory column system to simulate aquifer conditions in a flow through setup within the CO2-MoPa project. The calcite dissolution kinetics was determined for CO2-pressures of 6, 10, and 50 bars. The results were evaluated by using the PHREEQC code with a 1-D reactive transport model, applying a LASAGA (1984) -type kinetic dissolution equation (PALANDRI and KHARAKA, 2004; eq. 7). While PALANDRI and KHARAKA (2004) gave calcite dissolution rate constants originating from batch experiments of log kacid = -0.3 and log kneutral = -5.81, the data of the column experiment were best fitted using log kacid = -2.3 and log kneutral = -7.81, so that the rate constants fitted using the lab experiment applying 50 bars pCO2 were approximately 100 times lower than according to the literature data. Rate constants of experiments performed at less CO2 pressure (pCO2 = 6 bars: log kacid = -1.78; log kneutral = -7.29) were only 30 times lower than literature data. These discrepancies in the

Morphing of the Dissipative Reaction Mechanism

International Nuclear Information System (INIS)

Schroeder, W.U.; Toke, J.; Gawlikowicz, W.; Houck, M.A.; Lu, J.; Pienkowski, L.

2003-01-01

Important trends in the evolution of heavy-ion reaction mechanisms with bombarding energy and impact parameter are reviewed. Essential features of dissipative reactions appear preserved at E/A = 50-62 MeV, such as dissipative orbiting and multi-nucleon exchange. The relaxation of the A/Z asymmetry with impact parameter is slow. Non-equilibrium emission of light particles and clusters is an important process accompanying the evolution of the mechanism. Evidence is presented for a new mechanism of statistical cluster emission from hot, metastable primary reaction products, driven by surface entropy. These results suggest a plausible reinterpretation of multi-fragmentation. (authors)

Morphing of the Dissipative Reaction Mechanism

Energy Technology Data Exchange (ETDEWEB)

Schroeder, W.U.; Toke, J.; Gawlikowicz, W.; Houck, M.A.; Lu, J.; Pienkowski, L. [Rochester Univ., Dept. of Chemistry, Rochester, NY (United States)

2003-07-01

Important trends in the evolution of heavy-ion reaction mechanisms with bombarding energy and impact parameter are reviewed. Essential features of dissipative reactions appear preserved at E/A = 50-62 MeV, such as dissipative orbiting and multi-nucleon exchange. The relaxation of the A/Z asymmetry with impact parameter is slow. Non-equilibrium emission of light particles and clusters is an important process accompanying the evolution of the mechanism. Evidence is presented for a new mechanism of statistical cluster emission from hot, metastable primary reaction products, driven by surface entropy. These results suggest a plausible reinterpretation of multi-fragmentation. (authors)

A surface physicochemical rationale for calculus formation in the oral cavity

NARCIS (Netherlands)

Busscher, HJ; White, DJ; Kamminga-Rasker, HJ; van der Mei, HC

2004-01-01

Surface free energies of dental hard tissues, including salivary conditioning films on enamel, play a crucial role in mineralization, dissolution and adhesion processes at the tooth surface. These mineralization reactions at oral surfaces control the development and progression of various diseases.

A new method for alkaline dissolution of uranium metal foil

International Nuclear Information System (INIS)

Mondino, A.V.; Wilkinson, M.V.; Manzini, A.C.

2001-01-01

In order to develop a production process of 99 Mo by fission of low-enriched uranium, the first purification step, which consists of dissolution of a uranium metal foil target, was studied. It was found that alkaline NaClO gave good results, reaching the dissolution of up to 300 μm of uranium foil. The different conditions for the dissolution were studied and the optimum ones were found. The influence of NaClO and NaOH concentration, temperature, dissolving solution volume per unit of surface and dissolution time were investigated. During this step, a gas identified as H 2 , was generated, and a precipitate characterized as Na 2 U 2 O 7 was observed. A stoichiometric reaction for this uranium dissolution is proposed. (author)

An ecological mechanism to create regular patterns of surface dissolution in a low-relief carbonate landscape

Science.gov (United States)

Cohen, M. J.; Martin, J. B.; Mclaughlin, D. L.; Osborne, T.; Murray, A.; Watts, A. C.; Watts, D.; Heffernan, J. B.

2012-12-01

Development of karst landscapes is controlled by focused delivery of water undersaturated with respect to the soluble rock minerals. As that water comes to equilibrium with the rock, secondary porosity is incrementally reinforced creating a positive feedback that acts to augment the drainage network and subsequent water delivery. In most self-organizing systems, spatial positive feedbacks create features (in landscapes: patches; in karst aquifers: conduits) whose size-frequency relationship follows a power function, indicating a higher probability of large features than would occur with a random or Gaussian genesis process. Power functions describe several aspects of secondary porosity in the Upper Floridan Aquifer in north Florida. In contrast, a different pattern arises in the karst landscape in southwest Florida (Big Cypress National Preserve; BICY), where low-relief and a shallow aquiclude govern regional hydrology. There, the landscape pattern is highly regular (Fig. 1), with circular cypress-dominated wetlands occupying depressions that are hydrologically isolated and distributed evenly in a matrix of pine uplands. Regular landscape patterning results from spatially coupled feedbacks, one positive operating locally that expands patches coupled to another negative that operates at distance, eventually inhibiting patch expansion. The positive feedback in BICY is thought to derive from the presence of surface depressions, which sustain prolonged inundation in this low-relief setting, and facilitate wetland development that greatly augments dissolution potential of infiltrating water in response to ecosystem metabolic processes. In short, wetlands "drill" into the carbonate leading to both vertical and lateral basin expansion. Wetland expansion occurs at the expense of surrounding upland area, which is the local catchment that subsidizes water availability. A distal inhibitory feedback on basin expansion thus occurs as the water necessary to sustain prolonged

Magnesite dissolution and precipitation rates at hydrothermal conditions

International Nuclear Information System (INIS)

Saldi, Giuseppe

2009-01-01

Magnesite (MgCO 3 ) is the stable anhydrous member of a series of Mg-carbonates with different degrees of hydration. Despite its relative scarcity in the natural environments, it constitutes an important mineral phase for the permanent sequestration of CO 2 as carbonate minerals. Experimental determination of magnesite precipitation and dissolution rates at conditions representative of the storage sites is therefore fundamental for the assessment of magnesite sequestration potential in basaltic and ultramafic rocks and the optimization of the techniques of CO 2 storage. Magnesite precipitation rates have been measured using mixed-flow and batch reactors as a function of temperature (100 ≤ T ≤ 200 deg. C), solution composition and CO 2 partial pressure (up to 30 bar). Rates were found to be independent of aqueous solution ionic strength at 0.1 M 3 2- activity at pH > 8. All rates obtained from mixed flow reactor experiments were found to be consistent with the model of Pokrovsky et al. (1999) where magnesite precipitation rates are proportional to the concentration of the >MgOH 2 + surface species. The study of magnesite crystallization using hydrothermal atomic force microscopy (HAFM) demonstrated the consistency of the rates derived from microscopic measurements with those obtained from bulk experiments and showed that these rates are also consistent with a spiral growth mechanism. According to AFM observations this mechanism controls magnesite growth over a wide range of temperatures and saturation states (15≤ Ω ≤200 for 80 ≤T 2 to accelerate the rate of the overall carbonation process, avoiding the inhibiting effect of carbonate ions on magnesite precipitation and increasing the rates of Mg-silicate dissolution via acidification of reacting solutions. Determination of magnesite dissolution rates by mixed flow reactor at 150 and 200 deg. C and at neutral to alkaline conditions allowed us to improve and extend to high temperatures the surface

Thoria/thoria-urania dissolution studies for reprocessing application

International Nuclear Information System (INIS)

Srinivas, C.; Yalmali, Vrunda; Pente, A.S.; Wattal, P.K.; Misra, S.D.

2012-06-01

Thoria dissolution is normally conducted in 13M nitric acid in the presence of 0.03M sodium fluoride or HF as catalyst and 0.1M aluminium nitrate for mitigation of fluoride related corrosion of SS 304L dissolver vessel. Addition of aluminium nitrate in such high concentrations has undesirable consequences in the downstream high level radioactive liquid waste vitrification process at 900-1000 degC. Besides, because of the highly corrosive nature of fluoride ion, lowering its concentration in the dissolution reaction is advantageous in reducing the corrosion of dissolver and other downstream equipments. The present work was done with twin objectives of avoiding aluminium nitrate addition and lowering the fluoride ion concentration during dissolution reaction. High temperature sintered thoria and thoria-4 weight% urania dissolution reactions were investigated in the absence of aluminium nitrate and at reduced fluoride concentrations. Corrosion rates of SS 304L zircaloy in various dissolvent mixtures were studied by weight loss method. These studies clearly showed that aluminium nitrate addition for control of fluoride related corrosion of SS 304L can be avoided when zircaloy-clad thoria/thoria-urania pellets are dissolved. Dissolved zirconium ion was observed to be as effective as aluminium ion. Moreover, dissolution could be achieved with reasonable reaction rates at reduced fluoride concentration of 0.005-0.01M instead of 0.03M by changing the method of addition of the fluoride catalyst. (author)

The Effect of Simulated Microgravity Environment of RWV Bioreactors on Surface Reactions and Adsorption of Serum Proteins on Bone-bioactive Microcarriers

Science.gov (United States)

Radin, Shula; Ducheyne, P.; Ayyaswamy, P. S.

2003-01-01

Biomimetically modified bioactive materials with bone-like surface properties are attractive candidates for use as microcarriers for 3-D bone-like tissue engineering under simulated microgravity conditions of NASA designed rotating wall vessel (RWV) bioreactors. The simulated microgravity environment is attainable under suitable parametric conditions of the RWV bioreactors. Ca-P containing bioactive glass (BG), whose stimulatory effect on bone cell function had been previously demonstrated, was used in the present study. BG surface modification via reactions in solution, resulting formation of bone-like minerals at the surface and adsorption of serum proteins is critical for obtaining the stimulatory effect. In this paper, we report on the major effects of simulated microgravity conditions of the RWV on the BG reactions surface reactions and protein adsorption in physiological solutions. Control tests at normal gravity were conducted at static and dynamic conditions. The study revealed that simulated microgravity remarkably enhanced reactions involved in the BG surface modification, including BG dissolution, formation of bone-like minerals at the surface and adsorption of serum proteins. Simultaneously, numerical models were developed to simulate the mass transport of chemical species to and from the BG surface under normal gravity and simulated microgravity conditions. The numerical results showed an excellent agreement with the experimental data at both testing conditions.

Surface confined retro Diels-Alder reaction driven by the swelling of weak polyelectrolytes.

Science.gov (United States)

Lyu, Beier; Cha, Wenli; Mao, Tingting; Wu, Yuanzi; Qian, Hujun; Zhou, Yitian; Chen, Xiuli; Zhang, Shen; Liu, Lanying; Yang, Guang; Lu, Zhongyuan; Zhu, Qiang; Ma, Hongwei

2015-03-25

Recently, the type of reactions driven by mechanical force has increased significantly; however, the number of methods for activating those mechanochemical reactions stays relatively limited. Furthermore, in situ characterization of a reaction is usually hampered by the inherent properties of conventional methods. In this study, we report a new platform that utilizes mechanical force generated by the swelling of surface tethered weak polyelectrolytes. An initiator with Diels-Alder (DA) adduct structure was applied to prepare the polyelectrolyte-carboxylated poly(OEGMA-r-HEMA), so that the force could trigger the retro DA reaction. The reaction was monitored in real time by quartz crystal microbalance and confirmed with atomic force microscopy and X-ray photoelectron spectroscopy. Compared with the conventional heating method, the swelling-induced retro DA reaction proceeded rapidly with high conversion ratio and selectivity. A 23.61 kcal/mol theoretical energy barrier supported the practicability of this retro DA reaction being triggered mechanically at ambient temperature. During swelling, the tensile force was controllable and persistent. This unique feature imparts this mechanochemical platform the potential to "freeze" an intermediate state of a reaction for in situ spectroscopic observations, such as surface-enhanced Raman spectroscopy and frequency generation spectroscopy.

Dissolution and secondary mineral precipitation in basalts due to reactions with carbonic acid

Science.gov (United States)

Kanakiya, Shreya; Adam, Ludmila; Esteban, Lionel; Rowe, Michael C.; Shane, Phil

2017-06-01

One of the leading hydrothermal alteration processes in volcanic environments is when rock-forming minerals with high concentrations of iron, magnesium, and calcium react with CO2 and water to form carbonate minerals. This is used to the advantage of geologic sequestration of anthropogenic CO2. Here we experimentally investigate how mineral carbonation processes alter the rock microstructure due to CO2-water-rock interactions. In order to characterize these changes, CO2-water-rock alteration in Auckland Volcanic Field young basalts (less than 0.3 Ma) is studied before and after a 140 day reaction period. We investigate how whole core basalts with similar geochemistry but different porosity, permeability, pore geometry, and volcanic glass content alter due to CO2-water-rock reactions. Ankerite and aluminosilicate minerals precipitate as secondary phases in the pore space. However, rock dissolution mechanisms are found to dominate this secondary mineral precipitation resulting in an increase in porosity and decrease in rigidity of all samples. The basalt with the highest initial porosity and volcanic glass volume shows the most secondary mineral precipitation. At the same time, this sample exhibits the greatest increase in porosity and permeability, and a decrease in rock rigidity post reaction. For the measured samples, we observe a correlation between volcanic glass volume and rock porosity increase due to rock-fluid reactions. We believe this study can help understand the dynamic rock-fluid interactions when monitoring field scale CO2 sequestration projects in basalts.

A copper-catalyzed bioleaching process for enhancement of cobalt dissolution from spent lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Zeng, Guisheng, E-mail: zengguisheng@hotmail.com [Key Laboratory of Jiangxi Province for Ecological Diagnosis-Remediation and Pollution Control, Nanchang Hangkong University, Nanchang 330063 (China); College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082 (China); Deng, Xiaorong [Key Laboratory of Jiangxi Province for Ecological Diagnosis-Remediation and Pollution Control, Nanchang Hangkong University, Nanchang 330063 (China); School of Environment and Chemical Engineering, Nanchang Hangkong University, Nanchang 330063 (China); Luo, Shenglian, E-mail: sllou@hnu.edu.cn [Key Laboratory of Jiangxi Province for Ecological Diagnosis-Remediation and Pollution Control, Nanchang Hangkong University, Nanchang 330063 (China); College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082 (China); School of Environment and Chemical Engineering, Nanchang Hangkong University, Nanchang 330063 (China); Luo, Xubiao; Zou, Jianping [Key Laboratory of Jiangxi Province for Ecological Diagnosis-Remediation and Pollution Control, Nanchang Hangkong University, Nanchang 330063 (China); School of Environment and Chemical Engineering, Nanchang Hangkong University, Nanchang 330063 (China)

2012-01-15

Highlights: Black-Right-Pointing-Pointer Catalytic ion was first applied to the bioleaching process of spent lithium-ion batteries. Black-Right-Pointing-Pointer The bioleaching efficiency was great improved from 43.1% to 99.9% in the presence of copper ion. Black-Right-Pointing-Pointer A new reaction model was proposed to explain the catalytic mechanism. - Abstract: A copper-catalyzed bioleaching process was developed to recycle cobalt from spent lithium-ion batteries (mainly LiCoO{sub 2}) in this paper. The influence of copper ions on bioleaching of LiCoO{sub 2} by Acidithiobacillus ferrooxidans (A.f) was investigated. It was shown that almost all cobalt (99.9%) went into solution after being bioleached for 6 days in the presence of 0.75 g/L copper ions, while only 43.1% of cobalt dissolution was obtained after 10 days without copper ions. EDX, XRD and SEM analyses additionally confirmed that the cobalt dissolution from spent lithium-ion batteries could be improved in the presence of copper ions. The catalytic mechanism was investigated to explain the enhancement of cobalt dissolution by copper ions, in which LiCoO{sub 2} underwent a cationic interchange reaction with copper ions to form CuCo{sub 2}O{sub 4} on the surface of the sample, which could be easily dissolved by Fe{sup 3+}.

Aluminosilicate Dissolution and Silicate Carbonation during Geologic CO2 Sequestration

Science.gov (United States)

Min, Yujia

Geologic CO2 sequestration (GCS) is considered a promising method to reduce anthropogenic CO2 emission. Assessing the supercritical CO2 (scCO2) gas or liquid phase water (g, l)-mineral interactions is critical to evaluating the viability of GCS processes. This work contributes to our understanding of geochemical reactions at CO 2-water (g, l)-mineral interfaces, by investigating the dissolution of aluminosilicates in CO2-acidified water (l). Plagioclase and biotite were chosen as model minerals in reservoir rock and caprock, respectively. To elucidate the effects of brine chemistry, first, the influences of cations in brine including Na, Ca, and K, have been investigated. In addition to the cations, the effects of abundant anions including sulfate and oxalate were also examined. Besides the reactions in aqueous phase, we also examine the carbonation of silicates in water (g)-bearing supercritical CO2 (scCO2) under conditions relevant to GCS. For the metal carbonation, in particular, the effects of particle sizes, water, temperature, and pressure on the carbonation of wollastonite were systematically examined. For understanding the cations effects in brine, the impacts of Na concentrations up to 4 M on the dissolution of plagioclase and biotite were examined. High concentrations of Na significantly inhibited plagioclase dissolution by competing adsorption with proton and suppressing proton-promoted dissolution. Ca has a similar effect to Na, and their effects did not suppress each other when Na and Ca co-existed. For biotite, the inhibition effects of Na coupled with an enhancing effect due to ion exchange reaction between Na and interlayer K, which cracked the basal surfaces of biotite. The K in aqueous phase significantly inhibited the dissolution. If the biotite is equilibrated with NaCl solutions initially, the biotite dissolved faster than the original biotite and the dissolution was inhibited by Na and K in brine. The outcomes improve our current knowledge of

Modification of NaK (Na and K) dissolution device at the L.E.C.I

International Nuclear Information System (INIS)

Mansard, Bernard; Ducas, Serge; Riviere, Michel

1969-12-01

As three NaK dissolution devices had been operated since 1965 and as irradiation assemblies with a greater capacity (2 to 3 times) are now to be used, the modification of these dissolution devices is addressed. This requires a better control of the dissolution reaction (the NaK + alcohol reaction is highly exothermic and results in an effervescence which requires a greater volume). The objectives are therefore to delay the dissolution, to trigger it, to stop it, to control it at will, and to release heat. The new device is then described with its vessel, its cap, its ball valve, and its two tight sleeves. The operation principle is described, as well as the NaK draining process, and the NaK dissolution. Safety, time saving and raw matter saving issues are finally outlined

Contact Angle Measurements: an Alternative Approach Towards Understanding the Mechanism of Increased Drug Dissolution from Ethylcellulose Tablets Containing Surfactant and Exploring the Relationship Between Their Contact Angles and Dissolution Behaviors.

Science.gov (United States)

Liu, Tiaotiao; Hao, Jingqiang; Yang, Baixue; Hu, Beibei; Cui, Zhixiang; Li, Sanming

2018-05-01

The addition of surfactant in tablet was a well-defined approach to improve drug dissolution rate. While the selected surfactant played a vital role in improving the wettability of tablet by medium, it was equally important to improve the dissolution rate by permeation effect due to production of pores or the reduced inter-particle adhesion. Furthermore, understanding the mechanism of dissolution rate increased was significant. In this work, contact angle measurement was taken up as an alternative approach for understanding the dissolution rate enhancement for tablet containing surfactant. Ethylcellulose, as a substrate, was used to prepare tablet. Four surfactants, sodium dodecyl sulfate (SDS), sodium dodecylbenzenesulfonate (SDBS), dodecyltrimethylammonium bromide (DTAB), and sodium lauryl sulfonate (SLS), were used. Berberine hydrochloride, metformin hydrochloride, and rutin were selected as model drugs. The contact angle of tablet in the absence and presence of surfactant was measured to explore the mechanism. The dissolution test was investigated to verify the mechanism and to establish a correlation with the contact angle. The result showed that the mechanism was the penetration effect rather than the wetting effect. The dissolution increased with a reduction in the contact angle. DTAB was found to obtain the highest level of dissolution enhancement and the lowest contact angle, while SDS, SDBS, and SLS were found to be the less effective in both dissolution enhancement and contact angle decrease. Therefore, contact angle was a good indicator for dissolution behavior besides exploring the mechanism of increased dissolution, which shows great potential in formula screening.

Dissolution of covalent adaptable network polymers in organic solvent

Science.gov (United States)

Yu, Kai; Yang, Hua; Dao, Binh H.; Shi, Qian; Yakacki, Christopher M.

2017-12-01

It was recently reported that thermosetting polymers can be fully dissolved in a proper organic solvent utilizing a bond-exchange reaction (BER), where small molecules diffuse into the polymer, break the long polymer chains into short segments, and eventually dissolve the network when sufficient solvent is provided. The solvent-assisted dissolution approach was applied to fully recycle thermosets and their fiber composites. This paper presents the first multi-scale modeling framework to predict the dissolution kinetics and mechanics of thermosets in organic solvent. The model connects the micro-scale network dynamics with macro-scale material properties: in the micro-scale, a model is developed based on the kinetics of BERs to describe the cleavage rate of polymer chains and evolution of chain segment length during the dissolution. The micro-scale model is then fed into a continuum-level model with considerations of the transportation of solvent molecules and chain segments in the system. The model shows good prediction on conversion rate of functional groups, degradation of network mechanical properties, and dissolution rate of thermosets during the dissolution. It identifies the underlying kinetic factors governing the dissolution process, and reveals the influence of different material and processing variables on the dissolution process, such as time, temperature, catalyst concentration, and chain length between cross-links.

Lyoluminescence of irradiated carbohydrates - the role of dissolution rate and oxygen

International Nuclear Information System (INIS)

Baugh, P.J.; Laflin, P.

1980-01-01

The lyoluminescent emission from γ-irradiated carbohydrates is shown to be strictly controlled by the rate of dissolution of the solid and the availability of oxygen for reaction during dissolution. These effects are explained in terms of oxidation of trapped radicals diffusing from the dissolving carbohydrate which react in an 'active volume' set up at the onset of dissolution at the crystal-water interface. At irradiation doses greater than 82.5 krad for mannose there is a suppression of the emission which results from an incomplete oxidation of the diffusing radicals due to insufficient O 2 in the active volume leading to a reaction involving unoxidised radicals and peroxyl radicals which are believed to be the precursors of the emission. This reaction is suppressed when the oxygen supply to the 'active volume' is increased. This can be achieved by increasing the oxygen content of the injector gas and indirectly by decreasing the solubility of the carbohydrate. Under these conditions the linear dose range of the lyoluminescence response is extended to ca. 330 krad close to the dose at which trapped radicals saturate in the irradiated solid carbohydrate. Although lyoluminescence is a liquid surface-layer effect as expected the generation of the emission is greatly influenced by oxygen present in the injection atmosphere. Quenching of lyoluminescence by adding peroxyl radical quenchers Cu(II) ions and hydroquinone, suggests that the reaction involving these quenchers also occurs in the 'active volume'. The results generally can be interpreted in terms of a diffusion model. (author)

Reaction Mechanisms for the Electrochemical Reduction of CO2 to CO and Formate on the Cu(100) Surface at 298K from Quantum Mechanics Free Energy Calculations with Explicit Water.

Science.gov (United States)

Cheng, Tao; Xiao, Hai; Goddard, William A

2016-10-11

Copper is the only elemental metal that reduces a significant fraction of CO 2 to hydrocarbons and alcohols, but the atomistic reaction mechanism that controls the product distributions are not known because it has not been possible to detect the reaction intermediates on the electrode surface experimentally, or carry out Quantum Mechanics (QM) calculations with a realistic description of the electrolyte (water). Here, we carry out Quantum Mechanics (QM) calculations with an explicit description of water on the Cu(100) surface (experimentally shown to be stable under CO2RR conditions) to examine the initial reaction pathways to form CO and formate (HCOO - ) from CO 2 through free energy calculations at 298K and pH 7. We find that CO formation proceeds from physisorbed CO 2 to chemisorbed CO 2 (*CO 2 δ- ), with a free energy barrier of ΔG ‡ =0.43 eV, the rate determining step (RDS). The subsequent barriers of protonating *CO 2 δ- to form COOH* and then dissociating COOH* to form *CO are 0.37 eV and 0.30 eV, respectively. HCOO - formation proceeds through a very different pathway in which physisorbed CO 2 reacts directly with a surface H* (along with electron transfer), leading to ΔG ‡ = 0.80 eV. Thus, the competition between CO formation and HCOO - formation occurs in the first electron transfer step. On Cu(100), the RDS for CO formation is lower, making CO the predominant product. Thus, to alter the product distribution we need to control this first step of CO 2 binding, which might involve alloying or changing the structure at the nanoscale.

Numerical modelling of glass dissolution: gel layer morphology

Energy Technology Data Exchange (ETDEWEB)

Devreux, F. E-mail: fd@pmc.polytechnique.fr; Barboux, P

2001-09-01

Numerical simulations of glass dissolution are presented. The glass is modelized as a random binary mixture composed of two species representing silica and soluble oxides, such as boron and alkali oxides. The soluble species are dissolved immediately when they are in contact with the solution. For the species which represents silica, one introduces dissolution and condensation probabilities. It is shown that the morphology and the thickness of the surface hydration layer (the gel) are highly dependent on the dissolution model, especially on the parameter which controls the surface tension. Simulations with different glass surface area to solution volume ratio (S/V) show that this experimental parameter has important effects on both the shrinkage and the gel layer thickness.

Kinetics of dissolution of thorium and uranium doped britholite ceramics

Energy Technology Data Exchange (ETDEWEB)

Dacheux, N., E-mail: nicolas.dacheux@univ-montp2.f [Groupe de Radiochimie, Institut de Physique Nucleaire d' Orsay, Bat. 100, Universite Paris-Sud-11, 91406 Orsay (France); Institut de Chimie Separative de Marcoule, UMR 5257 (Universite Montpellier 2/CNRS/CEA/ENSCM), Bat. 426, Centre de Marcoule, BP 17171, 30207 Bagnols sur ceze cedex (France); Du Fou de Kerdaniel, E. [Groupe de Radiochimie, Institut de Physique Nucleaire d' Orsay, Bat. 100, Universite Paris-Sud-11, 91406 Orsay (France); Clavier, N. [Groupe de Radiochimie, Institut de Physique Nucleaire d' Orsay, Bat. 100, Universite Paris-Sud-11, 91406 Orsay (France); Institut de Chimie Separative de Marcoule, UMR 5257 (Universite Montpellier 2/CNRS/CEA/ENSCM), Bat. 426, Centre de Marcoule, BP 17171, 30207 Bagnols sur ceze cedex (France); Podor, R. [Institut de Chimie Separative de Marcoule, UMR 5257 (Universite Montpellier 2/CNRS/CEA/ENSCM), Bat. 426, Centre de Marcoule, BP 17171, 30207 Bagnols sur ceze cedex (France); Institut Jean Lamour - Departement CP2S - Equipe 206, Faculte des Sciences et Techniques - Nancy Universite, BP 70239, 54506 Vandoeuvre les Nancy cedex (France); Aupiais, J. [CEA DAM DIF, 91297 Arpajon (France); Szenknect, S. [Institut de Chimie Separative de Marcoule, UMR 5257 (Universite Montpellier 2/CNRS/CEA/ENSCM), Bat. 426, Centre de Marcoule, BP 17171, 30207 Bagnols sur ceze cedex (France)

2010-09-01

In the field of immobilization of actinides in phosphate-based ceramics, several thorium and uranium doped britholite samples were submitted to leaching tests. The normalized dissolution rates determined for several pH values, temperatures and acidic media from the calcium release range from 4.7 x 10{sup -2} g m{sup -2} d{sup -1} to 21.6 g m{sup -2} d{sup -1}. Their comparison with that determined for phosphorus, thorium and uranium revealed that the dissolution is clearly incongruent for all the conditions examined. Whatever the leaching solution considered, calcium and phosphorus elements were always released with higher R{sub L} values than the other elements (Nd, Th, U). Simultaneously, thorium was found to quickly precipitate as alteration product, leading to diffusion phenomena for uranium. For all the media considered, the uranium release is higher than that of thorium, probably due to its oxidation from tetravalent oxidation state to uranyl. Moreover, the evaluation of the partial order related to proton concentration and the apparent energy of activation suggest that the reaction of dissolution is probably controlled by surface chemical reactions occurring at the solid/liquid interface. Finally, comparative leaching tests performed in sulphuric acid solutions revealed a significant influence of such media on the chemical durability of the leached pellets, leading to higher normalized dissolution rates for all the elements considered. On the basis of the results of chemical speciation, this difference was mainly explained in the light of higher complexion constants by sulfate ions compared to nitrate, chloride and phosphate.

Dissolution characteristics of sericite in chalcopyrite bioleaching and its effect on copper extraction

Science.gov (United States)

Dong, Ying-bo; Li, Hao; Lin, Hai; Zhang, Yuan

2017-04-01

The effects of sericite particle size, rotation speed, and leaching temperature on sericite dissolution and copper extraction in a chalcopyrite bioleaching system were examined. Finer particles, appropriate temperature and rotation speed for Acidithiobacillus ferrooxidans resulted in a higher Al3+ dissolution concentration. The Al3+ dissolution concentration reached its highest concentration of 38.66 mg/L after 48-d leaching when the sericite particle size, temperature, and rotation speed were -43 μm, 30°C, and 160 r/min, respectively. Meanwhile, the sericite particle size, rotation speed, and temperature can affect copper extraction. The copper extraction rate is higher when the sericite particle size is finer. An appropriately high temperature is favorable for copper leaching. The dissolution of sericite fitted the shrinking core model, 1-(2/3) α-(1- α)2/3 = k 1 t, which indicates that internal diffusion is the decision step controlling the overall reaction rate in the leaching process. Scanning electron microscopy analysis showed small precipitates covered on the surface of sericite after leaching, which increased the diffusion resistance of the leaching solution and dissolved ions.

DNAPL remediation with in situ chemical oxidation using potassium permanganate - Part I. Mineralogy of Mn oxide and its dissolution in organic acids

Science.gov (United States)

Li, X. David; Schwartz, Franklin W.

2004-01-01

Previous studies on in situ chemical oxidation of trichloroethylene (TCE) with potassium permanganate indicated that the solid reaction product, Mn oxide, could reduce the permeability of the porous medium and impact the success of dense non-aqueous phase liquid (DNAPL) removal. In order to address the issue of permeability reduction caused by precipitation, this study investigated the mineralogy of Mn oxides and the possibilities of removing the solid precipitates by dissolution. The solid reaction product from the oxidation of TCE by permanganate is semi-amorphous potassium-rich birnessite, which has a layered mineral structure with an interlayer spacing of 7.3 Å. The chemical formula is K 0.854Mn 1.786O 4·1.55H 2O. It has a relatively small specific surface area at 23.6±0.82 m 2/g. Its point of zero charge (pzc) was measured as 3.7±0.4. This birnessite is a relatively active species and could participate in various reactions with existing organic and inorganic matter. The dissolution kinetics of Mn oxide was evaluated in batch experiments using solutions of citric acid, oxalic acid, and ethylenediaminetetraacetic acid (EDTA). Initial dissolution rates were determined to be 0.126 mM/m 2/h for citric acid, 1.35 mM/m 2/h for oxalic acid, and 5.176 mM/m 2/h for EDTA. These rates compare with 0.0025 mM/m 2/h for nitric acid at pH=2. Organic acids dissolve Mn oxide quickly. Reaction rates increase with acid concentration, as tested with citric acid. The dissolution mechanism likely involves proton and ligand-promoted dissolution and reductive dissolution. Citric and oxalic acid can induce ligand-promoted dissolution, while EDTA can induce ligand-promoted and reductive dissolutions. At low pH, proton-promoted dissolution seems to occur with all the acids tested, but this process is not dominant. Reductive dissolution appears to be the most effective process in dissolving the solid, followed by ligand-promoted dissolution. These experiments indicate the significant

Use of fission track for deciphering the dissolution mechanism of silicates glasses

International Nuclear Information System (INIS)

Petit, J.C.; Brousse, C.

1985-09-01

Polished sections of silicate glasses containing latent or pre-etched fission tracks have been subjected to corrosion in deionized water or NaCl brines at 20, 50 and 100 0 C. The evolution of glass surface helps deciphering among reported dissolution models. We show that ion-exchange is dominant in simple glasses while in complex ones, dissolution involves several steps including an in-situ transformation of the pristine material and a reprecipitation of dissolved species

Dissolution of uranium oxide TBP-HNO3 complex

International Nuclear Information System (INIS)

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

2002-12-01

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

Optimization of dissolution process parameters for uranium ore concentrate powders

Energy Technology Data Exchange (ETDEWEB)

Misra, M.; Reddy, D.M.; Reddy, A.L.V.; Tiwari, S.K.; Venkataswamy, J.; Setty, D.S.; Sheela, S.; Saibaba, N. [Nuclear Fuel Complex, Hyderabad (India)

2013-07-01

Nuclear fuel complex processes Uranium Ore Concentrate (UOC) for producing uranium dioxide powder required for the fabrication of fuel assemblies for Pressurized Heavy Water Reactor (PHWR)s in India. UOC is dissolved in nitric acid and further purified by solvent extraction process for producing nuclear grade UO{sub 2} powder. Dissolution of UOC in nitric acid involves complex nitric oxide based reactions, since it is in the form of Uranium octa oxide (U{sub 3}O{sub 8}) or Uranium Dioxide (UO{sub 2}). The process kinetics of UOC dissolution is largely influenced by parameters like concentration and flow rate of nitric acid, temperature and air flow rate and found to have effect on recovery of nitric oxide as nitric acid. The plant scale dissolution of 2 MT batch in a single reactor is studied and observed excellent recovery of oxides of nitrogen (NO{sub x}) as nitric acid. The dissolution process is automated by PLC based Supervisory Control and Data Acquisition (SCADA) system for accurate control of process parameters and successfully dissolved around 200 Metric Tons of UOC. The paper covers complex chemistry involved in UOC dissolution process and also SCADA system. The solid and liquid reactions were studied along with multiple stoichiometry of nitrous oxide generated. (author)

Small leak detection by measuring surface oscillation during sodium-water reaction in steam generator

International Nuclear Information System (INIS)

Nei, Hiromichi; Hori, Masao

1977-01-01

Small leak sodium-water reaction tests were conducted to develop various kinds of leak detectors for the sodium-heated steam generator in FBR. The super-heated steam was injected into sodium in a reaction vessel having a sodium free surface, simulating the steam generator. The level gauge in the reaction vessel generated the most reliable signal among detectors, as long as the leak rates were relatively high. The level gauge signal was estimated to be the sodium surface oscillation caused by hydrogen bubbles produced in sodium-water reaction. Experimental correlation was derived, predicting the amplitude as a function of leak rate, hydrogen dissolution ratio, bubble rise velocity and other parameters concerned, assuming that the surface oscillation is in proportion to the gas hold-up. The noise amplitude under normal operation without water leak was increased with sodium flow rate and found to be well correlated with Froud number. These two correlations predict that a water leak in a ''MONJU'' class (300 MWe) steam generator could possibly be detected by level gauges at a leak rate above 2 g/sec. (auth.)

Role of Adsorption Phenomena in Cubic Tricalcium Aluminate Dissolution.

Science.gov (United States)

Myers, Rupert J; Geng, Guoqing; Li, Jiaqi; Rodríguez, Erich D; Ha, Juyoung; Kidkhunthod, Pinit; Sposito, Garrison; Lammers, Laura N; Kirchheim, Ana Paula; Monteiro, Paulo J M

2017-01-10

The workability of fresh Portland cement (PC) concrete critically depends on the reaction of the cubic tricalcium aluminate (C 3 A) phase in Ca- and S-rich pH >12 aqueous solution, yet its rate-controlling mechanism is poorly understood. In this article, the role of adsorption phenomena in C 3 A dissolution in aqueous Ca-, S-, and polynaphthalene sulfonate (PNS)-containing solutions is analyzed. The zeta potential and pH results are consistent with the isoelectric point of C 3 A occurring at pH ∼12 and do not show an inversion of its electric double layer potential as a function of S or Ca concentration, and PNS adsorbs onto C 3 A, reducing its zeta potential to negative values at pH >12. The S and Ca K-edge X-ray absorption spectroscopy (XAS) data obtained do not indicate the structural incorporation or specific adsorption of SO 4 2- on the partially dissolved C 3 A solids analyzed. Together with supporting X-ray ptychography and scanning electron microscopy results, a model for C 3 A dissolution inhibition in hydrated PC systems is proposed whereby the formation of an Al-rich leached layer and the complexation of Ca-S ion pairs onto this leached layer provide the key inhibiting effect(s). This model reconciles the results obtained here with the existing literature, including the inhibiting action of macromolecules such as PNS and polyphosphonic acids upon C 3 A dissolution. Therefore, this article advances the understanding of the rate-controlling mechanism in hydrated C 3 A and thus PC systems, which is important to better controlling the workability of fresh PC concrete.

Revisiting classical silicate dissolution rate laws under hydrothermal conditions

Science.gov (United States)

Pollet-Villard, Marion; Daval, Damien; Saldi, Giuseppe; Knauss, Kevin; Wild, Bastien; Fritz, Bertrand

2015-04-01

In the context of geothermal energy, the relative intensities of primary mineral leaching and secondary mineral precipitation can affect porosity and permeability of the reservoir, thereby influencing its hydraulic performance and the efficiency of the geothermal power station. That is why the prediction of reaction kinetics of fluid/rock interactions represents a critical issue in this context. Moreover, in several geothermal systems such as the one of Soultz-sous-Forêts (Alsace, France), the circulation of aqueous fluids induces only modest modifications of their chemical composition. Therefore, fluid-rock interactions take place at close-to-equilibrium conditions, where the rate-affinity relations are poorly known and intensively debated [1]. To describe more precisely the dissolution processes, our strategy consists in investigating the dissolution of the main cleavages of K-spar minerals (one of the prevalent primary minerals in the reservoir of Soultz-sous-Forêts geothermal system) over a wide range of Gibbs free energy (ΔG) conditions. The aims are to decipher the impact of crystallographic orientation and microstructural surface modifications on the dissolution kinetics and to propose a relation between K-spar dissolution rate and ΔG. Our experimental work relies on a coupled approach which combines classical experiments of K-spar dissolution monitored by aqueous chemical analyses (ICP-AES) and innovative techniques of nm- to μm-scale characterization of solid surface (SEM, AFM, VSI) [2]. Our results confirm that K-spar dissolution is an anisotropic process: we measure a tenfold factor between the slowest and the fastest-dissolving surfaces. Moreover, the formation of etch pits on surfaces during their alteration has been evidenced on all of the different faces that have been studied. This complex evolution of the surface topography casts doubt of the relevance of a surface model based on shrinking particles and represents a possible cause of an

Dissolution study of tremolite and anthophyllite: pH effect on the reaction kinetics

International Nuclear Information System (INIS)

Rozalen, M.; Ramos, M.E.; Gervilla, F.; Kerestedjian, T.; Fiore, S.; Huertas, F.J.

2014-01-01

Highlights: • Dissolution rates strongly depend on pH and it is different for each mineral. • Anthophyllite dissolves up to 8 times faster than tremolite in similar conditions. • SEM images show different particle breakage and carbonation effects at basic pHs. • Our results are a good background to develop remediation processes of contaminated sites. - Abstract: The effect of pH on the kinetics of tremolite and anthophyllite dissolution was investigated at 25 °C in batch reactors over the pH range of 1–13.5, in inorganic buffered solutions. Dissolution rates were obtained based on the release of Si and Mg. Results obtained in this study show different behaviors for both minerals. For tremolite, dissolution rates show a noticeable dependence on pH between 1 and 8, decreasing as pH increases and reaching a minimum around neutral conditions. At basic pH this dependence becomes even stronger, but dissolution takes place together with collateral effects of saturation and carbonation. A preferential release of Ca and Mg is observed in acid media, lowering the Mg/Si ratio to the extent that Mg solubility decreases with pH. For anthophyllite, dissolution rates also show a strong dependence on pH, between 1 and 9.5. At the same pH, anthophyllite dissolves up to 8 times faster than tremolite. For pH > 9.5 this dependence is smooth, and it is probably associated with effects of saturation and carbonation. Dissolution is also non-stoichiometric with a faster release of Mg with respect to Si in acid media. SEM observations show differences in the breakage mechanism of the fibers. The anthophyllite particle breakage during dissolution consists of the splitting of bundle fibers parallel to the fiber longitudinal direction. However, for tremolite, other than fiber splitting, particles shorten induced by coalescence of etch pits developed perpendicular to c axe

Initial Drug Dissolution from Amorphous Solid Dispersions Controlled by Polymer Dissolution and Drug-Polymer Interaction.

Science.gov (United States)

Chen, Yuejie; Wang, Shujing; Wang, Shan; Liu, Chengyu; Su, Ching; Hageman, Michael; Hussain, Munir; Haskell, Roy; Stefanski, Kevin; Qian, Feng

2016-10-01

To identify the key formulation factors controlling the initial drug and polymer dissolution rates from an amorphous solid dispersion (ASD). Ketoconazole (KTZ) ASDs using PVP, PVP-VA, HMPC, or HPMC-AS as polymeric matrix were prepared. For each drug-polymer system, two types of formulations with the same composition were prepared: 1. Spray dried dispersion (SDD) that is homogenous at molecular level, 2. Physical blend of SDD (80% drug loading) and pure polymer (SDD-PB) that is homogenous only at powder level. Flory-Huggins interaction parameters (χ) between KTZ and the four polymers were obtained by Flory-Huggins model fitting. Solution (13)C NMR and FT-IR were conducted to investigate the specific drug-polymer interaction in the solution and solid state, respectively. Intrinsic dissolution of both the drug and the polymer from ASDs were studied using a Higuchi style intrinsic dissolution apparatus. PXRD and confocal Raman microscopy were used to confirm the absence of drug crystallinity on the tablet surface before and after dissolution study. In solid state, KTZ is completely miscible with PVP, PVP-VA, or HPMC-AS, demonstrated by the negative χ values of -0.36, -0.46, -1.68, respectively; while is poorly miscible with HPMC shown by a positive χ value of 0.23. According to solution (13)C NMR and FT-IR studies, KTZ interacts with HPMC-AS strongly through H-bonding and dipole induced interaction; with PVPs and PVP-VA moderately through dipole-induced interactions; and with HPMC weakly without detectable attractive interaction. Furthermore, the "apparent" strength of drug-polymer interaction, measured by the extent of peak shift on NMR or FT-IR spectra, increases with the increasing number of interacting drug-polymer pairs. For ASDs with the presence of considerable drug-polymer interactions, such as KTZ/PVPs, KTZ/PVP-VA, or KTZ /HPMC-AS systems, drug released at the same rate as the polymer when intimate drug-polymer mixing was ensured (i.e., the SDD systems

Dissolution kinetics of purified and synthetic smectites at 25°C and PH∼9

International Nuclear Information System (INIS)

Marty, Nicolas C.M.; Tournassat, Christophe; Gaucher, Eric C.; Chino, Daisuke; Sato, Tsutomu; Villieras, Frederic; Giffaut, Eric; Cama, Jordi; Soler, J.M.

2010-01-01

Document available in extended abstract form only. Mineral rate laws that account for the kinetics of dissolution/precipitation of clays and other minerals are used in reactive transport codes to simulate and evaluate the evolution of geochemical conditions in the near-field of high level radioactive waste (HLW) in deep geological repositories. Smectite is the main component in the compacted bentonite used in the Multi-barrier system to lower permeability. As a consequence, molecular diffusion becomes the main mechanism of mass transport, and dissolution and precipitation reactions take place in close-to-equilibrium conditions. Nonetheless, in the reactive transport codes, databases utilized mainly incorporate rate laws derived at far-from- equilibrium conditions, which are not representative of near-field and far-field conditions of concrete-clay or iron-clay interfaces. Hence, there is an important need to derive kinetic rate laws that allow extrapolation of mineral dissolution/precipitation as a function of the solution saturation state (i.e., Gibbs free energy, ΔG r ). Once the effect of the environmental variables, such as pH, T and ΔG r , etc. exert on smectite dissolution is discerned, evaluation of the evolution of geochemical conditions in the HLW repository is carried out using reactive transport codes that couple the rate laws with transport equations. Several studies related dissolution of natural smectites with pH, and just a few dealt with the rate dependency on Gibbs free energy. The present study aims at estimating dissolution rates of montmorillonite in conditions as close as possible to those expected in the Callovo-Oxfordian formation, i.e. pH∼7.2 and 25 deg. C. Dissolution kinetics of two montmorillonites (natural Na-montmorillonite purified from MX80 and synthetic smectite) were investigated by means of flow-through experiments and solution-chemistry data obtained. The calculated rates were based on release of Si, Al and Mg and normalized

Specific surface area behavior of a dissolving population of particles. Augmenting Mercer Dissolution Theory

International Nuclear Information System (INIS)

Scripsick, R.C.; Rothenberg, S.J.

1986-01-01

Specific surface area (Sp) measurements were made on two uranium oxide aerosol materials before and after in vitro dissolution studies were performed on the materials. The results of these Sp measurements were evaluated relative to predictions made from extending Mercer dissolution theory to describe the Sp behavior of a dissolving population of particles

Etude cinetique et thermodynamique de la dissolution de la fluorapatite dans l'acide phosphorique

International Nuclear Information System (INIS)

Brahim, K.; Khattech, I.; Dubes, J.P.; Jemal, M.

2005-01-01

A modification on the reversal cells of a C-80 SETARAM calorimeter allows a Joule effect in the reaction cells to determine a transfer function in experimental conditions close to those of dissolution of a solid in a liquid. The calorimeter was then used to determine in isothermal conditions both thermodynamic and kinetic parameters associated with dissolution of synthetic fluorapatite in phosphoric acid solutions. Due to the rapidity of reaction, the heat flow recordings were deconvoluted and the resulting curves were analyzed iteratively to obtain the rates of digestion and the enthalpy of dissolution at 298 K of fluorapatite in phosphoric acid solution containing 10, 18 or 30 wt% P 2 O 5 . The results agree with a two-step dissolution mechanism. The first step is the dissolution of the solid in phosphoric acid, and the second is the formation of the complex Ca(H 2 PO 4 ) +

The mechanism of reequilibration of solids in the presence of a fluid phase

International Nuclear Information System (INIS)

Putnis, Andrew; Putnis, Christine V.

2007-01-01

The preservation of morphology (pseudomorphism) and crystal structure during the transformation of one solid phase to another is regularly used as a criterion for a solid-state mechanism, even when there is a fluid phase present. However, a coupled dissolution-reprecipitation mechanism also preserves the morphology and transfers crystallographic information from parent to product by epitaxial nucleation. The generation of porosity in the product phase is a necessary condition for such a mechanism as it allows fluid to maintain contact with a reaction interface which moves through the parent phase from the original surface. We propose that interface-coupled dissolution-reprecipitation is a general mechanism for reequilibration of solids in the presence of a fluid phase. - Graphical abstract: A single crystal of KBr is transformed to a porous single crystal of KCl by immersion in saturated KCl solution. The image shows partial transformation of a crystal of KBr (core) to KCl (porous, milky rim) by an interface coupled dissolution-reprecipitation mechanism. The external dimensions and crystallographic orientation of the original crystal are preserved, while a reaction interface moves through the crystal

Impact of dissolution and carbonate precipitation on carbon storage in basalt

Science.gov (United States)

Wells, R. K.; Xiong, W.; Tadeoye, J.; Menefee, A.; Ellis, B. R.; Skemer, P. A.; Giammar, D.

2016-12-01

The spatial evolution of silicate mineral dissolution, carbonate precipitation, and the transport of fluids influence the viability of carbon storage in basalt reservoirs. Dissolution of natural basalt and subsequent carbonate precipitation in systems with different transport processes operating were characterized using static and flow-through (5 mL/hr) experiments at 50, 100, and 150 °C, and 100 bar CO2. Intact samples and cores with milled pathways that simulate fractures were tested. Spatial and mineralogical patterns in dissolution and precipitation were analyzed using optical and electron microscopy, microCT scanning, and surface roughness data. Precipitates and fluid chemistry were analyzed using Raman spectroscopy, SEM-EDS, and ICP-MS. Analysis of the bulk solution and surface topography suggests dissolution of olivine and pyroxene grains begins within hours of the start of the experiments. In flow-through experiments, total effluent cation concentrations reach a peak concentration within a few hours then drop towards a steady state within a few days. In static experiments, the initial rate of cation release is faster than it is after several weeks. In both cases Ca2+, Mg2+, and Fe2+ are the dominant cations in solution in the initial stages of reaction. Lower concentrations of Na2+, K+, and Al3+, and the preservation of feldspar and matrix grains after several weeks of reaction indicate the slow reactivity of these minerals. As the reaction progresses, the surface roughness increases steadily with cavities developing at the sites of olivine and pyroxene grains. Post-reaction analysis of basalt samples reacted at static conditions with milled pathways reveals that both siderite and amorphous silica precipitated within diffusion-limited zones as early as 4-6 weeks. Siderite abundance varies with distance along the pathway with the highest concentration of carbonates 1-2 cm below the fracture opening. Siderite precipitates are large enough to fill fracture

Improving dissolution and oral bioavailability of pranlukast hemihydrate by particle surface modification with surfactants and homogenization

Directory of Open Access Journals (Sweden)

Ha ES

2015-06-01

Full Text Available Eun-Sol Ha,1 In-hwan Baek,2 Jin-Wook Yoo,1 Yunjin Jung,1 Min-Soo Kim1 1College of Pharmacy, Pusan National University, 2College of Pharmacy, Kyungsung University, Busan, Republic of Korea Abstract: The present study was carried out to develop an oral formulation of pranlukast hemihydrate with improved dissolution and oral bioavailability using a surface-modified microparticle. Based on solubility measurements, surface-modified pranlukast hemihydrate microparticles were manufactured using the spray-drying method with hydroxypropylmethyl cellulose, sucrose laurate, and water and without the use of an organic solvent. The hydrophilicity of the surface-modified pranlukast hemihydrate microparticle increased, leading to enhanced dissolution and oral bioavailability of pranlukast hemihydrate without a change in crystallinity. The surface-modified microparticles with an hydroxypropylmethyl cellulose/sucrose laurate ratio of 1:2 showed rapid dissolution of up to 85% within 30 minutes in dissolution medium (pH 6.8 and oral bioavailability higher than that of the commercial product, with approximately 2.5-fold and 3.9-fold increases in area under the curve (AUC0→12 h and peak plasma concentration, respectively. Therefore, the surface-modified microparticle is an effective oral drug delivery system for the poorly water-soluble therapeutic pranlukast hemihydrate. Keywords: solubility, wettability, sucrose laurate, cellulose

Inhibition of cobalt active dissolution by benzotriazole in slightly alkaline bicarbonate aqueous media

Energy Technology Data Exchange (ETDEWEB)

Gallant, Danick [Departement de Chimie, Universite Laval, Quebec (Canada); Departement de Biologie, Chimie et Geographie, Universite du Quebec a Rimouski, 300, Allee des Ursulines, Rimouski, Quebec (Canada); E-mail: danick.gallant.1@ulaval.ca; Pezolet, Michel [Departement de Chimie, Universite Laval, Quebec (Canada)]. E-mail: michel.pezolet@chm.ulaval.ca; Simard, Stephan [Departement de Chimie, Universite Laval, Quebec (Canada); Departement de Biologie, Chimie et Geographie, Universite du Quebec a Rimouski, 300, Allee des Ursulines, Rimouski, Quebec (Canada); E-mail: stephan_simard@uqar.qc.ca

2007-04-20

The efficiency of benzotriazole as inhibiting agent for the corrosion of cobalt was probed at pH ranging from 8.3 to 10.2 in a sodium bicarbonate solution, chosen to simulate mild natural environments. From electrochemical, Raman spectroscopy, atomic force microscopy and ellipsometry experiments, we have demonstrated that benzotriazole markedly affects the electrodissolution reactions, which become modeled by the formation of a [Co(II)(BTA){sub 2}.H{sub 2}O] {sub n} film according to two different mechanisms. Surface-enhanced Raman spectroscopy has shown that the polarization of a cobalt electrode at cathodic potentials with respect to its potential of zero charge allows a mechanism of specific adsorption of the neutral form of benzotriazole to take place through a suspected metal-to-molecule electron transfer and which follows Frumkin's adsorption isotherms. At the onset of the anodic dissolution, some experimental evidence suggests that these adsorbed neutral benzotriazole molecules deprotonate to yield a very thin [Co(II)(BTA){sub 2}.H{sub 2}O] {sub n} polymer-like and water-insoluble protective film, responsible for the inhibition of active dissolution processes occurring at slightly more anodic potentials. In the anodic dissolution region, deprotonated benzotriazole species present in the bulk solution favors the formation of a multilayered [Co(II)(BTA){sub 2}.H{sub 2}O] {sub n} film, which also contributes to the inhibition of any further cobalt dissolution usually observed at higher electrode potentials.

Effect of Ti and C particle sizes on reaction behavior of thermal explosion reaction of Cu−Ti−C system under Ar and air atmospheres

Energy Technology Data Exchange (ETDEWEB)

Liang, Yunhong; Zhao, Qian; Li, Xiujuan; Zhang, Zhihui, E-mail: zhzh@jlu.edu.cn; Ren, Luquan

2016-09-15

The thermal explosion (TE) reaction behavior of Cu−Ti−C systems with different Ti and C particle sizes was investigated under air and Ar atmospheres. It was found that increasing the Ti and C particle sizes leads to higher ignition temperatures under both atmospheres and that the maximum combustion temperature decreases with increasing C particle size. The TE reaction is much easier to activate (i.e., it has a lower ignition temperature) in air because of the heat released from Ti oxidation and nitridation and Cu oxidation reactions on the Cu−Ti−C compact surface. TiC ceramic particles are successfully prepared in the bulk Cu−Ti−C compacts under both air and Ar atmospheres through a dissolution-diffusion-precipitation mechanism. Differential thermal and thermodynamic analyses show that the TE reaction ignition process in air is mainly controlled by the Ti particle size. - Highlights: • Variation of Ti and C particle sizes affects thermal reaction (TE) behaviors. • Ignition temperature under air is much lower than that under Ar atmosphere. • Heat of oxidation and nitridation reactions reduces ignition temperature under air.

Dissolution kinetics of smectite in geological repository system of TRU waste

International Nuclear Information System (INIS)

Sato, Tsutomu

2005-02-01

Extensive use of cement for encapsulation, mine timbering, and grouting purposes is envisaged in geological repositories of TRU waste. Degradation of cement materials in the repositories can produce a high pH pore fluid initially ranging from pH 13.0 to 13.5. The high pH pore fluids can migrate and react chemically with the host rock and bentonites which were employed to enhance repository's integrity. These chemical reactions can effect the capacity of the rocks and bentonites in retarding the migration of radionuclides. Smectite, main component of bentonite, can lose some of their desirable properties at the early stages of bentonite-cement fluid interaction. This has been a key research issue in performance assessment of TRU waste disposal. In this study, firstly, the factors affected on dissolution rate of smectite and equations describing dissolution rate were reviewed. Secondly, the effect of dissolved silica on the dissolution behavior of Na-montmorillonite was investigated. Bulk sample flow-through dissolution experiments at alkaline condition (pH 13.3) with different dissolved silica concentrations at different temperatures were performed. Titration experiments were also carried out at similar conditions. Atomic Force Microscopy (AFM) ex situ observations (i.e. on samples from flow-through experiments) was also performed to obtain the dissolution rate. Current results from bulk sample surface titration experiments indicate that dissolved silica has no pronounced effect on the surface titration behavior of Na-montmorillonite at any temperature. However, the trends for the surface titration behavior represent the averaged behavior of all particle sizes (i.e. including colloids) such that within an order of magnitude change cannot be quantified appreciably. Bulk flow-through dissolution experiments coupled with ex situ AFM observations indicate that there is also no effect of dissolved silica with comparatively low concentration of the reacting solution on

Disentangling the effects of polymer coatings on silver nanoparticle agglomeration, dissolution, and toxicity to determine mechanisms of nanotoxicity

International Nuclear Information System (INIS)

Zook, Justin M.; Halter, Melissa D.; Cleveland, Danielle; Long, Stephen E.

2012-01-01

Silver nanoparticles (AgNPs) are frequently coated with a variety of polymers, which may affect various interdependent mechanisms of toxicity or antimicrobial action, including agglomeration and dissolution rates. Here, we systematically measure how citrate, dextran, 5 and 20 kDa poly(ethylene glycol) (PEG), and poly(vinyl pyrrolidone) coatings affect AgNP agglomeration, dissolution, and toxicity. In addition, to disentangle the coatings’ effects on agglomeration from their other effects, we produce multiple stable agglomerate sizes of several of the coated ∼23 nm AgNPs ranging from singly-dispersed to mean agglomerate sizes of several hundred nanometers. These dispersions allow us to independently study the effects of agglomeration and polymer coating on dissolution rate and hemolytic toxicity. We find that both hemolytic toxicity and dissolution rate are highest for the 5 kDa PEG coating, and toxicity and dissolution rate decrease significantly with increasing agglomerate size independent of coating. This correlation between toxicity and dissolution rate suggests that both polymer coating and agglomeration may affect hemolytic toxicity largely through their effects on dissolution. Because both the AgNP dissolution rate and hemolysis decrease only moderately compared to the large increases in agglomerate size, AgNPs’ hemolytic toxicity may be caused by their large surface area and consequently high dissolution rate, rather than from other size-specific effects. At the silver concentrations used in this work, silver dissolved from AgNPs is expected to be primarily in the form of AgCl NPs, which are therefore more likely than Ag + ions to be the primary drivers of hemolytic toxicity. In addition, all AgNPs we tested are much more toxic to horse red blood cells than sheep red blood cells, highlighting the complexity of toxic responses and the need to test toxicity in multiple biological systems.

Disentangling the effects of polymer coatings on silver nanoparticle agglomeration, dissolution, and toxicity to determine mechanisms of nanotoxicity

Science.gov (United States)

Zook, Justin M.; Halter, Melissa D.; Cleveland, Danielle; Long, Stephen E.

2012-10-01

Silver nanoparticles (AgNPs) are frequently coated with a variety of polymers, which may affect various interdependent mechanisms of toxicity or antimicrobial action, including agglomeration and dissolution rates. Here, we systematically measure how citrate, dextran, 5 and 20 kDa poly(ethylene glycol) (PEG), and poly(vinyl pyrrolidone) coatings affect AgNP agglomeration, dissolution, and toxicity. In addition, to disentangle the coatings' effects on agglomeration from their other effects, we produce multiple stable agglomerate sizes of several of the coated 23 nm AgNPs ranging from singly-dispersed to mean agglomerate sizes of several hundred nanometers. These dispersions allow us to independently study the effects of agglomeration and polymer coating on dissolution rate and hemolytic toxicity. We find that both hemolytic toxicity and dissolution rate are highest for the 5 kDa PEG coating, and toxicity and dissolution rate decrease significantly with increasing agglomerate size independent of coating. This correlation between toxicity and dissolution rate suggests that both polymer coating and agglomeration may affect hemolytic toxicity largely through their effects on dissolution. Because both the AgNP dissolution rate and hemolysis decrease only moderately compared to the large increases in agglomerate size, AgNPs' hemolytic toxicity may be caused by their large surface area and consequently high dissolution rate, rather than from other size-specific effects. At the silver concentrations used in this work, silver dissolved from AgNPs is expected to be primarily in the form of AgCl NPs, which are therefore more likely than Ag+ ions to be the primary drivers of hemolytic toxicity. In addition, all AgNPs we tested are much more toxic to horse red blood cells than sheep red blood cells, highlighting the complexity of toxic responses and the need to test toxicity in multiple biological systems.

Disentangling the effects of polymer coatings on silver nanoparticle agglomeration, dissolution, and toxicity to determine mechanisms of nanotoxicity

Energy Technology Data Exchange (ETDEWEB)

Zook, Justin M., E-mail: jzook@nist.gov; Halter, Melissa D.; Cleveland, Danielle; Long, Stephen E. [National Institute of Standards and Technology, Material Measurement Laboratory (United States)

2012-10-15

Silver nanoparticles (AgNPs) are frequently coated with a variety of polymers, which may affect various interdependent mechanisms of toxicity or antimicrobial action, including agglomeration and dissolution rates. Here, we systematically measure how citrate, dextran, 5 and 20 kDa poly(ethylene glycol) (PEG), and poly(vinyl pyrrolidone) coatings affect AgNP agglomeration, dissolution, and toxicity. In addition, to disentangle the coatings' effects on agglomeration from their other effects, we produce multiple stable agglomerate sizes of several of the coated {approx}23 nm AgNPs ranging from singly-dispersed to mean agglomerate sizes of several hundred nanometers. These dispersions allow us to independently study the effects of agglomeration and polymer coating on dissolution rate and hemolytic toxicity. We find that both hemolytic toxicity and dissolution rate are highest for the 5 kDa PEG coating, and toxicity and dissolution rate decrease significantly with increasing agglomerate size independent of coating. This correlation between toxicity and dissolution rate suggests that both polymer coating and agglomeration may affect hemolytic toxicity largely through their effects on dissolution. Because both the AgNP dissolution rate and hemolysis decrease only moderately compared to the large increases in agglomerate size, AgNPs' hemolytic toxicity may be caused by their large surface area and consequently high dissolution rate, rather than from other size-specific effects. At the silver concentrations used in this work, silver dissolved from AgNPs is expected to be primarily in the form of AgCl NPs, which are therefore more likely than Ag{sup +} ions to be the primary drivers of hemolytic toxicity. In addition, all AgNPs we tested are much more toxic to horse red blood cells than sheep red blood cells, highlighting the complexity of toxic responses and the need to test toxicity in multiple biological systems.

Biologically mediated dissolution of volcanic glass in seawater

NARCIS (Netherlands)

Staudigel, H; Yayanos, A; Chastain, R; Davies, G.T.; Verdurmen, E.A Th; Schiffmann, P; Bourcier, R; de Baar, H.J.W.

1998-01-01

We studied the effects of biological mediation on the dissolution of basaltic glass in seawater. Experiments with typical seawater microbial populations were contrasted with a sterile control, and reactions were monitored chemically and isotopically. Biologically mediated experiments produce twice

Reaction mechanisms for barite dissolution and growth

Energy Technology Data Exchange (ETDEWEB)

Stack, Andrew G.

2010-07-26

In Stack and Rustad (2007), the reactive flux method (Rey and Hynes, 1996) and molecular dynamics (MD) were used to simulate the {001} barite-water interface structure and water exchange rate of aqueous barium ions and barium surface species. Atomic-level mineralwater interfacial structure and kinetics are being studied with increasing precision due to advances in spectroscopic methods at synchrotron x-ray sources as well as improved computational capacity. Better characterization of these interfaces in turn is leading to advances in the understanding of many macroscopic geochemical properties. Overall the barite-water interfacial structure was found to compare well to that estimated using X-ray reflectivity (XRR) measurements (Fenter et al., 2001), but there was an important difference: the MD predicted an intricate water structure present at the interface with one major peak and several minor peaks whereas the XRR found only a single layer of water. This discrepancy is thought to result from a limited resolution in the Fenter et al. (2001) study as well as over-coordination of surface sulfates by the MD model.

Investigation of Na-CO2 Reaction with Initial Reaction in Various Reacting Surface

International Nuclear Information System (INIS)

Kim, Hyun Su; Park, Gunyeop; Kim, Soo Jae; Park, Hyun Sun; Kim, Moo Hwan; Wi, Myung-Hwan

2015-01-01

The reaction products that cause oxidation and erosion are threaten the heat transfer tubes so that it is necessary to investigate Na-CO 2 reaction according to various experimental parameter. Unlike SWR, Na-CO 2 reaction is more complex to deal with reaction kinetics. Since a comprehensive understanding of Na-CO 2 reaction mechanism is crucial for the safety analysis, the reaction phenomenon under the various conditions was investigated. The current issue is to make a database for developing computational code for CO 2 gas leak situation because it is experimentally difficult to analyze the actual accident situation. Most studies on Na-CO 2 interaction reports that chemical reaction is getting vigorous as temperature increased and reactivity is sensitive as temperature change between 400 .deg. C and 600 .deg. C. Therefore, temperature range is determined based on the operating condition (450 - 500 .deg. C) of KALIMER-600 employed as supercritical CO 2 brayton cycle energy conversion system for Na-CO 2 heat exchanger. And next parameter is sodium surface area which contact between sodium and CO 2 when CO 2 is injected into sodium pool in the accident situation. So, the fundamental surface reaction is experimentally studied in the range of 8 - 12cm 2 . Additionally, it has been reported in recent years that CO 2 Flow rate affects reactivity less significantly and CO 2 flow rate is assumed that 5 SLPM (standard liter per minute) is suitable as a basis for a small leakage. The finally selected control parameters is sodium temperature and reacting surface area with constant CO 2 flow rate. Na-CO 2 reaction test is performed for investigating risk of potential accident which contacts with liquid sodium and CO 2 . Amount of reaction is saturated as time passed because of kept a balance between production of solid phase reaction products and amount of diffusivity. These results contribute to make a database for the SFR safety analysis and additional experiments are needed

Pore scale study of multiphase multicomponent reactive transport during CO2 dissolution trapping

Science.gov (United States)

Chen, Li; Wang, Mengyi; Kang, Qinjun; Tao, Wenquan

2018-06-01

Solubility trapping is crucial for permanent CO2 sequestration in deep saline aquifers. For the first time, a pore-scale numerical method is developed to investigate coupled scCO2-water two-phase flow, multicomponent (CO2(aq), H+, HCO3-, CO32- and OH-) mass transport, heterogeneous interfacial dissolution reaction, and homogeneous dissociation reactions. Pore-scale details of evolutions of multiphase distributions and concentration fields are presented and discussed. Time evolutions of several variables including averaged CO2(aq) concentration, scCO2 saturation, and pH value are analyzed. Specific interfacial length, an important variable which cannot be determined but is required by continuum models, is investigated in detail. Mass transport coefficient or efficient dissolution rate is also evaluated. The pore-scale results show strong non-equilibrium characteristics during solubility trapping due to non-uniform distributions of multiphase as well as slow mass transport process. Complicated coupling mechanisms between multiphase flow, mass transport and chemical reactions are also revealed. Finally, effects of wettability are also studied. The pore-scale studies provide deep understanding of non-linear non-equilibrium multiple physicochemical processes during CO2 solubility trapping processes, and also allow to quantitatively predict some important empirical relationships, such as saturation-interfacial surface area, for continuum models.

Dissolution of spherical cap CO2 bubbles attached to flat surfaces in air-saturated water

Science.gov (United States)

Peñas, Pablo; Parrales, Miguel A.; Rodriguez-Rodriguez, Javier

2014-11-01

Bubbles attached to flat surfaces immersed in quiescent liquid environments often display a spherical cap (SC) shape. Their dissolution is a phenomenon commonly observed experimentally. Modelling these bubbles as fully spherical may lead to an inaccurate estimate of the bubble dissolution rate. We develop a theoretical model for the diffusion-driven dissolution or growth of such multi-component SC gas bubbles under constant pressure and temperature conditions. Provided the contact angle of the bubble with the surface is large, the concentration gradients in the liquid may be approximated as spherically symmetric. The area available for mass transfer depends on the instantaneous bubble contact angle, whose dynamics is computed from the adhesion hysteresis model [Hong et al., Langmuir, vol. 27, 6890-6896 (2011)]. Numerical simulations and experimental measurements on the dissolution of SC CO2 bubbles immersed in air-saturated water support the validity of our model. We verify that contact line pinning slows down the dissolution rate, and the fact that any bubble immersed in a saturated gas-liquid solution eventually attains a final equilibrium size. Funded by the Spanish Ministry of Economy and Competitiveness through Grant DPI2011-28356-C03-0.

SON68 nuclear glass dissolution kinetics: Current state of knowledge and basis of the new GRAAL model

Energy Technology Data Exchange (ETDEWEB)

Frugier, P. [CEA Marcoule, DTCD/SECM/LCLT, BP 17171, 30207 Bagnols-sur-Ceze cedex (France)], E-mail: pierre.frugier@cea.fr; Gin, S.; Minet, Y.; Chave, T. [CEA Marcoule, DTCD/SECM/LCLT, BP 17171, 30207 Bagnols-sur-Ceze cedex (France); Bonin, B. [CEA Saclay, DEN/DIR/DS, 91191 Gif-sur-Yvette cedex (France); Godon, N.; Lartigue, J.-E.; Jollivet, P. [CEA Marcoule, DTCD/SECM/LCLT, BP 17171, 30207 Bagnols-sur-Ceze cedex (France); Ayral, A. [IEM/CNRS-ENSCM Universite Montpellier 2, CC 047, Place Eugene Bataillon, 34095 Montpellier cedex 5 (France); De Windt, L. [ENSMP, CG, 35 rue St Honore, 77305 Fontainebleau cedex (France); Santarini, G. [CEA Saclay HC/CAB, 91191 Gif-sur-Yvette cedex (France)

2008-10-15

This article summarizes the present state of knowledge concerning aqueous alteration of R7T7-type nuclear containment glasses, represented mainly by the inactive reference glass designated SON68. Based on this review, we propose to describe the glass alteration kinetics up to and including the final residual rate regime by means of a new mechanistic model known as GRAAL (glassreactivitywithallowanceforthealterationlayer). Phenomenological analysis findings are reviewed for the various glass alteration regimes: interdiffusion, initial rate, rate drop, residual rate and, under very particular circumstances, resumption of alteration. These alteration regimes are associated with predominant mechanisms. Published work interpreting and modeling these mechanisms was examined in detail. There is a broad consensus on the general mechanisms of the initial rate and even the interdiffusion regime, whereas the mechanisms controlling the rate drop remain a subject of dispute not only with regard to nuclear glasses but also for the dissolution of silicate minerals. The reaction affinity responsible for the rate drop is expressed differently by different authors and depending on the underlying theories. The disagreement concerns the nature of the phase (glass or gel) or the activated complex controlling the rate drop, which in turn determines the elements that must be taken into account in the overall affinity term. Progress in recent years, especially in identifying the mechanisms responsible for the residual rate, has shed new light on these issues, allowing us to propose new theoretical foundations for modeling the different kinetic regimes of SON68 nuclear glass dissolution. The GRAAL model considers that water diffusion in the passivating reaction zone (the gel formed under saturation conditions) is a rate-limiting step in the overall glass dissolution kinetics. Moreover, this passivation zone is a soluble phase whose stability is directly dependent on the nature of the

Mechanisms that control aqueous leaching of nuclear waste glass

International Nuclear Information System (INIS)

Simmons, J.H.; Barkatt, A.; Macedo, P.B.

1982-01-01

The development of predictive models and risk calculations for the time evolution of radioactive isotope leaching from fixation solids depends on many factors, including measurement accuracy, measurement relevance, a complete understanding of possible dissolution mechanisms, and the ability to project worst case conditions for all appropriate mechanisms. Some of the mechanisms observed and understood at present are the mechanisms of dissolution of glasses in neutral unbuffered water, the effects of structural disintegration of the glass protective layer, the effects of slowly flowing bath waters and possibly, the mechanisms of leach-rate reduction by solution saturation. The mechanisms that control radiation and temperature effects including alpha particle emission and nuclear transmutations are as yet little understood or investigated

Converged three-dimensional quantum mechanical reaction probabilities for the F + H2 reaction on a potential energy surface with realistic entrance and exit channels and comparisons to results for three other surfaces

Science.gov (United States)

Lynch, Gillian C.; Halvick, Philippe; Zhao, Meishan; Truhlar, Donald G.; Yu, Chin-Hui; Kouri, Donald J.; Schwenke, David W.

1991-01-01

Accurate three-dimensional quantum mechanical reaction probabilities are presented for the reaction F + H2 yields HF + H on the new global potential energy surface 5SEC for total angular momentum J = 0 over a range of translational energies from 0.15 to 4.6 kcal/mol. It is found that the v-prime = 3 HF vibrational product state has a threshold as low as for v-prime = 2.

Quantum mechanical/molecular mechanical modeling finds Diels-Alder reactions are accelerated less on the surface of water than in water.

Science.gov (United States)

Thomas, Laura L; Tirado-Rives, Julian; Jorgensen, William L

2010-03-10

Quantum and molecular mechanics calculations for the Diels-Alder reactions of cyclopentadiene with 1,4-naphthoquinone, methyl vinyl ketone, and acrylonitrile have been carried out at the vacuum-water interface and in the gas phase. In conjunction with previous studies of these cycloadditions in dilute solution, a more complete picture of aqueous environmental effects emerges with implications for the origin of observed rate accelerations using heterogeneous aqueous suspensions, "on water" conditions. The pure TIP4P water slab maintains the bulk density and hydrogen-bonding properties in central water layers. The bulk region merges to vacuum over a ca. 5 A band with progressive diminution of the density and hydrogen bonding. The relative free energies of activation and transition structures for the reactions at the interface are found to be intermediate between those calculated in the gas phase and in bulk water; i.e., for the reaction with 1,4-naphthoquinone, the DeltaDeltaG(++) values relative to the gas phase are -3.6 and -7.3 kcal/mol at the interface and in bulk water, respectively. Thus, the results do not support the notion that a water surface is more effective than bulk water for catalysis of such pericyclic reactions. The trend is in qualitative agreement with expectations based on density considerations and estimates of experimental rate constants for the gas phase, a heterogeneous aqueous suspension, and a dilute aqueous solution for the reaction of cyclopentadiene with methyl vinyl ketone. Computed energy pair distributions reveal a uniform loss of 0.5-1.0 hydrogen bond for the reactants and transition states in progressing from bulk water to the vacuum-water interface. Orientational effects are apparent at the surface; e.g., the carbonyl group in the methyl vinyl ketone transition structure is preferentially oriented into the surface. Also, the transition structure for the 1,4-naphthoquinone case is buried more in the surface, and the free energy of

Zinc deposition and dissolution in methanesulfonic acid onto a carbon composite electrode as the negative electrode reactions in a hybrid redox flow battery

International Nuclear Information System (INIS)

Leung, P.K.; Ponce-de-Leon, C.; Low, C.T.J.; Walsh, F.C.

2011-01-01

Highlights: → Use methanesulfonic acid to avoid dendrite formation during a long (>4 h) zinc electrodeposition. → Electrochemical characterization of Zn(II) deposition and its morphology using methanesulfonic acid solutions. → Use of additives to improve the efficiency of zinc deposition and dissolution as the half cell reaction of a redox flow battery. - Abstract: Electrodeposition and dissolution of zinc in methanesulfonic acid were studied as the negative electrode reactions in a hybrid redox flow battery. Cyclic voltammetry at a rotating disk electrode was used to characterize the electrochemistry and the effect of process conditions on the deposition and dissolution rate of zinc in aqueous methanesulfonic acid. At a sufficiently high current density, the deposition process became a mass transport controlled reaction. The diffusion coefficient of Zn 2+ ions was 7.5 x 10 -6 cm 2 s -1 . The performance of the zinc negative electrode in a parallel plate flow cell was also studied as a function of Zn 2+ ion concentration, methanesulfonic acid concentration, current density, electrolyte flow rate, operating temperature and the addition of electrolytic additives, including potassium sodium tartarate, tetrabutylammonium hydroxide, and indium oxide. The current-, voltage- and energy efficiencies of the zinc-half cell reaction and the morphologies of the zinc deposits are also discussed. The energy efficiency improved from 62% in the absence of additives to 73% upon the addition of 2 x 10 -3 mol dm -3 of indium oxide as a hydrogen suppressant. In aqueous methanesulfonic acid with or without additives, there was no significant dendrite formation after zinc electrodeposition for 4 h at 50 mA cm -2 .

All-cellulose composites of regenerated cellulose fibres by surface selective dissolution

NARCIS (Netherlands)

Soykeabkaew, N.; Nishino, T.; Peijs, Ton

2009-01-01

All-cellulose composites of Lyocell and high modulus/strength cellulose fibres were successfully prepared using a surface selective dissolution method. The effect of immersion time of the fibres in the solvent during composite's preparation and the effect of the starting fibre's structure on their

Corrosion mechanism of a Ni-based alloy in supercritical water: Impact of surface plastic deformation

International Nuclear Information System (INIS)

Payet, Mickaël; Marchetti, Loïc; Tabarant, Michel; Chevalier, Jean-Pierre

2015-01-01

Highlights: • The dissolution of Ni and Fe cations occurs during corrosion of Ni-based alloys in SCW. • The nature of the oxide layer depends locally on the alloy microstructure. • The corrosion mechanism changes when cold-work increases leading to internal oxidation. - Abstract: Ni–Fe–Cr alloys are expected to be a candidate material for the generation IV nuclear reactors that use supercritical water at temperatures up to 600 °C and pressures of 25 MPa. The corrosion resistance of Alloy 690 in these extreme conditions was studied considering the surface finish of the alloy. The oxide scale could suffer from dissolution or from internal oxidation. The presence of a work-hardened zone reveals the competition between the selective oxidation of chromium with respect to the oxidation of nickel and iron. Finally, corrosion mechanisms for Ni based alloys are proposed considering the effects of plastically deformed surfaces and the dissolution.

Effect of dissolution kinetics on flotation response of calcite with oleate

Directory of Open Access Journals (Sweden)

D. G. Horta

Full Text Available Abstract Phosphate flotation performance can be influenced by the dissolution kinetics of the minerals that compose the ore. The purpose of this work was to investigate the effect of dissolution kinetics on flotation response with oleate (collector of calcites from different origins and genesis. The calcite samples were first purified and characterized by x-ray Fluorescence (XRF and the Rietveld method applied to x-ray Diffractometry data (RXD. Experiments of calcite dissolution and microflotationwere performed at pH 8 and pH 10.The pH effect on the calcite dissolution and flotation indicates the possible influence of the carbonate/bicarbonate ions provided by the CO2 present in the air. In addition, the flotation response is greater as the dissolution increases, making more Ca2+ ions available to interact with collector molecules. This result corroborates the surface precipitation mechanism proposed foroleate adsorption on the calcite surface.

Mechanisms and kinetics laws of inactive R7T7 reference glass dissolution in water at 90 deg C: initial dissolution rate measurements

International Nuclear Information System (INIS)

Advocat, T.; Ghaleb, D.; Vernaz, E.

1993-02-01

The initial dissolution rate of inactive R7T7 reference glass was measured at 90 deg C in dilute aqueous solutions first at unspecified pH, then with imposed pH values. In distilled water, R7T7 glass corrosion initially involved preferential extraction of boron and network modifier elements (Li, Na, Ca) as long as the solution pH remained acid. When the solution pH became alkaline, glass dissolution was stoichiometric. These two mechanisms were confirmed by dissolution tests in aqueous solutions at imposed pH values under acid and alkaline conditions. The initial dissolution rate r 0 in mole.cm -3 .s -1 also increased significantly in alkaline media when the pH of the aqueous phase increased: in slightly acid media, selective glass dissolution formed a residual, de-alkalinized, hydrated glass that was characterized by transmission electron microscopy and secondary ion mass spectrometry. Under steady-state dissolution conditions, the initial glass corrosion rate (in mole.cm -3 .s -1 ) was: in acid and alkaline media, amorphous and crystallized alteration products formed after complete dissolution of the silicated glass network. The first products formed consisted mainly of Zr, Rare Earths, Fe and Al. (author). 67 refs., 29 figs., 26 tabs., 21 plates

Rationalizing the mechanism of HMDS degradation in air and effective control of the reaction byproducts

Science.gov (United States)

Seguin, Kevin; Dallas, Andrew J.; Weineck, Gerald

2008-03-01

The concern over molecular contamination on the surfaces of optics continues to grow. Most recently, this concern has focused on siloxane contamination resulting from hexamethyldisilazane (HMDS) which is commonly used as a wafer treatment to improve photoresist adhesion onto wafers. From this process, HMDS vapor can be found within FABs and process tools where it has been linked to issues related to lens hazing. This type of surface contamination is significantly detrimental to the imaging process and is generally corrected by extensive surface cleaning or even lens replacement. Additionally, this type of repair also requires adjustment of the optical axis, thereby contributing to an extended downtime. HMDS is known to be very sensitive to the presence of water and is therefore believed to degrade in humid airstreams. This research focuses on rationalizing the reaction mechanisms of HMDS in dry and humid airstreams and in the presence of several adsorbent surfaces. It is shown that HMDS hydrolyzes in humid air to trimethylsilanol (TMS) and ammonia (NH 3). Furthermore, it is shown that TMS can dimerize in air, or on specific types of adsorption media, to form hexamethyldisiloxane (HMDSO). Additionally, we report on the relative impact of these reaction mechanisms on the removal of both HMDS and its hydrolysis products (TMS, HMDSO and NH 3).

Thermodynamic and Kinetic Aspects of the Dissolution of Quartz-Kaolinite Mixtures by Alkalis Aspects thermodynamiques et cinétiques de la dissolution des mélanges quartz-kaolinite par les alcalis

Directory of Open Access Journals (Sweden)

Labrid J.

2006-11-01

Full Text Available Mineral-alkali interactions have received considerable attention in the recent literature dealing with enhanced oil recovery techniques and clay stabilization treatments. One of the critical factors to be considered is alkali consumption. Alkalinity decrease occurs through several mechanisms, which are ion exchange, precipitation, reaction with crude oil components, and dissolution of minerals. This paper describes the dissolution process. An original kinetic model is proposed to describe the alkaline dissolution of a clayey sandstone. This model is based first on results concerning quartz dissolution/condensation processes. It is also based on new experimental data, which demonstrate the inhibiting effect of aluminum and, as the reaction proceeds, the precipitation of an aluminosilicate whose the chemical composition has been determined. From these data, a kinetic scheme has been conceived in which adsorption of different chemical species is assumed to occur onto solid surfaces. These species play a more or less important role according to the extent of the reaction. In the mechanisms considered, the argillaceous fraction of the rock provides silicon and aluminum which inhibit the dissolution of the matrix while silicon coming from quartz interferes with clay attack. The kinetic model depicts the coupling of elementary dissolution processes and calculates dissolved silicon and aluminum. It has been tested for various operating conditions, providing initial reaction rates for quartz and clay. Results emphasize the definitive advantage of carbonate compared to other alkaline chemicals owing to the relative low pH of solutions, which is particularly favorable for promoting inhibition by aluminum and, as a general rule, for reducing mineral dissolution. Ce résumé contient des formules (*** qui ne peuvent s'afficher à l'écran L'emploi des agents alcalins pour améliorer la récupération du pétrole a été préconisé à l'origine dans le but

Role of nitrous acid during the dissolution of UO2 in nitric acid

International Nuclear Information System (INIS)

Deigan, N.; Pandey, N.K.; Kamachi Mudali, U.; Joshi, J.B.

2016-01-01

Understanding the dissolution behaviour of sintered UO 2 pellet in nitric acid is very important in designing an industrial scale dissolution system for the plutonium rich fast reactor MOX fuel. In the current article we have established the role of nitrous acid on the dissolution kinetics of UO 2 pellets in nitric acid. Under the chemical conditions that prevail in a typical Purex process, NO and NO 2 gases gets generated in the process streams. These gases produce nitrous acid in nitric acid medium. In addition, during the dissolution of UO 2 in nitric acid medium, nitrous acid is further produced in-situ at the pellet solution interface. As uranium dissolves oxidatively in nitric acid medium wherein it goes from U(IV) in solid to U(VI) in liquid, presence of nitrous acid (a good oxidizing agent) accelerates the reaction rate. Hence for determining the reaction mechanism of UO 2 dissolution in nitric acid medium, knowing the nitrous acid concentration profile during the course of dissolution is important. The current work involves the measurement of nitrous acid concentration during the course of dissolution of sintered UO 2 pellets in 8M starting nitric acid concentration as a function of mixing intensity from unstirred condition to 1500 RPM

A Comparison of Analytical and Numerical Methods for Modeling Dissolution and Other Reactions in Transport Limited Systems

Science.gov (United States)

Hochstetler, D. L.; Kitanidis, P. K.

2009-12-01

Modeling the transport of reactive species is a computationally demanding problem, especially in complex subsurface media, where it is crucial to improve understanding of geochemical processes and the fate of groundwater contaminants. In most of these systems, reactions are inherently fast and actual rates of transformations are limited by the slower physical transport mechanisms. There have been efforts to reformulate multi-component reactive transport problems into systems that are simpler and less demanding to solve. These reformulations include defining conservative species and decoupling of reactive transport equations so that fewer of them must be solved, leaving mostly conservative equations for transport [e.g., De Simoni et al., 2005; De Simoni et al., 2007; Kräutle and Knabner, 2007; Molins et al., 2004]. Complex and computationally cumbersome numerical codes used to solve such problems have also caused De Simoni et al. [2005] to develop more manageable analytical solutions. Furthermore, this work evaluates reaction rates and has reaffirmed that the mixing rate,▽TuD▽u, where u is a solute concentration and D is the dispersion tensor, as defined by Kitanidis [1994], is an important and sometimes dominant factor in determining reaction rates. Thus, mixing of solutions is often reaction-limiting. We will present results from analytical and computational modeling of multi-component reactive-transport problems. The results have applications to dissolution of solid boundaries (e.g., calcite), dissolution of non-aqueous phase liquids (NAPLs) in separate phases, and mixing of saltwater and freshwater (e.g. saltwater intrusion in coastal carbonate aquifers). We quantify reaction rates, compare numerical and analytical results, and analyze under what circumstances which approach is most effective for a given problem. References: DeSimoni, M., et al. (2005), A procedure for the solution of multicomponent reactive transport problems, Water Resources Research, 41

Aluminium dissolution for spray pulverization with nitric acid

International Nuclear Information System (INIS)

Rodrigo Otero, A.; Rodrigo Vilaseca, F.; Morales Calvo, G.

1977-01-01

A comparative study of the nitric acid dissolution of aluminium, by immersion and spray pulverization has been carried out in laboratory scale. As a result, the optimum operation conditions to control reaction in the plant are fixed. Operation costs are also evaluated. (author) [es

A kinetic model of the oxidative dissolution of brannerite, UTi2O6

International Nuclear Information System (INIS)

Thomas, B.S.; Zhang, Y.

2003-01-01

The aqueous dissolution of synthetic brannerite (UTi 2 O 6 ) in an open atmosphere has been investigated. Previous data in the literature have been combined with new experimental work, dealing with the release of uranium from brannerite as a function of solution pH and aqueous carbonate species, in oxygenated solutions. From these data we have developed a conceptual model for uranium release from brannerite consisting of two reaction steps: oxidation of surface uranium(IV) atoms, and subsequent detachment of U(VI) atoms into solution, which is catalysed by surface coordination with protons (acidic media) or carbonate species (alkaline media in equilibrium with the atmosphere). A kinetic rate law is derived for this simple reaction mechanism and fitted to experimental data. The resulting predictive equation for uranium release qualitatively describes the pH-dependent behaviour observed in experiment, and quantitatively gives an upper limit for uranium release from brannerite over a range of conditions and experiment types. (orig.)

Chemical kinetics and reaction mechanism

International Nuclear Information System (INIS)

Jung, Ou Sik; Park, Youn Yeol

1996-12-01

This book is about chemical kinetics and reaction mechanism. It consists of eleven chapters, which deal with reaction and reaction speed on reaction mechanism, simple reaction by rate expression, reversible reaction and simultaneous reaction, successive reaction, complicated reaction mechanism, assumption for reaction mechanism, transition state theory, successive reaction and oscillating reaction, reaction by solution, research method high except kinetics on reaction mechanism, high reaction of kinetics like pulsed radiolysis.

Chapter 9: Model Systems for Formation and Dissolution of Calcium Phosphate Minerals

Energy Technology Data Exchange (ETDEWEB)

Orme, C A; Giocondi, J L

2006-07-29

Calcium phosphates are the mineral component of bones and teeth. As such there is great interest in understanding the physical mechanisms that underlie their growth, dissolution, and phase stability. Control is often achieved at the cellular level by the manipulation of solution states and the use of crystal growth modulators such as peptides or other organic molecules. This chapter begins with a discussion of solution speciation in body fluids and relates this to important crystal growth parameters such as the supersaturation, pH, ionic strength and the ratio of calcium to phosphate activities. We then discuss the use of scanning probe microscopy as a tool to measure surface kinetics of mineral surfaces evolving in simplified solutions. The two primary themes that we will touch on are the use of microenvironments that temporally evolve the solution state to control growth and dissolution; and the use of various growth modifiers that interact with the solution species or with mineral surfaces to shift growth away from the lowest energy facetted forms. The study of synthetic minerals in simplified solution lays the foundation for understand mineralization process in more complex environments found in the body.

Chemical reactions on platinum-group metal surfaces studied by synchrotron-radiation-based spectroscopy

International Nuclear Information System (INIS)

Kondoh, Hiroshi; Nakai, Ikuyo; Nagasaka, Masanari; Amemiya, Kenta; Ohta, Toshiaki

2009-01-01

A new version of synchrotron-radiation-based x-ray spectroscopy, wave-length-dispersive near-edge x-ray absorption fine structure (dispersive-NEXAFS), and fast x-ray photoelectron spectroscopy have been applied to mechanistic studies on several surface catalytic reactions on platinum-group-metal surfaces. In this review, our approach using above techniques to understand the reaction mechanism and actual application studies on three well-known catalytic surface reactions, CO oxidation on Pt(111) and Pd(111), NO reduction on Rh(111), and H 2 O formation on Pt(111), are introduced. Spectroscopic monitoring of the progress of the surface reactions enabled us to detect reaction intermediates and analyze the reaction kinetics quantitatively which provides information on reaction order, rate constant, pre-exponential factor, activation energy and etc. Such quantitative analyses combined with scanning tunneling microscopy and kinetic Monte Carlo simulations revealed significant contribution of the adsorbate configurations and their dynamic changes to the reaction mechanisms of the above fundamental catalytic surface reactions. (author)

Effects of alteration product precipitation on glass dissolution

Energy Technology Data Exchange (ETDEWEB)

Strachan, Denis M.; Neeway, James J.

2014-06-01

Understanding the mechanisms that control the durability of nuclear waste glass is paramount if reliable models are to be constructed so that the glass dissolution rate in a given geological repository can be calculated. Presently, it is agreed that (boro)silicate glasses dissolve in water at a rate dependent on the solution concentration of orthosilicic acid (H₄SiO₄) with higher [H₄SiO₄] leading to lower dissolution rates. Once the reaction has slowed as a result of the buildup of H₄SiO₄, another increase in the rate has been observed that corresponds to the precipitation of certain silica-bearing alteration products. However, it has also been observed that the concentration of silica-bearing solution species does not significantly decrease, indicating saturation, while other glass tracer elements concentrations continue to increase, indicating that the glass is still dissolving. In this study, we have used the Geochemist’s Workbench code to investigate the relationship between glass dissolution rates and the precipitation rate of a representative zeolitic silica-bearing alteration product, analcime [Na(AlSi₂O₆)∙H₂O]. To simplify the calculations, we suppressed all alteration products except analcime, gibbsite (Al(OH)₃), and amorphous silica. The pseudo-equilibrium-constant matrix for amorphous silica was substituted for the glass pseudo-equilibrium-constant matrix because it has been shown that silicate glasses act as a silica-only solid with respect to kinetic considerations. In this article, we present the results of our calculations of the glass dissolution rate at different values for the analcime precipitation rate constant and the effects of varying the glass dissolution rate constant at a constant analcime precipitation rate constant. From the simulations we conclude, firstly, that the rate of glass dissolution is dependent on the kinetics of

Surface layer effects on waste glass corrosion

International Nuclear Information System (INIS)

Feng, X.

1993-01-01

Water contact subjects waste glass to chemical attack that results in the formation of surface alteration layers. Two principal hypotheses have been advanced concerning the effect of surface alteration layers on continued glass corrosion: (1) they act as a mass transport barrier and (2) they influence the chemical affinity of the glass reaction. In general, transport barrier effects have been found to be less important than affinity effects in the corrosion of most high-level nuclear waste glasses. However, they can be important under some circumstances, for example, in a very alkaline solution, in leachants containing Mg ions, or under conditions where the matrix dissolution rate is very low. The latter suggests that physical barrier effect may affect the long-term glass dissolution rate. Surface layers influence glass reaction affinity through the effects of the altered glass and secondary phases on the solution chemistry. The reaction affinity may be controlled by various precipitates and crystalline phases, amorphous silica phases, gel layer, or all the components of the glass. The surface alteration layers influence radionuclide release mainly through colloid formation, crystalline phase incorporation, and gel layer retention. This paper reviews current understanding and uncertainties

Chrysotile dissolution rates: Implications for carbon sequestration

International Nuclear Information System (INIS)

Thom, James G.M.; Dipple, Gregory M.; Power, Ian M.; Harrison, Anna L.

2013-01-01

Highlights: • Uncertainties in serpentine dissolution kinetics hinder carbon sequestration models. • A pH dependent, far from equilibrium dissolution rate law for chrysotile. • F chrysotile (mol/m 2 /s) = 10 −0.21pH−10.57 at 22 °C over pH 2–10. • Laboratory dissolution rates consistent with mine waste weathering observations. • Potential for carbon sequestration in mine tailings and aquifers is assessed. - Abstract: Serpentine minerals (e.g., chrysotile) are a potentially important medium for sequestration of CO 2 via carbonation reactions. The goals of this study are to report a steady-state, far from equilibrium chrysotile dissolution rate law and to better define what role serpentine dissolution kinetics will have in constraining rates of carbon sequestration via serpentine carbonation. The steady-state dissolution rate of chrysotile in 0.1 m NaCl solutions was measured at 22 °C and pH ranging from 2 to 8. Dissolution experiments were performed in a continuously stirred flow-through reactor with the input solutions pre-equilibrated with atmospheric CO 2 . Both Mg and Si steady-state fluxes from the chrysotile surface, and the overall chrysotile flux were regressed and the following empirical relationships were obtained: F Mg =-0.22pH-10.02;F Si =-0.19pH-10.37;F chrysotile =-0.21pH-10.57 where F Mg , F Si , and F chrysotile are the log 10 Mg, Si, and molar chrysotile fluxes in mol/m 2 /s, respectively. Element fluxes were used in reaction-path calculations to constrain the rate of CO 2 sequestration in two geological environments that have been proposed as potential sinks for anthropogenic CO 2 . Carbon sequestration in chrysotile tailings at 10 °C is approximately an order of magnitude faster than carbon sequestration in a serpentinite-hosted aquifer at 60 °C on a per kilogram of water basis. A serpentinite-hosted aquifer, however, provides a larger sequestration capacity. The chrysotile dissolution rate law determined in this study has

In situ Raman scattering study on a controllable plasmon-driven surface catalysis reaction on Ag nanoparticle arrays

International Nuclear Information System (INIS)

Dai, Z G; Xiao, X H; Zhang, Y P; Ren, F; Wu, W; Zhang, S F; Zhou, J; Jiang, C Z; Mei, F

2012-01-01

Control of the plasmon-driven chemical reaction for the transformation of 4-nitrobenzenethiol to p,p′-dimercaptoazobenzene by Ag nanoparticle arrays was studied. The Ag nanoparticle arrays were fabricated by means of nanosphere lithography. By changing the PS particle size, the localized surface plasmon resonance (LSPR) peaks of the Ag nanoparticle arrays can be tailored from 460 to 560 nm. The controlled reaction process was monitored by in situ surface-enhanced Raman scattering. The reaction can be dramatically influenced by varying the duration of laser exposure, Ag nanoparticle size, laser power and laser excitation wavelength. The maximum reaction speed was achieved when the LSPR wavelength of the Ag nanoparticle arrays matched the laser excitation wavelength. The experimental results reveal that the strong LSPR can effectively drive the transfer of the ‘hot’ electrons that decay from the plasmon to the reactants. The experimental results were confirmed by theoretical calculations. (paper)

Destructive electronics from electrochemical-mechanically triggered chemical dissolution

International Nuclear Information System (INIS)

Sim, Kyoseung; Wang, Xu; Yu, Cunjiang; Li, Yuhang; Linghu, Changhong; Song, Jizhou; Gao, Yang

2017-01-01

The considerable need to enhance data and hardware security suggest one possible future for electronics where it is possible to destroy them and even make them disappear physically. This paper reports a type of destructive electronics which features fast transience from chemical dissolution on-demand triggered in an electrochemical-mechanical manner. The detailed materials, mechanics, and device construction of the destructive electronics are presented. Experiment and analysis of the triggered releasing and transience study of electronic materials, resistors and metal-oxide-semiconductor field effect transistors illustrate the key aspects of the destructive electronics. The reported destructive electronics is useful in a wide range of areas from security and defense, to medical applications (paper)

The dissolution rate of silicate glasses and minerals: an alternative model based on several activated complexes

International Nuclear Information System (INIS)

Berger, G.

1997-01-01

Most of the mineral reactions in natural water-rock systems progress at conditions close to the chemical equilibrium. The kinetics of these reactions, in particular the dissolution rate of the primary minerals, is a major constrain for the numerical modelling of diagenetic and hydrothermal processes. In the case of silicates, recent experimental studies have pointed out the necessity to better understand the elementary reactions which control the dissolution process. This article presents several models that have been proposed to account for the observed dissolution rate/chemical affinity relationships. The case of glasses (R7T7), feldspars and clays, in water, in near neutral pH aqueous solutions and in acid/basic media, are reviewed. (A.C.)

Effect of metallic iron on the oxidative dissolution of UO2 doped with a radioactive alpha emitter in synthetic Callovian-Oxfordian groundwater

Science.gov (United States)

Odorowski, Mélina; Jegou, Christophe; De Windt, Laurent; Broudic, Véronique; Jouan, Gauthier; Peuget, Sylvain; Martin, Christelle

2017-12-01

UO2 and leads to low uranium concentrations (between 4 × 10-10 and 4 × 10-9 M), through a reactional mechanism located in the very first microns of the UO2/water reactional interface. The mechanism involves consumption of oxidizing species, in particular of H2O2 by Fe2+ at the precise place where these species are produced, and is accompanied by the precipitation of an akaganeite-type Fe3+ hydroxide on the surface. The higher the radioactivity of the samples, the greater the precipitation induced. Modeling has been developed, coupling chemistry with transport and based on the main reactional mechanisms identified, which enables accurate reproduction of the mineralogy of the system under study, giving the nature of the phases under observation as well as the location of their precipitation. Obviously without excluding a potential contribution from the hydrogen produced by the anoxic corrosion of the iron foil, this study has shown that iron plays a major role in this oxidizing dissolution inhibition process for the system investigated (localized alpha radiolysis). This inhibitor effect associated with iron is therefore strongly dependent on the location of the redox front, which is found on the surface in the case of alpha irradiation UO2/water reactional interface.

In situ fabrication of electrochemically grown mesoporous metallic thin films by anodic dissolution in deep eutectic solvents.

Science.gov (United States)

Renjith, Anu; Roy, Arun; Lakshminarayanan, V

2014-07-15

We describe here a simple electrodeposition process of forming thin films of noble metallic nanoparticles such as Au, Ag and Pd in deep eutectic solvents (DES). The method consists of anodic dissolution of the corresponding metal in DES followed by the deposition on the cathodic surface. The anodic dissolution process in DES overcomes the problems associated with copious hydrogen and oxygen evolution on the electrode surface when carried out in aqueous medium. The proposed method utilizes the inherent abilities of DES to act as a reducing medium while simultaneously stabilizing the nanoparticles that are formed. The mesoporous metal films were characterized by SEM, XRD and electrochemical techniques. Potential applications of these substrates in surface enhanced Raman spectroscopy and electrocatalysis have been investigated. A large enhancement of Raman signal of analyte was achieved on the mesoporous silver substrate after removing all the stabilizer molecules from the surface by calcination. The highly porous texture of the electrodeposited film provides superior electro catalytic performance for hydrogen evolution reaction (HER). The mechanisms of HER on the fabricated substrates were studied by Tafel analysis and electrochemical impedance spectroscopy (EIS). Copyright © 2014 Elsevier Inc. All rights reserved.

Kinetics of dissolution of sapphire in melts in the CaO-Al2O3-SiO2 system

Science.gov (United States)

Shaw, Cliff S. J.; Klausen, Kim B.; Mao, Huahai

2018-05-01

The dissolution rate of sapphire in melts in the CAS system of varying silica activity, viscosity and degree of alumina saturation has been determined at 1600 °C and 1.5 GPa. After an initiation period of up to 1800 s, dissolution is controlled by diffusion of cations through the boundary layer adjacent to the dissolving sapphire. The dissolution rate decreases with increasing silica activity, viscosity and molar Al2O3/CaO. The calculated diffusion matrix for each solvent melt shows that CAS 1 and 9 which have molar Al2O3/CaO of 0.33 and 0.6 and dissolution rate constants of 0.65 × 10-6 and 0.59 × 10-6 m/s0.5 have similar directions and magnitudes of diffusive coupling: DCaO-Al2O3 and DAl2O3-CaO are both negative are approximately equal. The solvent with the fastest dissolution rate: CAS 4, which has a rate constant of 1.5 × 10-6 m/s0.5 and Al2O3/CaO of 0.31 has positive DCaO-Al2O3 and negative DAl2O3-CaO and the absolute values vary by a factor of 4. Although many studies show that aluminium is added to the melts via the reaction: Si4+ =Al3+ + 0.5Ca2+ the compositional profiles show that this reaction is not the only one involved in accommodating the aluminium added during sapphire dissolution. Rather, aluminium is incorporated as both tetrahedrally coordinated Al charge balanced by Ca and as aluminium not charge balanced by Ca (termed Alxs). This reaction: AlIV -Ca =Alxs +CaNBO where CaNBO is a non-bridging oxygen associated with calcium, may involve the formation of aluminium triclusters. The shape of the compositional profiles and oxide-oxide composition paths is controlled by the aluminium addition reaction. When Alxs exceeds 2%, CaO diffusion becomes increasingly anomalous and since the bond strength of Alxs correlates with CaO/CaO + Al2O3, the presence of more than 2% Alxs leads to significantly slower dissolution than when Alxs is absent or at low concentration. Thus, dissolution is controlled by diffusion of cations through the boundary layer, but this

A dissolution-precipitation mechanism is at the origin of concrete creep in moist environments

Energy Technology Data Exchange (ETDEWEB)

Pignatelli, Isabella [Laboratory for the Chemistry of Construction Materials (LC2), Department of Civil and Environmental Engineering, University of California, Los Angeles, California 90095 (United States); Kumar, Aditya [Materials Science and Engineering Department, Missouri University of Science and Technology, Rolla, Missouri 65409 (United States); Alizadeh, Rouhollah [Giatec Scientific, Ottawa, Ontario K2H 9C4 (Canada); Le Pape, Yann [Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831 (United States); Bauchy, Mathieu, E-mail: bauchy@ucla.edu, E-mail: gsant@ucla.edu [Physics of AmoRphous and Inorganic Solids Laboratory (PARISlab), Department of Civil and Environmental Engineering, University of California, Los Angeles, California 90095 (United States); Sant, Gaurav, E-mail: bauchy@ucla.edu, E-mail: gsant@ucla.edu [Laboratory for the Chemistry of Construction Materials (LC2), Department of Civil and Environmental Engineering, University of California, Los Angeles, California 90095 (United States); California Nanosystems Institute (CNSI), University of California, Los Angeles, California 90095 (United States)

2016-08-07

Long-term creep (i.e., deformation under sustained load) is a significant material response that needs to be accounted for in concrete structural design. However, the nature and origin of concrete creep remain poorly understood and controversial. Here, we propose that concrete creep at relative humidity ≥ 50%, but fixed moisture content (i.e., basic creep), arises from a dissolution-precipitation mechanism, active at nanoscale grain contacts, as has been extensively observed in a geological context, e.g., when rocks are exposed to sustained loads, in liquid-bearing environments. Based on micro-indentation and vertical scanning interferometry data and molecular dynamics simulations carried out on calcium–silicate–hydrate (C–S–H), the major binding phase in concrete, of different compositions, we show that creep rates are correlated with dissolution rates—an observation which suggests a dissolution-precipitation mechanism as being at the origin of concrete creep. C–S–H compositions featuring high resistance to dissolution, and, hence, creep are identified. Analyses of the atomic networks of such C–S–H compositions using topological constraint theory indicate that these compositions present limited relaxation modes on account of their optimally connected (i.e., constrained) atomic networks.

Exploring Reaction Mechanism on Generalized Force Modified Potential Energy Surfaces (G-FMPES) for Diels-Alder Reaction

Science.gov (United States)

Jha, Sanjiv; Brown, Katie; Subramanian, Gopinath

We apply a recent formulation for searching minimum energy reaction path (MERP) and saddle point to atomic systems subjected to an external force. We demonstrate the effect of a loading modality resembling hydrostatic pressure on the trans to cis conformational change of 1,3-butadiene, and the simplest Diels-Alder reaction between ethylene and 1,3-butadiene. The calculated MERP and saddle points on the generalized force modified potential energy surface (G-FMPES) are compared with the corresponding quantities on an unmodified potential energy surface. Our study is performed using electronic structure calculations at the HF/6-31G** level as implemented in the AIMS-MOLPRO code. Our calculations suggest that the added compressive pressure lowers the energy of cis butadiene. The activation energy barrier for the concerted Diels-Alder reaction is found to decrease progressively with increasing compressive pressure.

Radiolytic modelling of spent fuel oxidative dissolution mechanism. Calibration against UO2 dynamic leaching experiments

International Nuclear Information System (INIS)

Merino, J.; Cera, E.; Bruno, J.; Quinones, J.; Casas, I.; Clarens, F.; Gimenez, J.; Pablo, J. de; Rovira, M.; Martinez-Esparza, A.

2005-01-01

Calibration and testing are inherent aspects of any modelling exercise and consequently they are key issues in developing a model for the oxidative dissolution of spent fuel. In the present work we present the outcome of the calibration process for the kinetic constants of a UO 2 oxidative dissolution mechanism developed for using in a radiolytic model. Experimental data obtained in dynamic leaching experiments of unirradiated UO 2 has been used for this purpose. The iterative calibration process has provided some insight into the detailed mechanism taking place in the alteration of UO 2 , particularly the role of · OH radicals and their interaction with the carbonate system. The results show that, although more simulations are needed for testing in different experimental systems, the calibrated oxidative dissolution mechanism could be included in radiolytic models to gain confidence in the prediction of the long-term alteration rate of the spent fuel under repository conditions

A literature review of surface alteration layer effects on waste glass behavior

International Nuclear Information System (INIS)

Feng, X.; Cunnane, J.C.; Bates, J.K.

1993-01-01

When in contact with an aqueous solution, nuclear waste glass is subject to a chemical attack that results in progressive alteration. During tills alteration, constituent elements of the glass pass into the solution; elements initially in solution diffuse into, or are adsorbed onto, the solid; and new phases appear. This results in the formation of surface layers on the reacted glass. The glass corrosion and radionuclide release can be better understood by investigating these surface layer effects. In the past decade, there have been numerous studies regarding the effects of surface layers on glass reactions. This paper presents a systematic analysis and summary of the past knowledge regarding the effects of surface layers on glass-water interaction. This paper describes the major formation mechanisms of surface layers; reviews the role of surface layers in controlling mass transport and glass reaction affinity (through crystalline phases, an amorphous silica, a gel layer, or all the components in the glass); and discusses how the surface layers contribute to the retention of radionuclides during glass dissolution

Reductive Dissolution of Goethite and Hematite by Reduced Flavins

Energy Technology Data Exchange (ETDEWEB)

Shi, Zhi; Zachara, John M.; Wang, Zheming; Shi, Liang; Fredrickson, Jim K.

2013-10-02

The abiotic reductive dissolution of goethite and hematite by the reduced forms of flavin mononucleotide (FMNH2) and riboflavin (RBFH2), electron transfer mediators (ETM) secreted by the dissimilatory iron-reducing bacterium Shewanella, was investigated under stringent anaerobic conditions. In contrast to the rapid redox reaction rate observed for ferrihydrite and lepidocrocite (Shi et al., 2012), the reductive dissolution of crystalline goethite and hematite was slower, with the extent of reaction limited by the thermodynamic driving force at circumneutral pH. Both the initial reaction rate and reaction extent increased with decreasing pH. On a unit surface area basis, goethite was less reactive than hematite between pH 4.0 and 7.0. AH2DS, the reduced form of the well-studied synthetic ETM anthraquinone-2,6-disulfonate (AQDS), yielded higher rates than FMNH2 under most reaction conditions, despite the fact that FMNH2 was a more effective reductant than AH2DS for ferryhydrite and lepidocrocite. Two additional model compounds, methyl viologen and benzyl viologen, were investigated under similar reaction conditions to explore the relationship between reaction rate and thermodynamic properties. Relevant kinetic data from the literature were also included in the analysis to span a broad range of half-cell potentials. Other conditions being equal, the surface area normalized initial reaction rate (ra) increased as the redox potential of the reductant became more negative. A non-linear, parabolic relationship was observed between log ra and the redox potential for eight reducants at pH 7.0, as predicted by Marcus theory for electron transfer. When pH and reductant concentration were fixed, log ra was positively correlated to the redox potential of four Fe(III) oxides over a wide pH range, following a non-linear parabolic relationship as well.

Controlled evaluation of silver nanoparticle dissolution using atomic force microscopy.

Science.gov (United States)

Kent, Ronald D; Vikesland, Peter J

2012-07-03

Incorporation of silver nanoparticles (AgNPs) into an increasing number of consumer products has led to concern over the potential ecological impacts of their unintended release to the environment. Dissolution is an important environmental transformation that affects the form and concentration of AgNPs in natural waters; however, studies on AgNP dissolution kinetics are complicated by nanoparticle aggregation. Herein, nanosphere lithography (NSL) was used to fabricate uniform arrays of AgNPs immobilized on glass substrates. Nanoparticle immobilization enabled controlled evaluation of AgNP dissolution in an air-saturated phosphate buffer (pH 7.0, 25 °C) under variable NaCl concentrations in the absence of aggregation. Atomic force microscopy (AFM) was used to monitor changes in particle morphology and dissolution. Over the first day of exposure to ≥10 mM NaCl, the in-plane AgNP shape changed from triangular to circular, the sidewalls steepened, the in-plane radius decreased by 5-11 nm, and the height increased by 6-12 nm. Subsequently, particle height and in-plane radius decreased at a constant rate over a 2-week period. Dissolution rates varied linearly from 0.4 to 2.2 nm/d over the 10-550 mM NaCl concentration range tested. NaCl-catalyzed dissolution of AgNPs may play an important role in AgNP fate in saline waters and biological media. This study demonstrates the utility of NSL and AFM for the direct investigation of unaggregated AgNP dissolution.

Self-activated, self-limiting reactions on Si surfaces

DEFF Research Database (Denmark)

Morgen, Per; Hvam, Jeanette; Bahari, Ali

The direct thermally activated reactions of oxygen and ammonia with Si surfaces in furnaces have been used for a very long time in the semiconductor industry for the growth of thick oxides and nitride layers respectively. The oxidation mechanism was described in the Deal-Grove model as a diffusion...... mechanism for the direct growth of ultrathin films (0-3 nm) of oxides and nitrides under ultrahigh vacuum conditions. Neutral oxygen and a microwave excited nitrogen plasma interact directly with Si surfaces kept at different temperatures during the reaction. The gas pressures are around 10-6 Torr...... energy of an oxide system, which happened for an ordered structure, at a thickness of 0.7-0.8 nm. Thus this thin oxide structure has definite crystalline features. We have closely monitored the reaction kinetics with normal x-ray induced photoelectron spectroscopies, and also the structure, composition...

Investigations on reducing microbiologically-influenced corrosion of aluminum by using super-hydrophobic surfaces

Energy Technology Data Exchange (ETDEWEB)

Liu Tao, E-mail: liutao@shmtu.edu.c [Institute of Marine Materials Science and Engineering, Shanghai Maritime University, Shanghai 201306 (China); Dong Lihua; Liu Tong; Yin Yansheng [Institute of Marine Materials Science and Engineering, Shanghai Maritime University, Shanghai 201306 (China)

2010-07-15

Electrochemical impedance spectroscopy, potentiodynamic polarization and scanning electron microscopy were carried out to determine the effect of super-hydrophobic surfaces on the marine bacterium Vibrio natriegens (V. natriegens) adhesion. Four different samples were prepared in order to investigate the anti-biocorrosion mechanism of super-hydrophobic surfaces. Potentiodynamic polarization suggested that the V. natriegens attached on the surface mainly enhanced the reaction kinetics of the anodic reaction and accelerated the dissolution of aluminum. EIS results were interpreted with different equivalent circuits to model the physicoelectric characteristics of the electrode/biofilm/solution interface. The results showed that neither anodization nor chemical modification could decrease the bacterial adhesion and corrosion rate individually. V. natriegens showed only weak attachment to the super-hydrophobic surface, and the biocorrosion mechanism was closely associated with surface energy and surface topography.

Investigations on reducing microbiologically-influenced corrosion of aluminum by using super-hydrophobic surfaces

International Nuclear Information System (INIS)

Liu Tao; Dong Lihua; Liu Tong; Yin Yansheng

2010-01-01

Electrochemical impedance spectroscopy, potentiodynamic polarization and scanning electron microscopy were carried out to determine the effect of super-hydrophobic surfaces on the marine bacterium Vibrio natriegens (V. natriegens) adhesion. Four different samples were prepared in order to investigate the anti-biocorrosion mechanism of super-hydrophobic surfaces. Potentiodynamic polarization suggested that the V. natriegens attached on the surface mainly enhanced the reaction kinetics of the anodic reaction and accelerated the dissolution of aluminum. EIS results were interpreted with different equivalent circuits to model the physicoelectric characteristics of the electrode/biofilm/solution interface. The results showed that neither anodization nor chemical modification could decrease the bacterial adhesion and corrosion rate individually. V. natriegens showed only weak attachment to the super-hydrophobic surface, and the biocorrosion mechanism was closely associated with surface energy and surface topography.

Transformation-Dissolution Reactions Partially Explain Adverse Effects of Metallic Silver Nanoparticles to Soil Nitrification in Different Soils.

Science.gov (United States)

Bollyn, Jessica; Willaert, Bernd; Kerré, Bart; Moens, Claudia; Arijs, Katrien; Mertens, Jelle; Leverett, Dean; Oorts, Koen; Smolders, Erik

2018-04-25

Risk assessment of metallic nanoparticles (NP) is critically affected by the concern that toxicity goes beyond that of the metallic ion. This study addressed this concern for soils with silver (Ag)-NP using the Ag-sensitive nitrification assay. Three agricultural soils (A,B,C) were spiked with equivalent Ag doses of either Ag-NP (d = 13 nm) or AgNO 3 . Soil solution was isolated and monitored over 97 days with due attention to accurate Ag fractionation at low (∼10 µg L -1 ) Ag concentrations. Truly dissolved (soils decreased with reaction half-lives of 4 to 22 days depending on the soil, denoting important Ag-ageing reactions. In contrast, truly dissolved Ag in Ag-NP-amended soils first increased by dissolution and subsequently decreased by ageing; the concentration never exceeding that in the AgNO 3 -amended soils. The half-lives of Ag-NP transformation-dissolution were about 4 days (soils A&B) and 36 days (soil C). The Ag toxic thresholds (EC10, mg Ag kg -1 soil) of nitrification, either evaluated at 21 or 35 days after spiking, were similar between the two Ag forms (soils A&B) but were factors 3 to 8 lower for AgNO 3 than for Ag-NP (soil C), largely corroborating with dissolution differences. This fate and bio-assay showed that Ag-NPs are not more toxic than AgNO 3 at equivalent total soil Ag concentrations and that differences in Ag-dissolution at least partially explain toxicity differences between the forms and among soils. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

Electrochemical studies of Copper, Tantalum and Tantalum Nitride surfaces in aqueous solutions for applications in chemical-mechanical and electrochemical-mechanical planarization

Science.gov (United States)

Sulyma, Christopher Michael

This report will investigate fundamental properties of materials involved in integrated circuit (IC) manufacturing. Individual materials (one at a time) are studied in different electrochemical environmental solutions to better understand the kinetics associated with the polishing process. Each system tries to simulate a real CMP environment in order to compare our findings with what is currently used in industry. To accomplish this, a variety of techniques are used. The voltage pulse modulation technique is useful for electrochemical processing of metal and alloy surfaces by utilizing faradaic reactions like electrodeposition and electrodissolution. A theoretical framework is presented in chapter 4 to facilitate quantitative analysis of experimental data (current transients) obtained in this approach. A typical application of this analysis is demonstrated for an experimental system involving electrochemical removal of copper surface layers, a relatively new process for abrasive-free electrochemical mechanical planarization of copper lines used in the fabrication of integrated circuits. Voltage pulse modulated electrodissolution of Cu in the absence of mechanical polishing is activated in an acidic solution of oxalic acid and hydrogen peroxide. The current generated by each applied voltage step shows a sharp spike, followed by a double-exponential decay, and eventually attains the rectangular shape of the potential pulses. For the second system in chapter 5, open-circuit potential measurements, cyclic voltammetry and Fourier transform impedance spectroscopy have been used to study pH dependent surface reactions of Cu and Ta rotating disc electrodes (RDEs) in aqueous solutions of succinic acid (SA, a complexing agent), hydrogen peroxide (an oxidizer), and ammonium dodecyl sulfate (ADS, a corrosion inhibitor for Cu). The surface chemistries of these systems are relevant for the development of a single-slurry approach to chemical mechanical planarization (CMP) of Cu

Chemical reaction on solid surface observed through isotope tracer technique

International Nuclear Information System (INIS)

Tanaka, Ken-ichi

1983-01-01

In order to know the role of atoms and ions on solid surfaces as the partners participating in elementary processes, the literatures related to the isomerization and hydrogen exchanging reaction of olefines, the hydrogenation of olefines, the metathesis reaction and homologation of olefines based on solid catalysts were reviewed. Various olefines, of which the hydrogen atoms were substituted with deuterium at desired positions, were reacted using various solid catalysts such as ZnO, K 2 CO 3 on C, MoS 2 (single crystal and powder) and molybdenum oxide (with various carriers), and the infra-red spectra of adsorbed olefines on catalysts, the isotope composition of reaction products and the production rate of the reaction products were measured. From the results, the bonding mode of reactant with the atoms and ions on solid surfaces, and the mechanism of the elementary process were considered. The author emphasized that the mechanism of the chemical reaction on solid surfaces and the role of active points or catalysts can be made clear to the considerable extent by combining isotopes suitably. (Yoshitake, I.)

Principles of calcite dissolution in human and artificial otoconia.

Directory of Open Access Journals (Sweden)

Leif Erik Walther

Full Text Available Human otoconia provide mechanical stimuli to deflect hair cells of the vestibular sensory epithelium for purposes of detecting linear acceleration and head tilts. During lifetime, the volume and number of otoconia are gradually reduced. In a process of degeneration morphological changes occur. Structural changes in human otoconia are assumed to cause vertigo and balance disorders such as benign paroxysmal positional vertigo (BPPV. The aim of this study was to investigate the main principles of morphological changes in human otoconia in dissolution experiments by exposure to hydrochloric acid, EDTA, demineralized water and completely purified water respectively. For comparison reasons artificial (biomimetic otoconia (calcite gelatin nanocomposits and natural calcite were used. Morphological changes were detected in time steps by the use of environmental scanning electron microscopy (ESEM. Under in vitro conditions three main dissolution mechanisms were identified as causing characteristic morphological changes of the specimen under consideration: pH drops in the acidic range, complex formation with calcium ions and changes of ion concentrations in the vicinity of otoconia. Shifts in pH cause a more uniform reduction of otoconia size (isotropic dissolution whereas complexation reactions and changes of the ionic concentrations within the surrounding medium bring about preferred attacks at specific areas (anisotropic dissolution of human and artificial otoconia. Owing to successive reduction of material, all the dissolution mechanisms finally produce fragments and remnants of otoconia. It can be assumed that the organic component of otoconia is not significantly attacked under the given conditions. Artificial otoconia serve as a suitable model system mimicking chemical attacks on biogenic specimens. The underlying principles of calcite dissolution under in vitro conditions may play a role in otoconia degeneration processes such as BPPV.

Anodic Dissolution of Spheroidal Graphite Cast Iron with Different Pearlite Areas in Sulfuric Acid Solutions

Directory of Open Access Journals (Sweden)

Yoshikazu Miyata

2013-01-01

Full Text Available The rate equation of anodic dissolution reaction of spheroidal graphite cast iron in sulfuric acid solutions at 298 K has been studied. The cast irons have different areas of pearlite. The anodic Tafel slope of 0.043 V decade−1 and the reaction order with respect to the hydroxyl ion activity of 1 are obtained by the linear potential sweep technique. The anodic current density does not depend on the area of pearlite. There is no difference in the anodic dissolution reaction mechanisms between pure iron and spheroidal graphite cast iron. The anodic current density of the cast iron is higher than that of the pure iron.

Mechanical stress-controlled tunable active frequency-selective surface

Science.gov (United States)

Huang, Bo-Cin; Hong, Jian-Wei; Lo, Cheng-Yao

2017-01-01

This study proposes a tunable active frequency-selective surface (AFSS) realized by mechanically expanding or contracting a split-ring resonator (SRR) array. The proposed AFSS transfers mechanical stress from its elastic substrate to the top of the SRR, thereby achieving electromagnetic (EM) modulation without the need for an additional external power supply, meeting the requirements for the target application: the invisibility cloak. The operating mechanism of the proposed AFSS differs from those of other AFSSs, supporting modulations in arbitrary frequencies in the target range. The proposed stress-controlled or strain-induced EM modulation proves the existence of an identical and linear relationship between the strain gradient and the frequency shift, implying its suitability for other EM modulation ranges and applications.

The effect of antimony presence in anodic copper on kinetics and mechanism of anodic dissolution and cathodic deposition of copper

Directory of Open Access Journals (Sweden)

Stanković Z.D.

2008-01-01

Full Text Available The influence of the presence of Sb atoms, as foreign metal atoms in anode copper, on kinetics, and, on the mechanism of anodic dissolution and cathodic deposition of copper in acidic sulfate solution has been investigated. The galvanostatic single-pulse method has been used. Results indicate that presence of Sb atoms in anode copper increase the exchange current density as determined from the Tafel analysis of the electrode reaction. It is attributed to the increase of the crystal lattice parameter determined from XRD analysis of the electrode material.

Investigation of Na-CO{sub 2} Reaction with Initial Reaction in Various Reacting Surface

Energy Technology Data Exchange (ETDEWEB)

Kim, Hyun Su; Park, Gunyeop; Kim, Soo Jae; Park, Hyun Sun; Kim, Moo Hwan [POSTECH, Pohang (Korea, Republic of); Wi, Myung-Hwan [KAERI, Daejeon (Korea, Republic of)

2015-10-15

The reaction products that cause oxidation and erosion are threaten the heat transfer tubes so that it is necessary to investigate Na-CO{sub 2} reaction according to various experimental parameter. Unlike SWR, Na-CO{sub 2} reaction is more complex to deal with reaction kinetics. Since a comprehensive understanding of Na-CO{sub 2} reaction mechanism is crucial for the safety analysis, the reaction phenomenon under the various conditions was investigated. The current issue is to make a database for developing computational code for CO{sub 2} gas leak situation because it is experimentally difficult to analyze the actual accident situation. Most studies on Na-CO{sub 2} interaction reports that chemical reaction is getting vigorous as temperature increased and reactivity is sensitive as temperature change between 400 .deg. C and 600 .deg. C. Therefore, temperature range is determined based on the operating condition (450 - 500 .deg. C) of KALIMER-600 employed as supercritical CO{sub 2} brayton cycle energy conversion system for Na-CO{sub 2} heat exchanger. And next parameter is sodium surface area which contact between sodium and CO{sub 2} when CO{sub 2} is injected into sodium pool in the accident situation. So, the fundamental surface reaction is experimentally studied in the range of 8 - 12cm{sup 2}. Additionally, it has been reported in recent years that CO{sub 2} Flow rate affects reactivity less significantly and CO{sub 2} flow rate is assumed that 5 SLPM (standard liter per minute) is suitable as a basis for a small leakage. The finally selected control parameters is sodium temperature and reacting surface area with constant CO{sub 2} flow rate. Na-CO{sub 2} reaction test is performed for investigating risk of potential accident which contacts with liquid sodium and CO{sub 2}. Amount of reaction is saturated as time passed because of kept a balance between production of solid phase reaction products and amount of diffusivity. These results contribute to make a

Mechanism of the transpassive dissolution and secondary passivation of chromium in sulphuric acid solutions

International Nuclear Information System (INIS)

Bojinov, M.; Betova, I.; Raicheff, R.; Fabricius, G.; Laitinen, T.; Saario, T.

1998-01-01

The transpassive dissolution and secondary passivation of Cr in 1..10 M H 2 SO 4 solutions were studied by a combination of different electrochemical methods. The steady-state polarization curves for transpassive dissolution exhibited a Tafel behaviour with a slope being independent on the acid concentration. Lower dissolution rates were measured for higher acid concentrations. Ring-disk measurements showed a release of both soluble Cr(VI) and Cr(III) during transpassivity. Impedance spectra were qualititatively similar in all acid concentrations, comprising one capacitive and two inductive semicircles. A kinetic model comprising two parallel transpassive dissolution paths was consistent with the experimental results. Typical passivation diagrams were observed for Cr in 10 M H 2 SO 4 , and a secondary passive state was established at higher potentials. The formation of the secondary passive film was confirmed by contact electric resistance (CER) measurements. A renewed version of the surface charge approach was consistent with the experimental results in the region of the secondary passivation. (orig.)

Simfuel dissolution studies in granitic groundwater

International Nuclear Information System (INIS)

Casas, I.; Caceci, M.S.; Bruno, J.; Sandino, A.; Ollila, K.

1991-09-01

The dissolution behavior of an unirradiated chemical analogue of spent nuclear fuel (SIMFUEL) has been studied in the presence of two different synthetic groundwater at 25 deg C and under both oxic and anoxic conditions. The release of U, Mo, Ba, Y and Sr was monitored during static (batch) leaching experiments of long duration (about 250 days). Preliminary results from continuous flow-through reactor experiments are also reported. The results obtained indicate the usefulness and limitations of SIMFUEL in the study of the kinetics and mechanism of dissolution of the minor components of spent nuclear fuel. Molybdenum, barium and strontium have shown a trend to congruent dissolution with the SIMFUEL matrix after a higher initial fractional release. Yttrium release has been found to be solubility controlled under the experimental conditions. A clear dependence on the partial pressure of O 2 of the rates of dissolution of uranium has been observed

SIMFUEL dissolution studies in granitic groundwater

International Nuclear Information System (INIS)

Casas, I.; Caceci, M.S.; Bruno, J; Sandino, A.

1991-09-01

The dissolution behavior of an unirradiated chemical analogue of spent nuclear fuel (SIMFUEL) has been studied in the presence of two different synthetic groundwaters at 25 degrees C and under both oxic and anoxic conditions. The release of U, Mo, Ba, Y and Sr was monitored during static (batch) leaching experiments of long duration (about 250 days). Preliminary results from continuous flow-through reactor experiments are also reported. The results obtained indicate the usefulness and limitations of SIMFUEL in the study of the kinetics and mechanism of dissolution of the minor components of spent nuclear fuel. Molybdenum, barium and strontium have shown a trend of congruent dissolution with the SIMFUEL matrix after a higher initial fractional release has been found to be solubility controlled under the experimental conditions. A clear dependence on the partial pressure of O 2 of the rate of dissolution of uranium has been observed. (au)

Ozone-surface reactions in five homes: surface reaction probabilities, aldehyde yields, and trends.

Science.gov (United States)

Wang, H; Morrison, G

2010-06-01

Field experiments were conducted in five homes during three seasons (summer 2005, summer 2006 and winter 2007) to quantify ozone-initiated secondary aldehyde yields, surface reaction probabilities, and trends any temporal over a 1.5-year interval. Surfaces examined include living room carpets, bedroom carpets, kitchen floors, kitchen counters, and living room walls. Reaction probabilities for all surfaces for all seasons ranged from 9.4 x 10(-8) to 1.0 x 10(-4). There were no significant temporal trends in reaction probabilities for any surfaces from summer 2005 to summer 2006, nor over the entire 1.5-year period, indicating that it may take significantly longer than this period for surfaces to exhibit any 'ozone aging' or lowering of ozone-surface reactivity. However, all surfaces in three houses exhibited a significant decrease in reaction probabilities from summer 2006 to winter 2007. The total yield of aldehydes for the summer of 2005 were nearly identical to that for summer of 2006, but were significantly higher than for winter 2007. We also observed that older carpets were consistently less reactive than in newer carpets, but that countertops remained consistently reactive, probably because of occupant activities such as cooking and cleaning. Ozone reactions taking place at indoor surfaces significantly influence personal exposure to ozone and volatile reaction products. These field studies show that indoor surfaces only slowly lose their ability to react with ozone over several year time frames, and that this is probably because of a combination of large reservoirs of reactive coatings and periodic additions of reactive coatings in the form of cooking, cleaning, and skin-oil residues. When considering exposure to ozone and its reaction products and in the absence of dramatic changes in occupancy, activities or furnishings, indoor surface reactivity is expected to change very slowly.

Towards a molecular understanding of cellulose dissolution in ionic liquids: anion/cation effect, synergistic mechanism and physicochemical aspects.

Science.gov (United States)

Li, Yao; Wang, Jianji; Liu, Xiaomin; Zhang, Suojiang

2018-05-07

Cellulose is one of the most abundant bio-renewable materials on the earth and its conversion to biofuels provides an appealing way to satisfy the increasing global energy demand. However, before carrying out the process of enzymolysis to glucose or polysaccharides, cellulose needs to be pretreated to overcome its recalcitrance. In recent years, a variety of ionic liquids (ILs) have been found to be effective solvents for cellulose, providing a new, feasible pretreatment strategy. A lot of experimental and computational studies have been carried out to investigate the dissolution mechanism. However, many details are not fully understood, which highlights the necessity to overview the current knowledge of cellulose dissolution and identify the research trend in the future. This perspective summarizes the mechanistic studies and microscopic insights of cellulose dissolution in ILs. Recent investigations of the synergistic effect of cations/anions and the distinctive structural changes of cellulose microfibril in ILs are also reviewed. Besides, understanding the factors controlling the dissolution process, such as the structure of anions/cations, viscosity of ILs, pretreatment temperature, heating rate, etc. , has been discussed from a structural and physicochemical viewpoint. At the end, the existing problems are discussed and future prospects are given. We hope this article would be helpful for deeper understanding of the cellulose dissolution process in ILs and the rational design of more efficient and recyclable ILs.

Organic ligand-induced dissolution kinetics of antimony trioxide

Institute of Scientific and Technical Information of China (English)

Xingyun Hu; Mengchang He

2017-01-01

The influence of low-molecular-weight dissolved organic matter (LMWDOM) on the dissolution rate of Sb2O3 was investigated.Some representative LMWDOMs with carboxyl,hydroxyl,hydrosulfuryl and amidogen groups occurring naturally in the solution were chosen,namely oxalic acid,citric acid,tartaric acid,EDTA,salicylic acid,phthalandione,glycine,thiolactic acid,xylitol,glucose and catechol.These LMWDOMs were dissolved in inert buffers at pH =3.7,6.6 and 8.6 and added to powdered Sb2O3 in a stirred,thermostatted reactor (25℃).The addition of EDTA,tartaric acid,thiolactic acid,citric acid and oxalic acid solutions at pH 3.7 and catechol at pH 8.6 increased the rate of release of antimony.In the 10 mmol/L thiolactic acid solution,up to 97％ by mass of the antimony was released after 120 min reaction.There was no effect on the dissolution of Sb2O3 for the other ligands.A weak correlation between dissolution rate with the dissociation constant of ligands and the stability of the dissolved complex was also found.All the results showed that the extent of the promoting effect of ligands on the dissolution of Sb2O3 was not determined by the stability of the dissolved complex,but by the dissociation constant of ligands and detachment rate of surface chelates from the mineral surface.This study can not only help in further understanding the effect of individual low-molecular-weight organic ligands,but also provides a reference to deduce the effect of natural organic matters with oxygen-bearing functional groups on the dissolution of antimony oxide minerals.

Basic reactions of osteoblasts on structured material surfaces

Directory of Open Access Journals (Sweden)

U. Meyer

2005-04-01

Full Text Available In order to assess how bone substitute materials determine bone formation in vivo it is useful to understand the mechanisms of the material surface/tissue interaction on a cellular level. Artificial materials are used in two applications, as biomaterials alone or as a scaffold for osteoblasts in a tissue engineering approach. Recently, many efforts have been undertaken to improve bone regeneration by the use of structured material surfaces. In vitro studies of bone cell responses to artificial materials are the basic tool to determine these interactions. Surface properties of materials surfaces as well as biophysical constraints at the biomaterial surface are of major importance since these features will direct the cell responses. Studies on osteoblast-like cell reactivity towards materials will have to focus on the different steps of protein and cell reactions towards defined surface properties. The introduction of new techniques allows nowadays the fabrication of materials with ordered surface structures. This paper gives a review of present knowledge on the various stages of osteoblast reactions on material surfaces, focused on basic cell events under in vitro conditions. Special emphasis is given to cellular reactions towards ordered nano-sized topographies.

Quantifying Silica Reactivity in Subsurface Environments: Reaction Affinity and Solute Matrix Controls on Quartz and SiO2 Glass Dissolution Kinetics

International Nuclear Information System (INIS)

Dove, Patricia M.

1999-01-01

Our goal is to develop a quantitative and mechanistic understanding of amorphous silica, SiO2(am), dissolution kinetics in aqueous solutions. A knowledge of fundamental controls on the reactivity of simple Si-O bonded phases is the baseline of behavior for understanding highly complex silica phases. In the Earth, silicate minerals comprise >70% of the crust and dominate virtually every subsurface system. More importantly for the objectives of this EMSP project, the silicates are important because compositionally complex glasses will become the front line of defense in containing radioactive wastes in the nation's long term and interim storage strategies. To date, the behavior of SiO2(am) is largely inferred from studies of the better known crystalline polymorphs (e.g. alpha-quartz). In the first step towards constructing a general model for amorphous silica reactivity in the complex fluid compositions of natural waters, we are determining the dissolution behavior as a function of temperature, solution pH and cation concentration. With these data we are determining relationships between SiO2 glass structure and dissolution rates in aqueous solutions, as described below

Effects of Surface Composition on the Aerosolisation and Dissolution of Inhaled Antibiotic Combination Powders Consisting of Colistin and Rifampicin

DEFF Research Database (Denmark)

Wang, Wenbo; Zhou, Qi Tony; Sun, Si-Ping

2016-01-01

is hygroscopic and rifampicin is hydrophobic, moisture absorption of combination formulations was significantly lower than the pure colistin formulation in the dynamic vapour sorption results. To investigate the dissolution characteristics, four dissolution test methods (diffusion Franz cell, modified Franz cell......, flow-through and beaker methods) were employed and compared. The modified Franz cell method was selected to test the dissolution behaviour of aerosolised powder formulations to eliminate the effect of membrane on dissolution. The results showed that surface enrichment of hydrophobic rifampicin neither...

The kinetics of Dissolution of Biologically Formed Calcific Deposits.

Science.gov (United States)

Rokidi, Stamatia; Koutsoukos, Petros

2015-04-01

order (ca.3) for the biominerals. This mode of dependence for both minerals studied, suggested surface diffusion controlled mechanism for their dissolution. The apparent rates of dissolution of the calcific deposits were higher in comparison to the corresponding value of the stoichiometric HAP. This finding is due to the higher apparent solubility of the carbonate and other metals containing biominerals. It should be noted that the dissolution affected the morphology of the prismatic crystallites which became thinner and shorter suggesting that the dissolution was rather uniform in the a, b and c axes of the prismatic crystallites. ACKNOWLEGMENT This research was partially funded by the European Union (European Social Fund-ESF) and Greek National Funds through the Operational program Education and Lifelong Learning' under the action Aristeia II (Code No 4420).

Ab initio R1 mechanism of photostimulated oxygen isotope exchange reaction on a defect TiO{sub 2} surface: The case of terminal oxygen atom exchange

Energy Technology Data Exchange (ETDEWEB)

Kevorkyants, Ruslan, E-mail: ruslan.kevorkyants@gmail.com; Sboev, Mikhail N.; Chizhov, Yuri V.

2017-05-01

Highlights: • DFT R1 mechanism of photostimulated oxygen isotope exchange between {sup 16}O{sup 18}O and terminal oxygen atom of a defect surface of nanocrystalline TiO{sub 2} is proposed. • The mechanism involves four adsorption intermediates and five transition states. • Activation energy of the reaction is 0.24 eV. • G-tensors of O{sub 3}{sup −} intermediates match EPR data on O{sub 2} adsorbed on UV-irradiated TiO{sub 2} surface. - Abstract: Based on density functional theory we propose R1 mechanism of photostimulated oxygen isotope exchange (POIEx) reaction between {sup 16}O{sup 18}O and terminal oxygen atom of a defect TiO{sub 2} surface, which is modeled by amorphous Ti{sub 8}O{sub 16} nanocluster in excited S{sup 1} electronic state. The proposed mechanism involves four adsorption intermediates and five transition states. The computed activation energy of the POIEx equals 0.24 eV. The computed g-tensors of the predicted ozonide O{sub 3}{sup −} chemisorption species match well EPR data on O{sub 2} adsorption on UV-irradiated nanocrystalline TiO{sub 2}. This match serves a mean of justification of the proposed R1 mechanism of the POIEx reaction. In addition, it is found that the proposed R1 POIEx reaction’s mechanism differs from R1 mechanism of thermo-assisted OIEx reaction on a surface of supported vanadium oxide catalyst VO{sub x}/TiO{sub 2} reported earlier.

The dissolution kinetics of major elements in municipal solid waste incineration bottom ash particles

Science.gov (United States)

Bendz, David; Tüchsen, Peter L.; Christensen, Thomas H.

2007-12-01

Leaching and tracer experiments in batches at L/S 20 were performed with 3-month-old MSWI bottom ash separated into eight different particle sizes. The time-dependent leaching of major elements (Ca 2+, K +, Na +, Cl - and SO 4- 2 ) was monitored for up to 747 h. Physical properties of the particles, the specific surface (BET), pore volume and pore volume distribution over pore sizes (BJH) were determined for all particle classes by N 2 adsorption/desorption experiments. Some common features of physical pore structure for all particles were revealed. The specific surface and the particle pore volume were found to be negatively correlated with particle size, ranging from 3.2 m 2/g to 25.7 m 2/g for the surface area and from 0.0086 cm 3/g to 0.091 cm 3/g for the pore volume. Not surprisingly, the specific surface area was found to be the major material parameter that governed the leaching behavior for all elements (Ca 2+, K +, Na +, Cl - and SO 4- 2 ) and particle sizes. The diffusion resistance was determined independently by separate tracer (tritium) experiments. Diffusion gave a significant contribution to the apparent leaching kinetics for all elements during the first 10-40 h (depending on the particle size) of leaching and surface reaction was the overall rate controlling mechanism at late times for all particle sizes. For Ca 2+ and SO 4- 2 , the coupled effect of diffusion resistance and the degree of undersaturation in the intra particle pore volume was found to be a major rate limiting dissolution mechanism for both early and late times. The solubility control in the intra particulate porosity may undermine any attempt to treat bottom ash by washing out the sulfate. Even for high liquid/solid ratios, the solubility in the intra-particular porosity will limit the release rate.

Study of the kinetics and mechanism of the dissolution of PUO2 by Cr(II) ion in acidic medium

International Nuclear Information System (INIS)

Machuron-Mandard, X.

1991-11-01

The study of the dissolution of actinides oxides is a topic of particular importance in nuclear energy production. The present study deals with the understanding of the reductive dissolution of PuO 2 in sulfuric acid media under the action of Cr 2+ aq ion. In the first chapter of the document, crystallographic and electronic properties of PuO 2 are described, followed by informations related to its dissolution in acidic media. The second chapter concerns the presentation of the different theories usable to interpret the kinetics of heterogeneous reaction and those for the understanding of electronic transfer applied to semi-conductors. With the help of the above mathematical tools an empirical law rate is established and a reactional model proposed. It appears that the electronic transfer is purely of the heterogenous nature and that the limiting step of the overall process corresponds certainly to the rupture of plutonium oxygen bond [fr

Mathematical modeling of drug dissolution.

Science.gov (United States)

Siepmann, J; Siepmann, F

2013-08-30

The dissolution of a drug administered in the solid state is a pre-requisite for efficient subsequent transport within the human body. This is because only dissolved drug molecules/ions/atoms are able to diffuse, e.g. through living tissue. Thus, generally major barriers, including the mucosa of the gastro intestinal tract, can only be crossed after dissolution. Consequently, the process of dissolution is of fundamental importance for the bioavailability and, hence, therapeutic efficacy of various pharmaco-treatments. Poor aqueous solubility and/or very low dissolution rates potentially lead to insufficient availability at the site of action and, hence, failure of the treatment in vivo, despite a potentially ideal chemical structure of the drug to interact with its target site. Different physical phenomena are involved in the process of drug dissolution in an aqueous body fluid, namely the wetting of the particle's surface, breakdown of solid state bonds, solvation, diffusion through the liquid unstirred boundary layer surrounding the particle as well as convection in the surrounding bulk fluid. Appropriate mathematical equations can be used to quantify these mass transport steps, and more or less complex theories can be developed to describe the resulting drug dissolution kinetics. This article gives an overview on the current state of the art of modeling drug dissolution and points out the assumptions the different theories are based on. Various practical examples are given in order to illustrate the benefits of such models. This review is not restricted to mathematical theories considering drugs exhibiting poor aqueous solubility and/or low dissolution rates, but also addresses models quantifying drug release from controlled release dosage forms, in which the process of drug dissolution plays a major role. Copyright © 2013 Elsevier B.V. All rights reserved.

Enhanced Colloidal Stability of CeO2 Nanoparticles by Ferrous Ions: Adsorption, Redox Reaction, and Surface Precipitation.

Science.gov (United States)

Liu, Xuyang; Ray, Jessica R; Neil, Chelsea W; Li, Qingyun; Jun, Young-Shin

2015-05-05

Due to the toxicity of cerium oxide (CeO2) nanoparticles (NPs), a better understanding of the redox reaction-induced surface property changes of CeO2 NPs and their transport in natural and engineered aqueous systems is needed. This study investigates the impact of redox reactions with ferrous ions (Fe2+) on the colloidal stability of CeO2 NPs. We demonstrated that under anaerobic conditions, suspended CeO2 NPs in a 3 mM FeCl2 solution at pH 4.8 were much more stable against sedimentation than those in the absence of Fe2+. Redox reactions between CeO2 NPs and Fe2+ lead to the formation of 6-line ferrihydrite on the CeO2 surfaces, which enhanced the colloidal stability by increasing the zeta potential and hydrophilicity of CeO2 NPs. These redox reactions can affect the toxicity of CeO2 NPs by increasing cerium dissolution, and by creating new Fe(III) (hydr)oxide reactive surface layers. Thus, these findings have significant implications for elucidating the phase transformation and transport of redox reactive NPs in the environment.

Modelling of the UO2 dissolution mechanisms in synthetic groundwater solutions. Dissolution experiments carried out under oxic conditions

International Nuclear Information System (INIS)

Cera, E.; Grive, M.; Bruno, J.; Ollila, K.

2001-02-01

The analytical data generated during the last three years within the 4th framework program of the European Community at VTT Chemical Technology concerning UO 2 dissolution under oxidising conditions have been modelled in the present work. The modelling work has been addressed to perform a kinetic study of the dissolution data generated by Ollila (1999) under oxidising conditions by using unirradiated uranium dioxide as solid sample. The average of the normalised UO 2 dissolution rates determined by using the initial dissolution data generated in all the experimental tests is (6.06 ± 3.64)* 10 -7 mol m -2 d -1 . This dissolution rate agrees with most of the dissolution rates reported in the literature under similar experimental conditions. The results obtained in this modelling exercise show that the same bicarbonate promoted oxidative dissolution processes operate for uranium dioxide, as a chemical analogue of the spent fuel matrix, independently of the composition of the aqueous solution used. (orig.)

Dissolution of metallic uranium and its alloys. Part 1. Review of analytical and process-scale metallic uranium dissolution

International Nuclear Information System (INIS)

Laue, C.A.; Gates-Anderson, D.; Fitch, T.E.

2004-01-01

This review focuses on dissolution/reaction systems capable of treating uranium metal waste to remove its pyrophoric properties. The primary emphasis is the review of literature describing analytical and production-scale dissolution methods applied to either uranium metal or uranium alloys. A brief summary of uranium's corrosion behavior is included since the corrosion resistance of metals and alloys affects their dissolution behavior. Based on this review, dissolution systems were recommended for subsequent screening studies designed to identify the best system to treat depleted uranium metal wastes at Lawrence Livermore National Laboratory (LLNL). (author)

The use of commercial microwave dissolution equipment for the fast and reliable dissolution of high-fired POX and MOX samples

International Nuclear Information System (INIS)

Tushingham, J.; McInnes, C.; Firkin, S.

1998-09-01

The use of commercially available microwave dissolution equipment for the fast and reliable dissolution of high-fired plutonium dioxide (POX) and mixed oxide (MOX) samples has been evaluated for application to Safeguards Analysis. Under the auspices of the UK R and D Support Programme to the IAEA, equipment has been purchased and tested for the high-pressure microwave dissolution of POX samples fired to 1250 deg. C and MOX samples fired to 1600 deg. C, in concentrated nitric acid and hydrofluoric acid mixture. Considerable problems were encountered during development of procedures for microwave dissolution, resulting largely from sudden changes in pressure within dissolution vessels, which resulted in actuation of safety interlocks designed to prevent overpressurisation. These difficulties were alleviated by controlling the microwave power to reduce the reaction temperature and pressure, and also by introducing additional safety valves into the digestion vessels. Using microwave digestion, dissolution times for high fired POX and MOX samples were substantially reduced. Samples which required ca. 10 hours to dissolve by conventional means could be dissolved in ca. 80 minutes by microwave digestion. Whilst a similar performance in terms of plutonium recovery was achieved for some materials by microwave and conventional dissolution, for other materials microwave dissolution gave higher plutonium recoveries but with poorer precision. This suggests the possible presence of some plutonium oxide within high-fired materials which is more difficult to dissolve than the bulk, and which is perhaps dissolved to an additional but variable degree by the current microwave dissolution procedure. Microwave dissolution has been demonstrated to increase the speed of dissolution of high-fired POX and MOX materials, compared with conventional dissolution. However, the technique has not yet proved satisfactory for the complete dissolution of all high-fired materials tested because of

The Carbonation of Wollastonite: A Model Reaction to Test Natural and Biomimetic Catalysts for Enhanced CO2 Sequestration

Directory of Open Access Journals (Sweden)

Fulvio Di Lorenzo

2018-05-01

Full Text Available One of the most promising strategies for the safe and permanent disposal of anthropogenic CO2 is its conversion into carbonate minerals via the carbonation of calcium and magnesium silicates. However, the mechanism of such a reaction is not well constrained, and its slow kinetics is a handicap for the implementation of silicate mineral carbonation as an effective method for CO2 capture and storage (CCS. Here, we studied the different steps of wollastonite (CaSiO3 carbonation (silicate dissolution → carbonate precipitation as a model CCS system for the screening of natural and biomimetic catalysts for this reaction. Tested catalysts included carbonic anhydrase (CA, a natural enzyme that catalyzes the reversible hydration of CO2(aq, and biomimetic metal-organic frameworks (MOFs. Our results show that dissolution is the rate-limiting step for wollastonite carbonation. The overall reaction progresses anisotropically along different [hkl] directions via a pseudomorphic interface-coupled dissolution–precipitation mechanism, leading to partial passivation via secondary surface precipitation of amorphous silica and calcite, which in both cases is anisotropic (i.e., (hkl-specific. CA accelerates the final carbonate precipitation step but hinders the overall carbonation of wollastonite. Remarkably, one of the tested Zr-based MOFs accelerates the dissolution of the silicate. The use of MOFs for enhanced silicate dissolution alone or in combination with other natural or biomimetic catalysts for accelerated carbonation could represent a potentially effective strategy for enhanced mineral CCS.

Influence of pH and temperature on alunite dissolution rates and products

Science.gov (United States)

Acero, Patricia; Hudson-Edwards, Karen

2015-04-01

Aluminium is one of the main elements in most mining-affected environments, where it may influence the mobility of other elements and play a key role on pH buffering. Moreover, high concentrations of Al can have severe effects on ecosystems and humans; Al intake, for example, has been implicated in neurological pathologies (e.g., Alzheimer's disease; Flaten, 2001). The behaviour of Al in mining-affected environments is commonly determined, at least partially, by the dissolution of Al sulphate minerals and particularly by the dissolution of alunite (KAl3(SO4)2(OH)6), which is one of the most important and ubiquitous Al sulphates in mining-affected environments (Nordstrom, 2011). The presence of alunite has been described in other acid sulphate environments, including some soils (Prietzel & Hirsch, 1998) and on the surface of Mars (Swayze et al., 2008). Despite the important role of alunite, its dissolution rates and products, and their controlling factors under conditions similar to those found in these environments, remain largely unknown. In this work, batch dissolution experiments have been carried out in order to shed light on the rates, products and controlling factors of alunite dissolution under different pH conditions (between 3 and 8) and temperatures (between 279 and 313K) similar to those encountered in natural systems. The obtained initial dissolution rates using synthetic alunite, based on the evolution of K concentrations, are between 10-9.7 and 10-10.9 mol-m-2-s-1, with the lowest rates obtained at around pH 4.8, and increases in the rates recorded with both increases and decreases in pH. Increases of temperature in the studied range also cause increases in the dissolution rates. The dissolution of alunite dissolution is incongruent, as has been reported for jarosite (isostructural with alunite) by Welch et al. (2008). Compared with the stoichiometric ratio in the bulk alunite (Al/K=3), K tends to be released to the solution preferentially over Al

The complexity of nanoparticle dissolution and its importance in nanotoxicological studies

International Nuclear Information System (INIS)

Misra, Superb K.; Dybowska, Agnieszka; Berhanu, Deborah; Luoma, Samuel N.; Valsami-Jones, Eugenia

2012-01-01

Dissolution of nanoparticles (NPs) is an important property that alters their abundance and is often a critical step in determining safety of nanoparticles. The dissolution status of the NPs in exposure media (i.e. whether they remain in particulate form or dissolve — and to what extent), strongly affects the uptake pathway, toxicity mechanisms and the environmental compartment in which NPs will have the highest potential impact. A review of available dissolution data on NPs demonstrates there is a range of potential outcomes depending on the NPs and the exposure media. For example two nominally identical nanoparticles, in terms of size and composition, could have totally different dissolution behaviours, subject to different surface modifications. Therefore, it is imperative that toxicological studies are conducted in conjunction with dissolution of NPs to establish the true biological effect of NPs and hence, assist in their regulation. -- Graphical abstract: Various physicochemical factors affecting dissolution of nanoparticles. Highlights: ► In this study we discuss dissolution of nanoparticles. ► Physicochemical properties of nanoparticles influence dissolution. ► Measuring dissolution of nanoparticles can help to understand their biological response.

The chemistry of the carbothermal synthesis of β-SiC : reaction mechanism, reaction rate and grain growth

NARCIS (Netherlands)

van Dijen, F.K.; Metselaar, R.

1991-01-01

Evidence is given that in the present case the reaction mechanism of ß-SiC formation from silica and carbon is a direct solid-state reaction in which silica migrates over the silicon carbide surface to the carbon. A high value (440 kJ/mol) of activation energy is obtained for this reaction. This

Organic ligand-induced dissolution kinetics of antimony trioxide.

Science.gov (United States)

Hu, Xingyun; He, Mengchang

2017-06-01

The influence of low-molecular-weight dissolved organic matter (LMWDOM) on the dissolution rate of Sb 2 O 3 was investigated. Some representative LMWDOMs with carboxyl, hydroxyl, hydrosulfuryl and amidogen groups occurring naturally in the solution were chosen, namely oxalic acid, citric acid, tartaric acid, EDTA, salicylic acid, phthalandione, glycine, thiolactic acid, xylitol, glucose and catechol. These LMWDOMs were dissolved in inert buffers at pH=3.7, 6.6 and 8.6 and added to powdered Sb 2 O 3 in a stirred, thermostatted reactor (25°C). The addition of EDTA, tartaric acid, thiolactic acid, citric acid and oxalic acid solutions at pH3.7 and catechol at pH8.6 increased the rate of release of antimony. In the 10mmol/L thiolactic acid solution, up to 97% by mass of the antimony was released after 120min reaction. There was no effect on the dissolution of Sb 2 O 3 for the other ligands. A weak correlation between dissolution rate with the dissociation constant of ligands and the stability of the dissolved complex was also found. All the results showed that the extent of the promoting effect of ligands on the dissolution of Sb 2 O 3 was not determined by the stability of the dissolved complex, but by the dissociation constant of ligands and detachment rate of surface chelates from the mineral surface. This study can not only help in further understanding the effect of individual low-molecular-weight organic ligands, but also provides a reference to deduce the effect of natural organic matters with oxygen-bearing functional groups on the dissolution of antimony oxide minerals. Copyright © 2016. Published by Elsevier B.V.

The Relationship Between the Evolution of an Internal Structure and Drug Dissolution from Controlled-Release Matrix Tablets.

Science.gov (United States)

Kulinowski, Piotr; Hudy, Wiktor; Mendyk, Aleksander; Juszczyk, Ewelina; Węglarz, Władysław P; Jachowicz, Renata; Dorożyński, Przemysław

2016-06-01

In the last decade, imaging has been introduced as a supplementary method to the dissolution tests, but a direct relationship of dissolution and imaging data has been almost completely overlooked. The purpose of this study was to assess the feasibility of relating magnetic resonance imaging (MRI) and dissolution data to elucidate dissolution profile features (i.e., kinetics, kinetics changes, and variability). Commercial, hydroxypropylmethyl cellulose-based quetiapine fumarate controlled-release matrix tablets were studied using the following two methods: (i) MRI inside the USP4 apparatus with subsequent machine learning-based image segmentation and (ii) dissolution testing with piecewise dissolution modeling. Obtained data were analyzed together using statistical data processing methods, including multiple linear regression. As a result, in this case, zeroth order release was found to be a consequence of internal structure evolution (interplay between region's areas-e.g., linear relationship between interface and core), which eventually resulted in core disappearance. Dry core disappearance had an impact on (i) changes in dissolution kinetics (from zeroth order to nonlinear) and (ii) an increase in variability of drug dissolution results. It can be concluded that it is feasible to parameterize changes in micro/meso morphology of hydrated, controlled release, swellable matrices using MRI to establish a causal relationship between the changes in morphology and drug dissolution. Presented results open new perspectives in practical application of combined MRI/dissolution to controlled-release drug products.

The Dissolution of Double Holliday Junctions

DEFF Research Database (Denmark)

Bizard, Anna H; Hickson, Ian D

2014-01-01

as "double Holliday junction dissolution." This reaction requires the cooperative action of a so-called "dissolvasome" comprising a Holliday junction branch migration enzyme (Sgs1/BLM RecQ helicase) and a type IA topoisomerase (Top3/TopoIIIα) in complex with its OB (oligonucleotide/oligosaccharide binding......Double Holliday junctions (dHJS) are important intermediates of homologous recombination. The separate junctions can each be cleaved by DNA structure-selective endonucleases known as Holliday junction resolvases. Alternatively, double Holliday junctions can be processed by a reaction known......) fold containing accessory factor (Rmi1). This review details our current knowledge of the dissolution process and the players involved in catalyzing this mechanistically complex means of completing homologous recombination reactions....

GLAMOR - Or How We Achieved A Common Understanding On The Decrease Of Glass Dissolution Kinetics Through International Cooperation

International Nuclear Information System (INIS)

Van Iseghem, Pierre; Aerstens, Marc; Gin, Stephane; Grambow, Bernd; Strachan, Denis M.; McGrail, B. Peter; Wicks, George G.; McMenamin, Thomas

2011-01-01

The objective of the EC funded GLAMOR project was to achieve a common understanding of the processes that control the decrease of the dissolution rate of high-level waste glass in water when silica becomes saturated. Is affinity control or a protective layer dominating? The following steps were taken: (1) review of the literature, (2) selection ofselect an experimental dataset, and selection of the models r(t) and GM2003, and (3) application apply by the GLAMOR partners of the models to the datasets. The main focus has beenwas on dissolution tests in pure water at different values of surface-to-volume and pH. Some of the main conclusions were: (1) both affinity and protective layer concepts must be considered in the interpretation of the rate decreasing stage, (2) the residual dissolution rate observed beyond the silica saturation stage is far more important in view of the long-term performance of the glass, and deserves more attention in future R and D. In the GLAMOR final report, we also discussed in detail the modeling parameters, such as the silica saturation concentration, the silica diffusion coefficient, the silica retention factor in the reaction layer, and the water diffusion coefficient.

In situ controlled crystallization as a tool to improve the dissolution of Glibenclamide.

Science.gov (United States)

Elkordy, Amal Ali; Jatto, Ayobami; Essa, Ebtessam

2012-05-30

For pharmaceutical purpose, micro-sized drugs are needed for many delivery systems, such as pulmonary and oral drug delivery systems. Many strategies have been employed to reduce the particle size of poorly water soluble drugs. Microcrystals could be produced by controlled association of drug in order to obtain naturally grown particles. The aim of this work was to increase the aqueous solubility and dissolution of Glibenclamide. The in situ controlled crystallization process was conducted in the presence of the non-ionic surfactants, Cremophor RH40 and Solutol HS-15 (0.75 and 1.5%, w/v), as protective stabilizing agents against agglomeration. In addition, these surfactants inhibit P-glycoprotein that reduces intestinal absorption of Glibenclamide by efflux transportation. Crystal shape was changed and particle size was reduced by about 15-folds, compared to control untreated drug. Differential Scanning Calorimetry (DSC) results indicated no interaction between the drug and the stabilizer. Microcrystals showed marked increase in the drug dissolution, Solutol HS-15 at 1.5% (w/v) concentration showing the highest dissolution efficiency. It could be concluded that in situ controlled crystallization using surfactants are promising method to improve dissolution of Glibeclamide as a model poorly water soluble drug. Copyright © 2012 Elsevier B.V. All rights reserved.

Dissolution and Precipitation Behaviour during Continuous Heating of Al–Mg–Si Alloys in a Wide Range of Heating Rates

Science.gov (United States)

Osten, Julia; Milkereit, Benjamin; Schick, Christoph; Kessler, Olaf

2015-01-01

In the present study, the dissolution and precipitation behaviour of four different aluminium alloys (EN AW-6005A, EN AW-6082, EN AW-6016, and EN AW-6181) in four different initial heat treatment conditions (T4, T6, overaged, and soft annealed) was investigated during heating in a wide dynamic range. Differential scanning calorimetry (DSC) was used to record heating curves between 20 and 600 °C. Heating rates were studied from 0.01 K/s to 5 K/s. We paid particular attention to control baseline stability, generating flat baselines and allowing accurate quantitative evaluation of the resulting DSC curves. As the heating rate increases, the individual dissolution and precipitation reactions shift to higher temperatures. The reactions during heating are significantly superimposed and partially run simultaneously. In addition, precipitation and dissolution reactions are increasingly suppressed as the heating rate increases, whereby exothermic precipitation reactions are suppressed earlier than endothermic dissolution reactions. Integrating the heating curves allowed the enthalpy levels of the different initial microstructural conditions to be quantified. Referring to time–temperature–austenitisation diagrams for steels, continuous heating dissolution diagrams for aluminium alloys were constructed to summarise the results in graphical form. These diagrams may support process optimisation in heat treatment shops.

Dissolution and Precipitation Behaviour during Continuous Heating of Al–Mg–Si Alloys in a Wide Range of Heating Rates

Directory of Open Access Journals (Sweden)

Julia Osten

2015-05-01

Full Text Available In the present study, the dissolution and precipitation behaviour of four different aluminium alloys (EN AW-6005A, EN AW-6082, EN AW-6016, and EN AW-6181 in four different initial heat treatment conditions (T4, T6, overaged, and soft annealed was investigated during heating in a wide dynamic range. Differential scanning calorimetry (DSC was used to record heating curves between 20 and 600 °C. Heating rates were studied from 0.01 K/s to 5 K/s. We paid particular attention to control baseline stability, generating flat baselines and allowing accurate quantitative evaluation of the resulting DSC curves. As the heating rate increases, the individual dissolution and precipitation reactions shift to higher temperatures. The reactions during heating are significantly superimposed and partially run simultaneously. In addition, precipitation and dissolution reactions are increasingly suppressed as the heating rate increases, whereby exothermic precipitation reactions are suppressed earlier than endothermic dissolution reactions. Integrating the heating curves allowed the enthalpy levels of the different initial microstructural conditions to be quantified. Referring to time–temperature–austenitisation diagrams for steels, continuous heating dissolution diagrams for aluminium alloys were constructed to summarise the results in graphical form. These diagrams may support process optimisation in heat treatment shops.

Mechanistic Analysis of Cocrystal Dissolution as a Function of pH and Micellar Solubilization.

Science.gov (United States)

Cao, Fengjuan; Amidon, Gordon L; Rodriguez-Hornedo, Nair; Amidon, Gregory E

2016-03-07

The purpose of this work is to provide a mechanistic understanding of the dissolution behavior of cocrystals under the influence of ionization and micellar solubilization. Mass transport models were developed by applying Fick's law of diffusion to dissolution with simultaneous chemical reactions in the hydrodynamic boundary layer adjacent to the dissolving cocrystal surface to predict the pH at the dissolving solid-liquid interface (i.e., interfacial pH) and the flux of cocrystals. To evaluate the predictive power of these models, dissolution studies of carbamazepine-saccharin (CBZ-SAC) and carbamazepine-salicylic acid (CBZ-SLC) cocrystals were performed at varied pH and surfactant concentrations above the critical stabilization concentration (CSC), where the cocrystals were thermodynamically stable. The findings in this work demonstrate that the pH dependent dissolution behavior of cocrystals with ionizable components is dependent on interfacial pH. This mass transport analysis demonstrates the importance of pH, cocrystal solubility, diffusivity, and micellar solubilization on the dissolution rates of cocrystals.

Setting accelerated dissolution test for PLGA microspheres containing peptide, investigation of critical parameters affecting drug release rate and mechanism.

Science.gov (United States)

Tomic, I; Vidis-Millward, A; Mueller-Zsigmondy, M; Cardot, J-M

2016-05-30

The objective of this study was development of accelerated in vitro release method for peptide loaded PLGA microspheres using flow-through apparatus and assessment of the effect of dissolution parameters (pH, temperature, medium composition) on drug release rate and mechanism. Accelerated release conditions were set as pH 2 and 45°C, in phosphate buffer saline (PBS) 0.02M. When the pH was changed from 2 to 4, diffusion controlled phases (burst and lag) were not affected, while release rate during erosion phase decreased two-fold due to slower ester bonds hydrolyses. Decreasing temperature from 45°C to 40°C, release rate showed three-fold deceleration without significant change in release mechanism. Effect of medium composition on drug release was tested in PBS 0.01M (200 mOsm/kg) and PBS 0.01M with glucose (380 mOsm/kg). Buffer concentration significantly affected drug release rate and mechanism due to the change in osmotic pressure, while ionic strength did not have any effect on peptide release. Furthermore, dialysis sac and sample-and-separate techniques were used, in order to evaluate significance of dissolution technique choice on the release process. After fitting obtained data to different mathematical models, flow-through method was confirmed as the most appropriate for accelerated in vitro dissolution testing for a given formulation. Copyright © 2016 Elsevier B.V. All rights reserved.

Aqueous corrosion mechanisms of the nuclear glass R7T7. Experimental approach. Kinetics and thermodynamic simulation

International Nuclear Information System (INIS)

Advocat, T.

1991-01-01

An inactive borosilicate glass made of about 30 oxides is studied. The composition was developed by the CEA for encapsulation of calcinated fission product solutions from reprocessing. Hydration energy of glass is first calculated for 8 glasses and results are compared to experimental data. Dissolution of R7T7 glass is examined at 90 0 C in a large range of pH and S/V ratios (glass surface/solution volume). In dilute media (S/V = 0.1 cm -1 ) dissolution is selective at acid pH and stoichiometric at basic pH. In alkaline media dissolution rate increases with pH. Corrosion products, generally amorphous or badly crystallized are observed on glass surface. For high S/V ratios (4, 20, 80 and 200 cm -1 ) the very low dissolution rate is explained by saturation. Orthosilic acid controls corrosion kinetics. A kinetic equation is proposed taking into account pH, S/V ratio and dissolved silica concentration. Geochemical consequences of R7T7 dissolution are modelled at 100 0 C and 90 0 C. Affinity of dissolution reaction depends upon many factors (pH, silica concentration, nature and crystallinity of secondary phases. Reaction affinity is not constant for the long-term [fr

Possible factors that control calcite dissolution in the western tropical Indian Ocean

Digital Repository Service at National Institute of Oceanography (India)

Naik, S.S.; Naidu, P.D.

and preservation of calcium carbonate in deep-sea sedi- ments 1 . Carbon dioxide dissolved in sea water is present as CO 2 gas, H 2 CO 3 , HCO – 3 and CO = 3 . All these species together con- stitute the Dissolved Inorganic Carbon (DIC) 2 which controls... the sea water pH, which in turn controls preservation/ dissolution of CaCO 3 . Precipitation of carbonate carbon results in an increase in ocean pCO 2 , and with it an increase in atmospheric CO 2 concentration. Con- versely, dissolution of CaCO 3...

Enhancement of dissolution of Telmisartan through use of solid dispersion technique surface solid dispersion

Directory of Open Access Journals (Sweden)

Bhumika Patel

2012-01-01

Full Text Available The present study was aimed to increase the solubility of the poorly water soluble drug Telmisartan by using Surface solid dispersion (SSD made of polymers like Poloxamer 407, PEG 6000 by Solvent evaporation method. The drug was solubilized by surfactants and/or polymers then adsorbed onto the surface of extremely fine carriers to increase its surface area and to form the SSD which give the more Surface area for absorption of the drug. A 2 2 full factorial design was used to investigate for each carrier the joint influence of formulation variables: Amount of carrier and adsorbent. Saturation solubility studies shows the improvement in solubility of drug batch SSD 8 give more solubility improvement than the other batch, in-vitro dissolution of pure drug, physical mixtures and SSDs were carried out in that SSDs were found to be effective in increasing the dissolution rate of Telmisartan in form of SSD when compared to pure drug. Also FT-IR spectroscopy, differential scanning calorimetry and X-ray diffractometry studies were carried out in order to characterize the drug and Surface solid dispersion. Furthermore, both DSC and X-ray diffraction showed a decrease in the melting enthalpy and reduced drug crystallinity consequently in SSDs. However, infrared spectroscopy revealed no drug interactions with the carriers.

Kinetics and mechanisms of interactions of nitrogen and carbon monoxide with liquid niobium

International Nuclear Information System (INIS)

Park, H.G.

1990-01-01

The kinetics and mechanisms of interactions of N 2 and CO with liquid niobium were investigated in the temperature range of 2,700 to 3,000 K in samples levitated in N 2 /Ar and CO/Ar streams. The nitrogen absorption and desorption processes were found to be second-order with respect to nitrogen concentration, indicating that the rate controlling step is either the adsorption of nitrogen molecules on the liquid surface or dissociation of absorbed nitrogen molecules into adsorbed atoms. The carbon and oxygen dissolution in liquid niobium from CO gas is an exothermic process and the solubilities of carbon and oxygen (C Ce , C Oe in at%) are related to the temperature and the partial pressure of CO. The reaction CO → [C] + [O] along with the evaporation of niobium oxide takes place during C and O dissolution, whereas C and O desorption occurs via CO evolution only

Photocatalysis reaction on ordered arrays of Au nanorads with controlled orientations

Energy Technology Data Exchange (ETDEWEB)

Kim, Min Jung; Han, Sang Woo [Dept. of Chemistry and KI for the NanoCentury, KAIST, Daejeon (Korea, Republic of)

2015-03-15

Surface photocatalysis reactions of aromatic compounds self-assembled on metal surfaces have been extensively explored for the past decades. Despite the numerous studies on the surface photocatalysis reactions of aromatic compounds, that on Au surface has rarely been reported due to the inefficiency of Au toward these reactions compared to Ag. The detailed experimental and theoretical studies on the mechanism of the enhanced photocatalytic function of the AuNR arrays are currently underway.

Controlled in-situ dissolution of an alkali metal

Science.gov (United States)

Jones, Jeffrey Donald; Dooley, Kirk John; Tolman, David Donald

2012-09-11

A method for the controllable dissolution of one or more alkali metals from a vessel containing a one or more alkali metals and/or one or more partially passivated alkali metals. The vessel preferably comprising a sodium, NaK or other alkali metal-cooled nuclear reactor that has been used. The alkali metal, preferably sodium, potassium or a combination thereof, in the vessel is exposed to a treatment liquid, preferably an acidic liquid, more preferably citric acid. Preferably, the treatment liquid is maintained in continuous motion relative to any surface of unreacted alkali metal with which the treatment liquid is in contact. The treatment liquid is preferably pumped into the vessel containing the one or more alkali metals and the resulting fluid is extracted and optionally further processed. Preferably, the resulting off-gases are processed by an off-gas treatment system and the resulting liquids are processed by a liquid disposal system. In one preferred embodiment, an inert gas is pumped into the vessel along with the treatment liquid.

Surface Characterization and Electrocatalytic Properties of the Ti/Ir0.3Ti(0.7-xPbx O2-Coated Electrodes for Oxygen Evolution Reaction in Acidic Media

Directory of Open Access Journals (Sweden)

Oliveira-Sousa Adriana de

2002-01-01

Full Text Available In this work a systematic investigation was carried out of the surface characterization and electrocatalytic activity of Ti/Ir0.3Ti(0.7-xPb x O2-coated electrodes (0 <= x <= 0.7, using the oxygen evolution reaction (OER in 0.5 mol dm-3 H2SO4 as model. The electrodes were prepared by thermal decomposition of IrCl3, TiCl3 and Pb(NO32 at 600 °C for 1 h using Ti as support. X-ray diffraction shows that the layers are crystalline and that the corresponding metal oxides are present. The surface morphology of the samples, before and after use under extensive oxygen evolution (Tafel experiment, was characterized by Scanning Electron Microscopy and the micrograph analyses show that the OER promotes the dissolution of the oxide layer. The redox processes occurring on the surface were characterized by cyclic voltammetry at 20 mV s-1 in 0.5 mol dm-3 aqueous H2SO4, at room temperature, and were controlled by the Ir3+/Ir4+ couple. The measured anodic voltammetric charge is related to the active area of the electrode showing that the replacement of TiO2 by PbO2 increases the surface area with the higher value being at 50 mol% PbO2. After oxygen evolution, the surface area increases slightly. Tafel slopes are independent of Pb content with the values around 60 mV decade-1, which suggest that only Ir sites are active for OER. The values of normalized current (i/q a show some inhibition of the OER as TiO2 is replaced by PbO2 suggesting that PbO2, can be a good choice, with potential to improve the selectivity of the system. The reaction order with respect to H+ ion is zero at constant overpotential and ionic strength. The values of Tafel slope and reaction order indicate that a single reaction mechanism is operating.

Multifractal scaling analysis of autopoisoning reactions over a rough surface

International Nuclear Information System (INIS)

Chaudhari, Ajay; Yan, Ching-Cher Sanders; Lee, S.-L.

2003-01-01

Decay type diffusion-limited reactions (DLR) over a rough surface generated by a random deposition model were performed. To study the effect of the decay profile on the reaction probability distribution (RPD), multifractal scaling analysis has been carried out. The dynamics of these autopoisoning reactions are controlled by the two parameters in the decay function, namely, the initial sticking probability (P ini ) of every site and the decay rate (m). The smaller the decay rate, the narrower is the range of α values in the α-f(α) multifractal spectrum. The results are compared with the earlier work of DLR over a surface of diffusion-limited aggregation (DLA). We also considered here the autopoisoning reactions over a smooth surface for comparing our results, which show clearly how the roughness affects the chemical reactions. The q-τ(q) multifractal curves for the smooth surface are linear whereas those for the rough surface are nonlinear. The range of α values in the case of a rough surface is wider than that of the smooth surface

Supersonic molecular beam experiments on surface chemical reactions.

Science.gov (United States)

Okada, Michio

2014-10-01

The interaction of a molecule and a surface is important in various fields, and in particular in complex systems like biomaterials and their related chemistry. However, the detailed understanding of the elementary steps in the surface chemistry, for example, stereodynamics, is still insufficient even for simple model systems. In this Personal Account, I review our recent studies of chemical reactions on single-crystalline Cu and Si surfaces induced by hyperthermal oxygen molecular beams and by oriented molecular beams, respectively. Studies of oxide formation on Cu induced by hyperthermal molecular beams demonstrate a significant role of the translational energy of the incident molecules. The use of hyperthermal molecular beams enables us to open up new chemical reaction paths specific for the hyperthermal energy region, and to develop new methods for the fabrication of thin films. On the other hand, oriented molecular beams also demonstrate the possibility of understanding surface chemical reactions in detail by varying the orientation of the incident molecules. The steric effects found on Si surfaces hint at new ways of material fabrication on Si surfaces. Controlling the initial conditions of incoming molecules is a powerful tool for finely monitoring the elementary step of the surface chemical reactions and creating new materials on surfaces. Copyright © 2014 The Chemical Society of Japan and Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Combining water-rock interaction experiments with reaction path and reactive transport modelling to predict reservoir rock evolution in an enhanced geothermal system

Science.gov (United States)

Kuesters, Tim; Mueller, Thomas; Renner, Joerg

2016-04-01

Reliably predicting the evolution of mechanical and chemical properties of reservoir rocks is crucial for efficient exploitation of enhanced geothermal systems (EGS). For example, dissolution and precipitation of individual rock forming minerals often result in significant volume changes, affecting the hydraulic rock properties and chemical composition of fluid and solid phases. Reactive transport models are typically used to evaluate and predict the effect of the internal feedback of these processes. However, a quantitative evaluation of chemo-mechanical interaction in polycrystalline environments is elusive due to poorly constrained kinetic data of complex mineral reactions. In addition, experimentally derived reaction rates are generally faster than reaction rates determined from natural systems, likely a consequence of the experimental design: a) determining the rate of a single process only, e.g. the dissolution of a mineral, and b) using powdered sample materials and thus providing an unrealistically high reaction surface and at the same time eliminating the restrictions on element transport faced in-situ for fairly dense rocks. In reality, multiple reactions are coupled during the alteration of a polymineralic rocks in the presence of a fluid and the rate determining process of the overall reactions is often difficult to identify. We present results of bulk rock-water interaction experiments quantifying alteration reactions between pure water and a granodiorite sample. The rock sample was chosen for its homogenous texture, small and uniform grain size (˜0.5 mm in diameter), and absence of pre-existing alteration features. The primary minerals are plagioclase (plg - 58 vol.%), quartz (qtz - 21 vol.%), K-feldspar (Kfs - 17 vol.%), biotite (bio - 3 vol.%) and white mica (wm - 1 vol.%). Three sets of batch experiments were conducted at 200 ° C to evaluate the effect of reactive surface area and different fluid path ways using (I) powders of the bulk rock with

A Novel Approach to Experimental Studies of Mineral Dissolution Kinetics

Energy Technology Data Exchange (ETDEWEB)

Chen Zhu

2006-08-31

Currently, DOE is conducting pilot CO{sub 2} injection tests to evaluate the concept of geological sequestration. One strategy that potentially enhances CO{sub 2} solubility and reduces the risk of CO{sub 2} leak back to the surface is dissolution of indigenous minerals in the geological formation and precipitation of secondary carbonate phases, which increases the brine pH and immobilizes CO{sub 2}. Clearly, the rates at which these dissolution and precipitation reactions occur directly determine the efficiency of this strategy. However, one of the fundamental problems in modern geochemistry is the persistent two to five orders of magnitude discrepancy between laboratory measured and field derived feldspar dissolution rates. To date, there is no real guidance as to how to predict silicate reaction rates for use in quantitative models. Current models for assessment of geological carbon sequestration have generally opted to use laboratory rates, in spite of the dearth of such data for compositionally complex systems, and the persistent disconnect between laboratory and field applications. Therefore, a firm scientific basis for predicting silicate reaction kinetics in CO2 injected geological formations is urgently needed to assure the reliability of the geochemical models used for the assessments of carbon sequestration strategies. The funded experimental and theoretical study attempts to resolve this outstanding scientific issue by novel experimental design and theoretical interpretation to measure silicate dissolution rates and iron carbonate precipitation rates at conditions pertinent to geological carbon sequestration. In the second year of the project, we completed CO{sub 2}-Navajo sandstone interaction batch and flow-through experiments and a Navajo sandstone dissolution experiment without the presence of CO{sub 2} at 200 C and 250-300 bars, and initiated dawsonite dissolution and solubility experiments. We also performed additional 5-day experiments at the

Plant-Level Modeling and Simulation of Used Nuclear Fuel Dissolution

Energy Technology Data Exchange (ETDEWEB)

de Almeida, Valmor F. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

2012-09-07

for the dissolver device; this simulation is currently at reach for computational fluid mechanics given the existing CAD geometry. From chemical transport phenomena, a simulation of the particle-scale dissolution front is needed to derive an improved solid dissolution kinetics law by predicting the local surface area change; an example was provided in this report. In addition, the associated reaction mechanisms for dissolution are presently largely untested and simplified, hence even a parallel experimental program in reaction kinetics is needed to support modeling and simulation efforts. Last but not least, a simple account of finite rates of solid feed and transfer can be readily introduced via a coupled delayed model. These are some of the theoretical benefits of a rational plant-level modeling approach which guides the development of smaller length and time scale modeling. Practical, and other theoretical benefits have been presented on a previous report.

Iron dissolution from volcanic ash in low-pH atmospheric water: a key control on volcanic iron input to the surface ocean?

Science.gov (United States)

Maters, E.; Delmelle, P.; Ayris, P. M.; Opfergelt, S.

2012-12-01

to 6 h suggest that early Fe release is not due solely to the dissolution of surface salts, as has been suggested in previous ash leach studies. The initial preferential release of Al, Fe, Mg, Ca, Na and K relative to Si may indicate silicate leaching by proton exchange.The approach of leachate ratios to bulk ratios over time suggests progression towards congruent dissolution of the silicate network. Notably, the two samples which exhibited the highest Fe release were unique in displaying a preferential release of Fe2+ relative to Fe3+ (Fe2+/Fe3+leachate = 4.3 and 2.1), suggesting that Fe speciation in the ash may act as a key control on ash Fe solubility. Remarkably, the ash from the second explosive phase of the 2010 Eyjafjallajökull eruption, Iceland, which exhibited a strong enrichment in soluble fluoride (F) inherited from gas-ash interaction within the eruption plume, displayed a total Fe release 5 to 10 times greater than that of the other ash samples. Calculations of silicate glass dissolution rates based on ash and leachate compositions suggest that the presence of soluble F significantly enhances Fe solubility in this sample. Therefore, plume processing of the ash is posited to exert a key control on the Fe release behaviour in solution of volcanic ash sourced from different eruptions.

Dissolution of thorium/uranium mixed oxide in nitric acid-hydrofluoric acid solution

International Nuclear Information System (INIS)

Filgueiras, S.A.C.

1984-01-01

The dissolution process of thorium oxide and mixed uranium-thorium oxide is studied, as a step of the head-end of the fuel reprocessing. An extensive bibliography was analysed, concerning the main aspects of the system, specially the most important process variables. Proposed mechanisms and models for the thorium oxide dissolution are presented. The laboratory tests were performed in two phases: at first, powdered thoria was used as the material to be dissolved. The objective was to know how changes in he concentrations of the dissolvent solution components HNO 3 , HF and Al(NO 3 ) 3 affect the dissolution rate. The tests were planned according to the fractional factorial method. Thes results showed that it is advantageous to work with powdered material, since the reaction occurs rapidly. And, if the Thorex solution (HNO 3 13M, HF 0.05M and Al(NO 3 ) 3 0.10M) is a suitable dissolvent, it was verified that it is possible to reduce the concentration of either nitric or fluoridric acid, without reducing the reaction rate to an undesirable value. It was also observed significant interaction between the components of the dissolvent solution. In the second phase of the tests, (Th, 5%U)O 2 sintered pellets were used. The main goals were to know the pellets dissolution behaviour and to compare the results for different pellets among themselves. It was observed that the metallurgical history of the material strongly influences its dissolution, specially the density and the microstructure. It was also studied how the (Th,U)O 2 mass/Thorex solution volume ratio affects the time needed to obtain an 1 M Th/liter solution. The activation energy for the reaction was obtained. (Author) [pt

Effect of drug loading method against drug dissolution mechanism of encapsulated amoxicillin trihydrate in matrix of semi-IPN chitosan-poly(N-vinylpyrrolidone) hydrogel with KHCO3 as pore forming agent in floating drug delivery system

Science.gov (United States)

Fimantari, Khansa; Budianto, Emil

2018-04-01

Helicobacterpylori infection can be treated using trihydrate amoxicillin. However, this treatment is not effective enough, as the conventional dosage treatment has a relatively short retention time in the human stomach. In the present study, the amoxicillin trihydrate drug will be encapsulated into a semi-IPN K-PNVP hydrogel matrix with 7,5% KHCO3 as a pore-forming agent. The encapsulated drug is tested with in vitro method to see the efficiency of its encapsulation and dissolution. The hydrogel in situ loading produces an encapsulation efficiency value. The values of the encapsulation efficiency are 95% and 98%, while post loading hydrogel yields an encapsulation efficiency value is 77% and the dissolution is 84%. The study of drug dissolution mechanism was done by using mathematical equation model to know its kinetics and its mechanism of dissolution. The post loading hydrogel was done by using thefirst-order model, while hydrogel in situ loading used Higuchi model. The Korsmeyer-Peppas model shows that post loading hydrogel dissolution mechanism is a mixture of diffusion and erosion, and in situ loading hydrogel in the form of diffusion. It is supported by the results of hydrogel characterization, before and after dissolution test with an optical microscope. The results of the optical microscope show that the hydrogel surface before and after the dissolution tested for both methods shows the change becomes rougher.

Accelerated dissolution of iron oxides in ice

Directory of Open Access Journals (Sweden)

D. Jeong

2012-11-01

Full Text Available Iron dissolution from mineral dusts and soil particles is vital as a source of bioavailable iron in various environmental media. In this work, the dissolution of iron oxide particles trapped in ice was investigated as a new pathway of iron supply. The dissolution experiments were carried out in the absence and presence of various organic complexing ligands under dark condition. In acidic pH conditions (pH 2, 3, and 4, the dissolution of iron oxides was greatly enhanced in the ice phase compared to that in water. The dissolved iron was mainly in the ferric form, which indicates that the dissolution is not a reductive process. The extent of dissolved iron was greatly affected by the kind of organic complexing ligands and the surface area of iron oxides. The iron dissolution was most pronounced with high surface area iron oxides and in the presence of strong iron binding ligands. The enhanced dissolution of iron oxides in ice is mainly ascribed to the "freeze concentration effect", which concentrates iron oxide particles, organic ligands, and protons in the liquid like ice grain boundary region and accelerates the dissolution of iron oxides. The ice-enhanced dissolution effect gradually decreased when decreasing the freezing temperature from −10 to −196 °C, which implies that the presence and formation of the liquid-like ice grain boundary region play a critical role. The proposed phenomenon of enhanced dissolution of iron oxides in ice may provide a new pathway of bioavailable iron production. The frozen atmospheric ice with iron-containing dust particles in the upper atmosphere thaws upon descending and may provide bioavailable iron upon deposition onto the ocean surface.

Dissolution testing of orally disintegrating tablets.

Science.gov (United States)

Kraemer, Johannes; Gajendran, Jayachandar; Guillot, Alexis; Schichtel, Julian; Tuereli, Akif

2012-07-01

For industrially manufactured pharmaceutical dosage forms, product quality tests and performance tests are required to ascertain the quality of the final product. Current compendial requirements specify a disintegration and/or a dissolution test to check the quality of oral solid dosage forms. These requirements led to a number of compendial monographs for individual products and, at times, the results obtained may not be reflective of the dosage form performance. Although a general product performance test is desirable for orally disintegrating tablets (ODTs), the complexity of the release controlling mechanisms and short time-frame of release make such tests difficult to establish. For conventional oral solid dosage forms (COSDFs), disintegration is often considered to be the prerequisite for subsequent dissolution. Hence, disintegration testing is usually insufficient to judge product performance of COSDFs. Given the very fast disintegration of ODTs, the relationship between disintegration and dissolution is worthy of closer scrutiny. This article reviews the current status of dissolution testing of ODTs to establish the product quality standards. Based on experimental results, it appears that it may be feasible to rely on the dissolution test without a need for disintegration studies for selected ODTs on the market. © 2012 The Authors. JPP © 2012 Royal Pharmaceutical Society.

Controlled dissolution of colossal quantities of nitrogen in stainless steel

DEFF Research Database (Denmark)

Christiansen, Thomas; Somers, Marcel A. J.

2006-01-01

The solubility of nitrogen in austenitic stainless steel was investigated thermogravimetrically by equilibrating thin foils of AISI 304 and AISI 316 in ammonia/hydrogen gas mixtures. Controlled dissolution of colossal amounts of nitrogen under metastable equilibrium conditions was realized...

Synthesis and dissolution studies of nickel ferrite in PDCA based formulations

International Nuclear Information System (INIS)

Ranganathan, S.; Raghavan, P.S.; Gopalan, R.; Srinivasan, M.P.; Narasimhan, S.V.

2000-01-01

Nickel ferrite is one of the important corrosion product in the pipeline surfaces of water cooled nuclear reactors. The dissolution of the nickel ferrite by chelating agents is very sensitive to nature of the chelant, nature of the reductant used in the formulation and the temperature at which the dissolution studies have been performed. The dissolution is dominated by the adsorption of the complexing agent at the oxide surface, but mainly controlled by the reductive dissolution of the ferrite particles. This is due to the in situ release of Fe 2+ ions or the generation of Fe 2+ ions by the reduction of Fe 3+ ions by the reductants in the solution. This study deals with the leaching of iron and nickel from nickel ferrite prepared by the solid state method. The prepared nickel ferrite samples are characterised by XRD to confirm the ferrite formation. The dissolution studies are performed in PDCA formulations containing organic reductants like ascorbic acid and LOMI reductants like Fe(II)-PDCA. The dissolution rate of nickel ferrite at 85degC increased with the increase of Fe 2+ ion content in the crystal lattice. Fe(II)-PDCA was found to be better reductants in dissolving the nickel ferrite in comparison with ascorbic acid. (author)

Surface structure-dependent pyrite oxidation in relatively dry and moist air: Implications for the reaction mechanism and sulfur evolution

Science.gov (United States)

Zhu, Jianxi; Xian, Haiyang; Lin, Xiaoju; Tang, Hongmei; Du, Runxiang; Yang, Yiping; Zhu, Runliang; Liang, Xiaoliang; Wei, Jingming; Teng, H. Henry; He, Hongping

2018-05-01

Pyrite oxidation not only is environmentally significant in the formation of acid mine (or acid rock) drainage and oxidative acidification of lacustrine sediment but also is a critical stage in geochemical sulfur evolution. The oxidation process is always controlled by the reactivity of pyrite, which in turn is controlled by its surface structure. In this study, the oxidation behavior of naturally existing {1 0 0}, {1 1 1}, and {2 1 0} facets of pyrite was investigated using a comprehensive approach combining X-ray photoelectron spectroscopy, diffuse reflectance Fourier transform infrared spectroscopy, and time-of-flight secondary-ion mass spectrometry with periodic density functional theoretical (DFT) calculations. The experimental results show that (i) the initial oxidation rates of both pyrite {1 1 1} and {2 1 0} are much greater than that of pyrite {1 0 0}; (ii) the initial oxidation rate of pyrite {2 1 0} is greater than that of pyrite {1 1 1} in low relative humidity, which is reversed in high relative humidity; and (iii) inner sphere oxygen-bearing sulfur species are originally generated from surface reactions and then converted to outer sphere species. The facet dependent rate law can be expressed as: r{hkl} =k{hkl}haP0.5(t + 1) - 0.5 , where r{hkl} is the orientation dependent reaction rate, k{hkl} is the orientation dependent rate constant, h is the relative humidity, P is the oxygen partial pressure, and t is the oxidation time in seconds. {1 1 1} is the most sensitive facet for pyrite oxidation. Combined with DFT theoretical investigations, water catalyzed electron transfer is speculated as the rate-limiting step. These findings disclose the structure-reactivity dependence of pyrite, which not only presents new insight into the mechanism of pyrite oxidation but also provides fundamental data to evaluate sulfur speciation evolution, suggesting that the surface structure sensitivity should be considered to estimate the reactivity at the mineral

Geoengineering impact of open ocean dissolution of olivine on atmospheric CO2, surface ocean pH and marine biology

International Nuclear Information System (INIS)

Köhler, Peter; Abrams, Jesse F; Völker, Christoph; Hauck, Judith; Wolf-Gladrow, Dieter A

2013-01-01

Ongoing global warming induced by anthropogenic emissions has opened the debate as to whether geoengineering is a ‘quick fix’ option. Here we analyse the intended and unintended effects of one specific geoengineering approach, which is enhanced weathering via the open ocean dissolution of the silicate-containing mineral olivine. This approach would not only reduce atmospheric CO 2 and oppose surface ocean acidification, but would also impact on marine biology. If dissolved in the surface ocean, olivine sequesters 0.28 g carbon per g of olivine dissolved, similar to land-based enhanced weathering. Silicic acid input, a byproduct of the olivine dissolution, alters marine biology because silicate is in certain areas the limiting nutrient for diatoms. As a consequence, our model predicts a shift in phytoplankton species composition towards diatoms, altering the biological carbon pumps. Enhanced olivine dissolution, both on land and in the ocean, therefore needs to be considered as ocean fertilization. From dissolution kinetics we calculate that only olivine particles with a grain size of the order of 1 μm sink slowly enough to enable a nearly complete dissolution. The energy consumption for grinding to this small size might reduce the carbon sequestration efficiency by ∼30%. (letter)

Status report on dissolution model development

International Nuclear Information System (INIS)

Jackson, D.D.

1983-07-01

The computer program PROTOCOL models the dissolution reactions of chemical species in water. It is being developed particularly to study the dissolution of proposed nuclear waste forms and related phases. Experimentally derived leaching rate functions are coupled to thermochemical equilibrium calculations and water flow rates. The program has been developed over a period of years. This report describes improvements that have been done in the past year

Groundwater flow and its effect on salt dissolution in Gypsum Canyon watershed, Paradox Basin, southeast Utah, USA

Science.gov (United States)

Reitman, Nadine G.; Ge, Shemin; Mueller, Karl

2014-09-01

Groundwater flow is an important control on subsurface evaporite (salt) dissolution. Salt dissolution can drive faulting and associated subsidence on the land surface and increase salinity in groundwater. This study aims to understand the groundwater flow system of Gypsum Canyon watershed in the Paradox Basin, Utah, USA, and whether or not groundwater-driven dissolution affects surface deformation. The work characterizes the groundwater flow and solute transport systems of the watershed using a three-dimensional (3D) finite element flow and transport model, SUTRA. Spring samples were analyzed for stable isotopes of water and total dissolved solids. Spring water and hydraulic conductivity data provide constraints for model parameters. Model results indicate that regional groundwater flow is to the northwest towards the Colorado River, and shallow flow systems are influenced by topography. The low permeability obtained from laboratory tests is inconsistent with field observed discharges, supporting the notion that fracture permeability plays a significant role in controlling groundwater flow. Model output implies that groundwater-driven dissolution is small on average, and cannot account for volume changes in the evaporite deposits that could cause surface deformation, but it is speculated that dissolution may be highly localized and/or weaken evaporite deposits, and could lead to surface deformation over time.

Geo-Chemo-Mechanical Studies for Permanent CO{sub 2} Storage in Geologic Reservoirs

Energy Technology Data Exchange (ETDEWEB)

Kelemen, Peter; Park, Ah-hyung; Matter, Jurg; Gadikota, Greeshma; Lisabeth, Harrison; Zhu, Wenlu

2013-09-30

This two-pronged study investigated the rates and mechanisms of formation of Ca and Mg carbonate minerals via reaction of aqueous fluids with silicate minerals and rocks, and the geomechanical effects of such reactions. The kinetic studies focused on the separation of variables, following from previous studies demonstrating rapid formation of carbonates via reaction of the mineral olivine with aqueous fluids rich in NaHCO{sub 3} (plus KHCO{sub 3} and RbHCO{sub 3}) and NaCl at a high partial pressure of CO{sub 2}. We wished to separate and quantify the effects of NaHCO{sub 3} and NaCl, and to investigate whether bicarbonate-rich, aqueous fluids would also cause rapid formation of carbonates via reaction with other minerals and rocks. Further, we wished to improve upon previous work by adding precise characterization of grain size distributions and surface area, and their changes as a result of reaction. We confirmed previous reports of very rapid olivine carbonation. We found that at a given temperature and CO{sub 2} partial pressure the previously observed rate enhancement in olivine carbonation is due mainly to NaHCO{sub 3}, and not to dissolved NaCl. Further, though reaction of the mineral plagioclase, and two rock compositions, were all faster in the presence of NaHCO{sub 3}-rich fluids, compared with saline and de-ionized water, they were all much slower than reaction of olivine. In the experiments showing the fastest reaction rate, average grain size tended to increase during experiments, presumably due to dissolution of small reactant grains plus growth of product phases on reactant surfaces. Porosity/surface area of grains tended to change with reaction progress, due to the formation of dissolution pits and irregular growth of product phases on reactant grain surfaces. Development of a passivating phase (e.g., a layer of silica) due to incongruent dissolution of solid reactants and/or precipitation of solid products was detected, but was relatively minor and

The impact of changing surface ocean conditions on the dissolution of aerosol iron

Science.gov (United States)

Fishwick, Matthew P.; Sedwick, Peter N.; Lohan, Maeve C.; Worsfold, Paul J.; Buck, Kristen N.; Church, Thomas M.; Ussher, Simon J.

2014-11-01

The proportion of aerosol iron (Fe) that dissolves in seawater varies greatly and is dependent on aerosol composition and the physicochemical conditions of seawater, which may change depending on location or be altered by global environmental change. Aerosol and surface seawater samples were collected in the Sargasso Sea and used to investigate the impact of these changing conditions on aerosol Fe dissolution in seawater. Our data show that seawater temperature, pH, and oxygen concentration, within the range of current and projected future values, had no significant effect on the dissolution of aerosol Fe. However, the source and composition of aerosols had the most significant effect on the aerosol Fe solubility, with the most anthropogenically influenced samples having the highest fractional solubility (up to 3.2%). The impact of ocean warming and acidification on aerosol Fe dissolution is therefore unlikely to be as important as changes in land usage and fossil fuel combustion. Our experimental results also reveal important changes in the size distribution of soluble aerosol Fe in solution, depending on the chemical conditions of seawater. Under typical conditions, the majority (77-100%) of Fe released from aerosols into ambient seawater existed in the colloidal (0.02-0.4 µm) size fraction. However, in the presence of a sufficient concentration of strong Fe-binding organic ligands (10 nM) most of the aerosol-derived colloidal Fe was converted to soluble Fe (<0.02 µm). This finding highlights the potential importance of organic ligands in retaining aerosol Fe in a biologically available form in the surface ocean.

Dissolution studies on Nickel ferrite in dilute chemical decontamination formulations

Energy Technology Data Exchange (ETDEWEB)

Ranganathan, S. [New Brunswick Univ., Fredericton, NB (Canada). Dept. of Chemical Engineering; Srinivasan, M.P. [Bhabha Atomic Research Centre (BARC) (India). Water and Steam Chemistry Laboratory; Raghavan, P.S. [Madras Christian College, Chennai (India); Narasimhan, S.V. [Bhabha Atomic Research Centre, Bombay (India); Gopalan, R. [Madras Christian College, Chennai (India). Department of Chemistry

2004-09-01

Nickel ferrite is one of the important corrosion products in the pipeline surfaces of water-cooled nuclear reactors. The dissolution of the nickel ferrite by chelating agents is very sensitive to the nature of the chelant, the nature of the reductant used in the formulation and the temperature at which the dissolution studies are performed. The dissolution is mainly controlled by the reductive dissolution of the ferrite particles, but complexing agents also play a significant role in the dissolution process. This study deals with the leaching of iron and nickel from nickel ferrite prepared by the solid-state method. The dissolution studies are performed in pyridine-2,6-dicarboxylic acid (PDCA), nitrilotriacetic acid (NTA), and ethylenediaminetetraacetic acid (EDTA) formulations containing organic reductants like ascorbic acid and low oxidation state transition metal ion reductants like Fe(II)-L (where L = PDCA, NTA, EDTA) at 85 C. The dissolution of nickel ferrite in PDCA, NTA and EDTA formulations is influenced by the presence of reductants in the formulations. The addition of Fe(II)-L in the formulation greatly enhances the dissolution of nickel ferrite. The preferential leaching of nickel over iron during the dissolution of nickel ferrite was observed in all the formulations. (orig.)

Dissolution studies on Nickel ferrite in dilute chemical decontamination formulations

International Nuclear Information System (INIS)

Ranganathan, S.; Narasimhan, S.V.; Gopalan, R.

2004-01-01

Nickel ferrite is one of the important corrosion products in the pipeline surfaces of water-cooled nuclear reactors. The dissolution of the nickel ferrite by chelating agents is very sensitive to the nature of the chelant, the nature of the reductant used in the formulation and the temperature at which the dissolution studies are performed. The dissolution is mainly controlled by the reductive dissolution of the ferrite particles, but complexing agents also play a significant role in the dissolution process. This study deals with the leaching of iron and nickel from nickel ferrite prepared by the solid-state method. The dissolution studies are performed in pyridine-2,6-dicarboxylic acid (PDCA), nitrilotriacetic acid (NTA), and ethylenediaminetetraacetic acid (EDTA) formulations containing organic reductants like ascorbic acid and low oxidation state transition metal ion reductants like Fe(II)-L (where L = PDCA, NTA, EDTA) at 85 C. The dissolution of nickel ferrite in PDCA, NTA and EDTA formulations is influenced by the presence of reductants in the formulations. The addition of Fe(II)-L in the formulation greatly enhances the dissolution of nickel ferrite. The preferential leaching of nickel over iron during the dissolution of nickel ferrite was observed in all the formulations. (orig.)

Make and break - Facile synthesis of cocrystals and comprehensive dissolution studies

Science.gov (United States)

Batzdorf, L.; Zientek, N.; Rump, D.; Fischer, F.; Maiwald, M.; Emmerling, F.

2017-04-01

Mechanochemistry is increasingly used as a 'green alternative' for synthesizing various materials including pharmaceutical cocrystals. Herein, we present the mechanochemical synthesis of three new cocrystals containing the API carbamazepine (cocrystals CBZ:Indometacin 1:1, CBZ:Benzamide 1:1, and CBZ:Nifedipine 1:1). The mechanochemical reaction was investigated in situ documenting a fast and complete reaction within one minute. Online NMR spectroscopy proved the direct influence of the dissolution behaviour of the coformers to the dissolution behaviour of the API carbamazepine. The dissolution behaviour of the organic cocrystals is compared to the behaviour of the pure drug indicating a general applicability of this approach for detailed cocrystal dissolution studies.

Controlled dissolution of silicon dioxide layers for depth resolved multielement analysis by inductively coupled plasma-mass spectrometry

International Nuclear Information System (INIS)

Lorge, Susan E.; Houk, R.S.

2009-01-01

Dissolution procedures were developed to control the number of surface layers removed, in an attempt to achieve depth resolved analysis by inductively coupled plasma-mass spectrometry (ICP-MS). NIST 612 glass was chosen because it is a homogeneous material with many elements at interesting concentrations, ∼ 50 ppm. Varying dissolution time and HF concentration resulted in the reproducible removal of SiO 2 layers as thin as 70 A deep. Dissolved trace metals were determined after dilution by inductively coupled plasma-mass spectrometry (ICP-MS) with a magnetic sector instrument. The amount removed was determined from the concentration of a major element, Ca. With the exception of Zn, trace metal concentrations agreed reasonably well with their certified values for removal depths of 500, 300 and 150 A. Zinc concentration was significantly high in all dissolutions indicating either a contamination problem or that Zn is removed at a faster rate than Ca. For the dissolutions that removed 70 A of SiO 2 , Cr, Mn, Co, Sr, Cd, Ce, Dy, Er, Yb and U recovery results agreed with their certified values (∼ 50 ppm); Ti, As, Mo, Ba, and Th could not be determined because net intensities were below 3σ of the blank; and measured concentrations for Cu, Pb and Zn were well above the certified values.

Mechanism of nuclear dissipation in fission and heavy-ion reactions

International Nuclear Information System (INIS)

Nix, J.R.; Sierk, A.J.

1986-01-01

Recent advances in the theoretical understanding of nuclear dissipation at intermediate excitation energies are reviewed, with particular emphasis on a new surface-plus-window mechanism that involves interactions of either one or two nucleons with the moving nuclear surface and also, for dumbbell-like shapes encountered in fission and heavy-ion reactions, the transfer of nucleons through the window separating the two portions of the system. This novel dissipation mechanism provides a unified macroscopic description of such diverse phenomena as widths of isoscalar giant quadrupole and giant octupole resonances, mean fission-fragment kinetic energies and excitation energies, dynamical thresholds for compound-nucleus formation, enhancement in neutron emission prior to fission, and widths of mass and charge distributions in deep-inelastic heavy-ion reactions. 41 refs., 8 figs

The dynamics of the Hg + Br2 reaction: elucidation of the reaction mechanism for the Br exchange reaction.

Science.gov (United States)

Jambrina, P G; Menéndez, M; Aoiz, F J

2017-06-28

In spite of its importance in the Hg atmospheric chemistry, the dynamics of the Hg + Br 2 → HgBr + Br reaction is poorly understood. In this article, we have carried out a comprehensive study of the reaction mechanism of this reaction by means of quasiclassical trajectories (QCTs) on an existing ab initio potential energy surface (PES). The reaction has a non trivial dynamics, as a consequence of its large endothermicity, the presence of a deep potential well, and the competition between the Br exchange and the collision induced dissociation processes. Our calculations demonstrate that insertion is only relevant at energies just above the reaction threshold and that, at energies above 2.3 eV, HgBr formation typically takes place via a sort of frustrated dissociation. In order to compare directly with the results obtained in extensive cross molecular beam experiments for the homologous reaction with I 2 , angular distributions in the laboratory frame for Hg + Br 2 have been simulated under similar experimental conditions. The lack of agreement at the highest energies considered suggests that either the two reactions have substantially different mechanisms or that calculations on a single PES cannot account for the dynamics at those energies.

Antagonistic Effects of Ocean Acidification and Rising Sea Surface Temperature on the Dissolution of Coral Reef Carbonate Sediments

Directory of Open Access Journals (Sweden)

Daniel Trnovsky

2016-11-01

Full Text Available Increasing atmospheric CO2 is raising sea surface temperature (SST and increasing seawater CO2 concentrations, resulting in a lower oceanic pH (ocean acidification; OA, which is expected to reduce the accretion of coral reef ecosystems. Although sediments comprise most of the calcium carbonate (CaCO3 within coral reefs, no in situ studies have looked at the combined effects of increased SST and OA on the dissolution of coral reef CaCO3 sediments. In situ benthic chamber incubations were used to measure dissolution rates in permeable CaCO3 sands under future OA and SST scenarios in a coral reef lagoon on Australia’s Great Barrier Reef (Heron Island. End of century (2100 simulations (temperature +2.7°C and pH -0.3 shifted carbonate sediments from net precipitating to net dissolving. Warming increased the rate of benthic respiration (R by 29% per 1°C and lowered the ratio of productivity to respiration (P/R; ΔP/R = -0.23, which increased the rate of CaCO3 sediment dissolution (average net increase of 18.9 mmol CaCO3 m-2 d-1 for business as usual scenarios. This is most likely due to the influence of warming on benthic P/R which, in turn, was an important control on sediment dissolution through the respiratory production of CO2. The effect of increasing CO2 on CaCO3 sediment dissolution (average net increase of 6.5 mmol CaCO3 m-2 d-1 for business as usual scenarios was significantly less than the effect of warming. However, the combined effect of increasing both SST and pCO2 on CaCO3 sediment dissolution was non-additive (average net increase of 5.6 mmol CaCO3 m-2 d-1 due to the different responses of the benthic community. This study highlights that benthic biogeochemical processes such as metabolism and associated CaCO3 sediment dissolution respond rapidly to changes in SST and OA, and that the response to multiple environmental changes are not necessarily additive.

A method for phenomenological and chemical kinetics study of autocatalytic reactive dissolution by optical microscopy. The case of uranium dioxide dissolution in nitric acid media

Science.gov (United States)

Marc, Philippe; Magnaldo, Alastair; Godard, Jérémy; Schaer, Éric

2018-03-01

Dissolution is a milestone of the head-end of hydrometallurgical processes, as the stabilization rates of the chemical elements determine the process performance and hold-up. This study aims at better understanding the chemical and physico-chemical phenomena of uranium dioxide dissolution reactions in nitric acid media in the Purex process, which separates the reusable materials and the final wastes of the spent nuclear fuels. It has been documented that the attack of sintering-manufactured uranium dioxide solids occurs through preferential attack sites, which leads to the development of cracks in the solids. Optical microscopy observations show that in some cases, the development of these cracks leads to the solid cleavage. It is shown here that the dissolution of the detached fragments is much slower than the process of the complete cleavage of the solid, and occurs with no disturbing phenomena, like gas bubbling. This fact has motivated the measurement of dissolution kinetics using optical microscopy and image processing. By further discriminating between external resistance and chemical reaction, the "true" chemical kinetics of the reaction have been measured, and the highly autocatalytic nature of the reaction confirmed. Based on these results, the constants of the chemical reactions kinetic laws have also been evaluated.

A method for phenomenological and chemical kinetics study of autocatalytic reactive dissolution by optical microscopy. The case of uranium dioxide dissolution in nitric acid media

Directory of Open Access Journals (Sweden)

Marc Philippe

2018-01-01

Full Text Available Dissolution is a milestone of the head-end of hydrometallurgical processes, as the stabilization rates of the chemical elements determine the process performance and hold-up. This study aims at better understanding the chemical and physico-chemical phenomena of uranium dioxide dissolution reactions in nitric acid media in the Purex process, which separates the reusable materials and the final wastes of the spent nuclear fuels. It has been documented that the attack of sintering-manufactured uranium dioxide solids occurs through preferential attack sites, which leads to the development of cracks in the solids. Optical microscopy observations show that in some cases, the development of these cracks leads to the solid cleavage. It is shown here that the dissolution of the detached fragments is much slower than the process of the complete cleavage of the solid, and occurs with no disturbing phenomena, like gas bubbling. This fact has motivated the measurement of dissolution kinetics using optical microscopy and image processing. By further discriminating between external resistance and chemical reaction, the “true” chemical kinetics of the reaction have been measured, and the highly autocatalytic nature of the reaction confirmed. Based on these results, the constants of the chemical reactions kinetic laws have also been evaluated.

Hydration of dicalcium silicate and diffusion through neo-formed calcium-silicate-hydrates at weathered surfaces control the long-term leaching behaviour of basic oxygen furnace (BOF) steelmaking slag.

Science.gov (United States)

Stewart, Douglas I; Bray, Andrew W; Udoma, Gideon; Hobson, Andrew J; Mayes, William M; Rogerson, Mike; Burke, Ian T

2018-04-01

Alkalinity generation and toxic trace metal (such as vanadium) leaching from basic oxygen furnace (BOF) steel slag particles must be properly understood and managed by pre-conditioning if beneficial reuse of slag is to be maximised. Water leaching under aerated conditions was investigated using fresh BOF slag at three different particle sizes (0.5-1.0, 2-5 and 10 × 10 × 20 mm blocks) and a 6-month pre-weathered block. There were several distinct leaching stages observed over time associated with different phases controlling the solution chemistry: (1) free-lime (CaO) dissolution (days 0-2); (2) dicalcium silicate (Ca 2 SiO 4 ) dissolution (days 2-14) and (3) Ca-Si-H and CaCO 3 formation and subsequent dissolution (days 14-73). Experiments with the smallest size fraction resulted in the highest Ca, Si and V concentrations, highlighting the role of surface area in controlling initial leaching. After ~2 weeks, the solution Ca/Si ratio (0.7-0.9) evolved to equal those found within a Ca-Si-H phase that replaced dicalcium silicate and free-lime phases in a 30- to 150-μm altered surface region. V release was a two-stage process; initially, V was released by dicalcium silicate dissolution, but V also isomorphically substituted for Si into the neo-formed Ca-Si-H in the alteration zone. Therefore, on longer timescales, the release of V to solution was primarily controlled by considerably slower Ca-Si-H dissolution rates, which decreased the rate of V release by an order of magnitude. Overall, the results indicate that the BOF slag leaching mechanism evolves from a situation initially dominated by rapid hydration and dissolution of primary dicalcium silicate/free-lime phases, to a slow diffusion limited process controlled by the solubility of secondary Ca-Si-H and CaCO 3 phases that replace and cover more reactive primary slag phases at particle surfaces.

The kinetics and mechanisms of amorphous calcium carbonate (ACC) crystallization to calcite, via vaterite.

Science.gov (United States)

Rodriguez-Blanco, Juan Diego; Shaw, Samuel; Benning, Liane G

2011-01-01

The kinetics and mechanisms of nanoparticulate amorphous calcium carbonate (ACC) crystallization to calcite, via vaterite, were studied at a range of environmentally relevant temperatures (7.5-25 °C) using synchrotron-based in situ time-resolved Energy Dispersive X-ray Diffraction (ED-XRD) in conjunction with high-resolution electron microscopy, ex situ X-ray diffraction and infrared spectroscopy. The crystallization process occurs in two stages; firstly, the particles of ACC rapidly dehydrate and crystallize to form individual particles of vaterite; secondly, the vaterite transforms to calcite via a dissolution and reprecipitation mechanism with the reaction rate controlled by the surface area of calcite. The second stage of the reaction is approximately 10 times slower than the first. Activation energies of calcite nucleation and crystallization are 73±10 and 66±2 kJ mol(-1), respectively. A model to calculate the degree of calcite crystallization from ACC at environmentally relevant temperatures (7.5-40 °C) is also presented.

Role of surfaces and interfaces in controlling the mechanical properties of metallic alloys.

Science.gov (United States)

Lee, Won-Jong; Chia, Wen-Jui; Wang, Jinliu; Chen, Yanfeng; Vaynman, Semyon; Fine, Morris E; Chung, Yip-Wah

2010-11-02

This article explores the subtle effects of surfaces and interfaces on the mechanical properties of bulk metallic alloys using three examples: environmental effects on fatigue life, hydrogen embrittlement effects on the ductility of intermetallics, and the role of coherent precipitates in the toughness of steels. It is demonstrated that the marked degradation of the fatigue life of metals is due to the strong chemisorption of adsorbates on exposed slip steps that are formed during fatigue deformation. These adsorbates reduce the reversibility of slip, thus accelerating fatigue damage in a chemically active gas environment. For certain intermetallic alloys such as Ni(3)Al and Ni(3)Fe, the ductility depends on the ambient gas composition and the atomic ordering in these alloys, both of which govern the complex surface chemical reactions taking place in the vicinity of crack tips. Finally, it is shown that local stresses at a coherent precipitate-matrix interface can activate dislocation motion at low temperatures, thus improving the fracture toughness of bulk alloys such as steels at cryogenic temperatures. These examples illustrate the complex interplay between surface chemistry and mechanics, often yielding unexpected results.

Dissolution model for a glass having an adherent insoluble surface layer

International Nuclear Information System (INIS)

Harvey, K.B.; Larocque, C.A.B.

1990-01-01

Waste form glasses that contain substantial quantities of iron, manganese, and aluminum oxides, such as the Savannah River SRL TDS-131 glass, form a thick, hydrated surface layer when placed in contact with water. The dissolution of such a glass has been modeled with the Savannah River Model. The authors showed previously that the equations of the Savannah River Model could be fitted to published experimental data if a time-dependent diffusion coefficient was assumed for species of diffusing through the surface layer. The Savannah River Model assumes that all of the material dissolved from the glass enters solution, whereas it was observed that substantial quantities of material were retained in the surface layer. An alternative model, presented contains a mass balance equation that allows material either to enter solution or to be retained in the surface layer. It is shown that the equations derived using this model can be fitted to the published experimental data assuming a constant diffusion coefficient for species diffusing through the surface layer

Studies on the kinetics of UO2 dissolution in carbonate-bicarbonate medium using sodium hypochlorite as oxidant

International Nuclear Information System (INIS)

Sharma, J.N.; Bhattacharya, K.; Swami, R.G.; Tangri, S.K.; Mukherjee, T.K.

1996-01-01

The dissolution of UO 2 in carbonate-bicarbonate solutions containing sodium hypochlorite as an oxidant has been investigated. The effect of temperature, sodium hypochlorite concentration and stirring speed was examined. In the temperature range of 303 to 318 K, the leaching reaction displayed linear kinetics. Apparent activation energy obtained from the differential approach was found to be 57 kJ mol -1 . This relatively high activation energy value indicates a chemically controlled behavior of UO 2 dissolution. The order of reaction with respect to sodium hypochlorite concentration was found to be unity. (author). 18 refs., 6 figs

Exploring chemical reaction mechanisms through harmonic Fourier beads path optimization.

Science.gov (United States)

Khavrutskii, Ilja V; Smith, Jason B; Wallqvist, Anders

2013-10-28

Here, we apply the harmonic Fourier beads (HFB) path optimization method to study chemical reactions involving covalent bond breaking and forming on quantum mechanical (QM) and hybrid QM∕molecular mechanical (QM∕MM) potential energy surfaces. To improve efficiency of the path optimization on such computationally demanding potentials, we combined HFB with conjugate gradient (CG) optimization. The combined CG-HFB method was used to study two biologically relevant reactions, namely, L- to D-alanine amino acid inversion and alcohol acylation by amides. The optimized paths revealed several unexpected reaction steps in the gas phase. For example, on the B3LYP∕6-31G(d,p) potential, we found that alanine inversion proceeded via previously unknown intermediates, 2-iminopropane-1,1-diol and 3-amino-3-methyloxiran-2-ol. The CG-HFB method accurately located transition states, aiding in the interpretation of complex reaction mechanisms. Thus, on the B3LYP∕6-31G(d,p) potential, the gas phase activation barriers for the inversion and acylation reactions were 50.5 and 39.9 kcal∕mol, respectively. These barriers determine the spontaneous loss of amino acid chirality and cleavage of peptide bonds in proteins. We conclude that the combined CG-HFB method further advances QM and QM∕MM studies of reaction mechanisms.

Theoretical Investigation of the Interfacial Reactions during Hot-Dip Galvanizing of Steel

Science.gov (United States)

Mandal, G. K.; Balasubramaniam, R.; Mehrotra, S. P.

2009-03-01

In the modern galvanizing line, as soon as the steel strip enters the aluminum-containing zinc bath, two reactions occur at the strip and the liquid-zinc alloy interface: (1) iron rapidly dissolves from the strip surface, raising the iron concentration in the liquid phase at the strip-liquid interface; and (2) aluminum forms a stable aluminum-iron intermetallic compound layer at the strip-coating interface due to its greater affinity toward iron. The main objective of this study is to develop a simple and realistic mathematical model for better understanding of the kinetics of galvanizing reactions at the strip and the liquid-zinc alloy interface. In the present study, a model is proposed to simulate the effect of various process parameters on iron dissolution in the bath, as well as, aluminum-rich inhibition layer formation at the substrate-coating interface. The transient-temperature profile of the immersed strip is predicted based on conductive and convective heat-transfer mechanisms. The inhibition-layer thickness at the substrate-coating interface is predicted by assuming the cooling path of the immersed strip consists of a series of isothermal holds of infinitesimal time-step. The influence of galvanizing reaction is assessed by considering nucleation and growth mechanisms at each hold time, which is used to estimate the total effect of the immersion time on the formation mechanism of the inhibition layer. The iron- dissolution model is developed based on well established principles of diffusion taking into consideration the area fraction covered by the intermetallic on the strip surface during formation of the inhibition layer. The model can be effectively used to monitor the dross formation in the bath by optimizing the process parameters. Theoretical predictions are compared with the findings of other researchers. Simulated results are in good agreement with the theoretical and experimental observation carried out by other investigators.

Quantifying Fenton reaction pathways driven by self-generated H2O2 on pyrite surfaces

Science.gov (United States)

Gil-Lozano, C.; Davila, A. F.; Losa-Adams, E.; Fairén, A. G.; Gago-Duport, L.

2017-03-01

Oxidation of pyrite (FeS2) plays a significant role in the redox cycling of iron and sulfur on Earth and is the primary cause of acid mine drainage (AMD). It has been established that this process involves multi-step electron-transfer reactions between surface defects and adsorbed O2 and H2O, releasing sulfoxy species (e.g., S2O32-, SO42-) and ferrous iron (Fe2+) to the solution and also producing intermediate by-products, such as hydrogen peroxide (H2O2) and other reactive oxygen species (ROS), however, our understanding of the kinetics of these transient species is still limited. We investigated the kinetics of H2O2 formation in aqueous suspensions of FeS2 microparticles by monitoring, in real time, the H2O2 and dissolved O2 concentration under oxic and anoxic conditions using amperometric microsensors. Additional spectroscopic and structural analyses were done to track the dependencies between the process of FeS2 dissolution and the degradation of H2O2 through the Fenton reaction. Based on our experimental results, we built a kinetic model which explains the observed trend of H2O2, showing that FeS2 dissolution can act as a natural Fenton reagent, influencing the oxidation of third-party species during the long term evolution of geochemical systems, even in oxygen-limited environments.

Process control plan for Single Shell Tank (SST) Saltcake Dissolution Proof of Concept

International Nuclear Information System (INIS)

ESTEY, S.D.

2001-01-01

This document describes the process controls for the tank 241-U-107 (U-107) saltcake dissolution proof-of-concept operations. Saltcake dissolution is defined as a method by which water-soluble salts will be retrieved from the Hanford Site radioactive waste tanks utilizing dissolution as the mobilizing mechanism. The proof-of-concept operations will monitor the retrieval process and transfer at least 100 kgal of fluid from tank U-107 to the double-shell tank (DST) system during the performance period. Tank U-107 has been identified as posing the highest long-term risk to the Columbia River of all single shell tanks (SSTs). This is because of the high content of mobile, long-lived radionuclides mostly in the saltcake waste in the tank. To meet current contractual and consent decree commitments, tank U-107 is being prepared for interim stabilization in August 2001. It is currently scheduled for saltcake retrieval in 2023, near the end of the SST retrieval campaign because of a lack of infrastructure in U-Farm. The proof-of-concept test will install a system to dissolve and retrieve a portion of the saltcake as part of, and operating in parallel with, the standard interim stabilization system to be installed on tank U-107. This proof-of-concept should provide key information on spray nozzle selection and effective spray patterns, leak detection, monitoring, and mitigation (LDMM) and in-tank saltcake solubility data that will help in the design of a full-tank retrieval demonstration system

Analysis of kinetic reaction mechanisms

CERN Document Server

Turányi, Tamás

2014-01-01

Chemical processes in many fields of science and technology, including combustion, atmospheric chemistry, environmental modelling, process engineering, and systems biology, can be described by detailed reaction mechanisms consisting of numerous reaction steps. This book describes methods for the analysis of reaction mechanisms that are applicable in all these fields. Topics addressed include: how sensitivity and uncertainty analyses allow the calculation of the overall uncertainty of simulation results and the identification of the most important input parameters, the ways in which mechanisms can be reduced without losing important kinetic and dynamic detail, and the application of reduced models for more accurate engineering optimizations. This monograph is invaluable for researchers and engineers dealing with detailed reaction mechanisms, but is also useful for graduate students of related courses in chemistry, mechanical engineering, energy and environmental science and biology.

MECHANISMS CONTROLLING Ca ION RELEASE FROM SOL-GEL DERIVED IN SITU APATITE-SILICA NANOCOMPOSITE POWDER

Directory of Open Access Journals (Sweden)

Seyed Mohsen Latifi

2015-03-01

Full Text Available Ca ion release from bioactive biomaterials could play an important role in their bioactivity and osteoconductivity properties. In order to improve hydroxyapatite (HA dissolution rate, in situ apatite-silica nanocomposite powders with various silica contents were synthesized via sol-gel method and mechanisms controlling the Ca ion release from them were investigated. Obtained powders were characterized by X-ray diffraction (XRD and transmission electron spectroscopy (TEM techniques, acid dissolution test, and spectroscopy by atomic absorption spectrometer (AAS. Results indicated the possible incorporation of (SiO44- into the HA structure and tendency of amorphous silica to cover the surface of HA particles. However, 20 wt. % silica was the lowest amount that fully covered HA particles. All of the nanocomposite powders showed more Ca ion release compared with pure HA, and HA - 10 wt. % silica had the highest Ca ion release. The crystallinity, the crystallite size, and the content of HA, along with the integrity, thickness, and ion diffusion possibility through the amorphous silica layer on the surface of HA, were factors that varied due to changes in the silica content and were affected the Ca ion release from nanocomposite powders.

Behavior of iodine in the dissolution of spent nuclear fuels

Energy Technology Data Exchange (ETDEWEB)

Sakurai, Tsutomu; Komatsu, Kazunori; Takahashi, A. [Japan Atomic Energy Research Institute, Ibaraki-ken (Japan)

1997-08-01

The results of laboratory-scale experiments concerning the behavior of iodine in the dissolution of spent nuclear fuels, which were carried out at the Japan Atomic Energy Research Institute, are summarized. Based on previous and new experimental results, the difference in quantity of residual iodine in the fuel solution between laboratory-scale experiments and reprocessing plants is discussed, Iodine in spent fuels is converted to the following four states: (1) oxidation into I{sub 2} by nitric acid, (2) oxidation into I{sub 2} by nitrous acid generated in the dissolution, (3) formation of a colloid of insoluble iodides such as AgI and PdI{sub 2}, and (4) deposition on insoluble residue. Nitrous acid controls the amount of colloid formed. As a result, up to 10% of iodine in spent fuels is retained in the fuel solution, up to 3% is deposited on insoluble residue, and the balance volatilizes to the off-gas, Contrary to earlier belief, when the dissolution is carried out in 3 to 4 M HNO{sub 3} at 100{degrees}C, the main iodine species in a fuel solution is a colloid, not iodate, Immediately after its formation, the colloid is unstable and decomposes partially in the hot nitric acid solution through the following reaction: AgI(s) + 2HNO{sub 3}(aq) = {1/2}I{sub 2}(aq) + AgNO{sub 3}(aq) + NO{sub 2}(g) + H{sub 2}O(1). For high concentrations of gaseous iodine, I{sub 2}(g), and NO{sub 2}, this reaction is reversed towards formation of the colloid (AgI). Since these concentrations are high near the liquid surface of a plant-scale dissolver, there is a possibility that the colloid is formed there through this reversal, Simulations performed in laboratory-scale experiments demonstrated this reversal, This phenomenon can be one reason the quantity of residual iodine in spent fuels is higher in reprocessing plants than in laboratory-scale experiments. 17 refs., 5 figs., 3 tabs.

Resistive switching in ZrO2 films: physical mechanism for filament formation and dissolution

International Nuclear Information System (INIS)

Parreira, Pedro; McVitie, Stephen; MacLaren, D A

2014-01-01

Resistive switching devices, also called memristors, have attracted much attention due to their potential memory, logic and even neuromorphic applications. Multiple physical mechanisms underpin the non-volatile switching process and are ultimately believed to give rise to the formation and dissolution of a discrete conductive filament within the active layer. However, a detailed nanoscopic analysis that fully explains all the contributory events remains to be presented. Here, we present aspects of the switching events that are correlated back to tunable details of the device fabrication process. Transmission electron microscopy and atomically resolved electron energy loss spectroscopy (EELS) studies of electrically stressed devices will then be presented, with a view to understanding the driving forces behind filament formation and dissolution

Hydrothermal reaction of albite and a sodium aluminosilicate glass: A solid-state NMR study

Science.gov (United States)

Yang, Wang-hong Alex; Kirkpatrick, R. James

1989-04-01

We present here a solid-state NMR study of the structure and chemical composition of the products and mechanisms of the reaction of crystalline low albite and a glass of nearly albite composition with aqueous solutions of pH from 1 to 11 at 250°C. For the crystalline albite, there are no detectable bulk or surface structural changes due to aqueous attack, consistent with the idea that both cation exchange and disruption of the aluminosilicate framework occur only near the mineral/solution interface and that the hydrated surface layer, if it exists, is not more than about 30 Å thick. This reaction occurs by solution/reprecipitation, and its rate decreases with increasing solution pH, supporting the idea that the dissolution of feldspar is initiated by cation-exchange. For the glass, the reaction proceeds by cation exchange of protons for Na +, incorporation of molecular water into the bulk glass, and a small amount of depolymerization of the aluminosilicate framework in the interior of the glass. Cation exchange becomes less important with increasing solution pH. The incorporation of molecular water and cation-exchange cause structural changes in the glass via solidstate adjustment without dissolution/reprecipitation. The large cations in the hydrated glass (Na and K) probably have a shell of water molecules around them, with a maximum average coordination number of six. The secondary phases formed from both albite and the glass are often amorphous and can be well characterized by NMR. The compositional and structural variations of the amorphous phases are important factors in these reactions and cannot be ignored in theoretical models of aluminosilicate dissolution. As expected, the aluminum coordination in the secondary phases changes from six-fold to four-fold as the solution pH increases.

Structural characterization of M(IV)1-xLn(III)xO2-x/2 (M = Ce, Th) mixed-oxides prepared from oxalate precursors. Multi-parametric study of dissolution and microstructural evolution

International Nuclear Information System (INIS)

Horlait, D.

2011-01-01

In the framework of Gen IV program development, several physico-chemical properties of some foreseen fuels, including the chemical durability, have to be evaluated. In this aim, a study was undertaken on M(IV) 1-x Ln(III) x O 2 (M=Ce,Th) model compounds prepared from oxalate precursors. The fluorite-type structure of CeO 2 and ThO 2 remains stable up to x ≅ 0.4, the substitution of M(IV) by Ln(III) occurring simultaneously to the formation of oxygen vacancies. For higher x values, a cubic superstructure is formed as a result of oxygen vacancies ordering. The normalized dissolution rates of such solids were found to be strongly enhanced by the Ln(III) fraction. On the contrary, the nature of the M(IV) and Ln(III) elements did not modify significantly the normalized dissolution rates. The effect of temperature and acid concentration suggested the existence of surface-controlling dissolution reactions. Simultaneously, the microstructural evolution of both powdered and sintered samples revealed some important changes in the reactive surface during dissolution tests. ESEM images allowed observing the existence of preferential dissolution sites located at grains boundaries and around crystalline defects, leading to the formation of corrosion pits. In addition, the formation of gelatinous phases, acting as diffusion barriers (thus slowing down the dissolution process) was also evidenced. (author) [fr

Enzymatic Dissolution of Biocomposite Solids Consisting of Phosphopeptides to Form Supramolecular Hydrogels

KAUST Repository

Shi, Junfeng; Yuan, Dan; Haburcak, Richard; Zhang, Qiang; Zhao, Chao; Zhang, Xixiang; Xu, Bing

2015-01-01

Enzyme-catalyzed dephosphorylation is essential for biomineralization and bone metabolism. Here we report the exploration of using enzymatic reaction to transform biocomposites of phosphopeptides and calcium (or strontium) ions to supramolecular hydrogels as a mimic of enzymatic dissolution of biominerals. 31P NMR shows that strong affinity between the phosphopeptides and alkaline metal ions (e.g., Ca2+ or Sr2+) induces the formation of biocomposites as precipitates. Electron microscopy reveals that the enzymatic reaction regulates the morphological transition from particles to nanofibers. Rheology confirms the formation of a rigid hydrogel. As the first example of enzyme-instructed dissolution of a solid to form supramolecular nanofibers/hydrogels, this work provides an approach to generate soft materials with desired properties, expands the application of supramolecular hydrogelators, and offers insights to control the demineralization of calcified soft tissues.

Enzymatic Dissolution of Biocomposite Solids Consisting of Phosphopeptides to Form Supramolecular Hydrogels

KAUST Repository

Shi, Junfeng

2015-10-14

Enzyme-catalyzed dephosphorylation is essential for biomineralization and bone metabolism. Here we report the exploration of using enzymatic reaction to transform biocomposites of phosphopeptides and calcium (or strontium) ions to supramolecular hydrogels as a mimic of enzymatic dissolution of biominerals. 31P NMR shows that strong affinity between the phosphopeptides and alkaline metal ions (e.g., Ca2+ or Sr2+) induces the formation of biocomposites as precipitates. Electron microscopy reveals that the enzymatic reaction regulates the morphological transition from particles to nanofibers. Rheology confirms the formation of a rigid hydrogel. As the first example of enzyme-instructed dissolution of a solid to form supramolecular nanofibers/hydrogels, this work provides an approach to generate soft materials with desired properties, expands the application of supramolecular hydrogelators, and offers insights to control the demineralization of calcified soft tissues.

Study of the dissolution velocity of dispersed solid particles. Development of a calculation method for analyzing the kinetic curves. Extension to the study of composed kinetics

International Nuclear Information System (INIS)

Jorda, Michel.

1976-01-01

The dissolution of a solid in an aqueous phase is studied, the solid consisting of dispersed particles. A continuous colorimetric analysis method is developed to study the dissolution process and a two-parameter optimization method is established to investigate the kinetic curves obtained. This method is based on the differential equation dx/dt=K(1-x)sup(n). (n being the decrease in the dissolution velocity when the dissolved part increases and K a velocity parameter). The dissolution of SO 4 Cu and MnO 4 K in water and UO 3 in SO 4 H 2 is discussed. It is shown that the dissolution velocity of UO 3 is proportional to the concentration of the H + ions in the solution as far as this one is not higher than 0.25N. The study of the temperature dependence of the UO 3 dissolution reaction shows that a transition phase takes place from 25 to 65 0 C between a phase in which the dissolution is controlled by the diffusion of the H + ions and the chemical reaction at the interface and a phase in which the kinetics is only controlled by the diffusion [fr

Comparison of uranium dissolution rates from spent fuel and uranium dioxide

International Nuclear Information System (INIS)

Steward, S.A.; Gray, W.J.

1994-01-01

Two similar sets of dissolution experiments, resulting from a statistical experimental design were performed in order to examine systematically the effects of temperature (25--75 degree C), dissolved oxygen (0.002-0.2 atm overpressure), pH (8--10) and carbonate concentrations (2--200 x 10 -4 molar) on aqueous dissolution of UO 2 and spent fuel. The average dissolution rate was 8.6 mg/m 2 ·day for UO 2 and 3.1 mg/m 2 ·day for spent fuel. This is considered to be an insignificant difference; thus, unirradiated UO 2 and irradiated spent fuel dissolved at about the same rate. Moreover, regression analyses indicated that the dissolution rates of UO 2 and spent fuel responded similarly to changes in pH, temperature, and carbonate concentration. However, the two materials responded very differently to dissolved oxygen concentration. Approximately half-order reaction rates with respect to oxygen concentration were found for UO 2 at all conditions tested. At room temperature, spent fuel dissolution (reaction) rates were nearly independent of oxygen concentration. At 75 degree C, reaction orders of 0.35 and 0.73 were observed for spent fuel, and there was some indication that the reaction order with respect to oxygen concentration might be dependent on pH and/or carbonate concentration as well as on temperature

Double porosity model to describe both permeability change and dissolution processes

International Nuclear Information System (INIS)

Niibori, Yuichi; Usui, Hideo; Chida, Taiji

2015-01-01

Cement is a practical material for constructing the geological disposal system of radioactive wastes. The dynamic behavior of both permeability change and dissolution process caused by a high pH groundwater was explained using a double porosity model assuming that each packed particle consists of the sphere-shaped aggregation of smaller particles. This model assumes two kinds of porosities between the particle clusters and between the particles, where the former porosity change mainly controls the permeability change of the bed, and the latter porosity change controls the diffusion of OH"- ions inducing the dissolution of silica. The fundamental equations consist of a diffusion equation of spherical coordinates of OH"- ions including the first-order reaction term and some equations describing the size changes of both the particles and the particle clusters with time. The change of over-all permeability of the packed bed is evaluated by Kozeny-Carman equation and the calculated radii of particle clusters. The calculated result well describes the experimental result of both permeability change and dissolution processes. (author)

The Use of Artificial Neural Network for Prediction of Dissolution Kinetics

Directory of Open Access Journals (Sweden)

H. Elçiçek

2014-01-01

Full Text Available Colemanite is a preferred boron mineral in industry, such as boric acid production, fabrication of heat resistant glass, and cleaning agents. Dissolution of the mineral is one of the most important processes for these industries. In this study, dissolution of colemanite was examined in water saturated with carbon dioxide solutions. Also, prediction of dissolution rate was determined using artificial neural networks (ANNs which are based on the multilayered perceptron. Reaction temperature, total pressure, stirring speed, solid/liquid ratio, particle size, and reaction time were selected as input parameters to predict the dissolution rate. Experimental dataset was used to train multilayer perceptron (MLP networks to allow for prediction of dissolution kinetics. Developing ANNs has provided highly accurate predictions in comparison with an obtained mathematical model used through regression method. We conclude that ANNs may be a preferred alternative approach instead of conventional statistical methods for prediction of boron minerals.

Theoretical study of the influence of chemical reactions and physical parameters on the convective dissolution of CO2 in aqueous solutions

Science.gov (United States)

Loodts, Vanessa; Rongy, Laurence; De Wit, Anne

2014-05-01

Subsurface carbon sequestration has emerged as a promising solution to the problem of increasing atmospheric carbon dioxide (CO2) levels. How does the efficiency of such a sequestration process depend on the physical and chemical characteristics of the storage site? This question is emblematic of the need to better understand the dynamics of CO2 in subsurface formations, and in particular, the properties of the convective dissolution of CO2 in the salt water of aquifers. This dissolution is known to improve the safety of the sequestration by reducing the risks of leaks of CO2 to the atmosphere. Buoyancy-driven convection makes this dissolution faster by transporting dissolved CO2 further away from the interface. Indeed, upon injection, the less dense CO2 phase rises above the aqueous layer where it starts to dissolve. The dissolved CO2 increases the density of the aqueous solution, thereby creating a layer of denser CO2-rich solution above less dense solution. This unstable density gradient in the gravity field is at the origin of convection. In this framework, we theoretically investigate the effect of CO2 pressure, salt concentration, temperature, and chemical reactions on the dissolution-driven convection of CO2 in aqueous solutions. On the basis of a linear stability analysis, we assess the stability of the time-dependent density profiles developing when CO2 dissolves in an aqueous layer below it. We predict that increasing CO2 pressure destabilizes the system with regard to buoyancy-driven convection, because it increases the density gradient at the origin of the instability. By contrast, increasing salt concentration or temperature stabilizes the system via effects on CO2 solubility, solutal expansion coefficient, diffusion coefficient and on the viscosity and density of the solution. We also show that a reaction of CO2 with chemical species dissolved in the aqueous solution can either enhance or decrease the amplitude of the convective dissolution compared

UO2 dissolution rates: A review

International Nuclear Information System (INIS)

McKenzie, W.F.

1992-09-01

This report reviews literature data on UO 2 dissolution kinetics and provides a framework for guiding future experimental studies as well as theoretical modeling studies. Under oxidizing conditions, UO 2 dissolution involves formation of an oxidized surface layer which is then dissolved by formation of aqueous complexes. Higher oxygen pressures or other oxidants are required at higher temperatures to have dissolution rates independent of oxygen pressure. At high oxygen pressures (1-5 atm, 25-70 C), the dissolution rate has a one-half order dependence on oxygen pressure, whereas at oxygen pressures below 0.2 atm, Grandstaff (1976), but nobody else, observed a first-order dependence on dissolution rate. Most people found a first-order dependence on carbonate concentration; Posey-Dowty (1987) found independence of carbonate at pH 7 to 8.2. Dissolution rates increase with temperature except in experiments involving granitic groundwater. Dissolution rates were generally greater under acid or basic conditions than near neutral pH

Long-term safety of radioactive waste disposal: Chemical reaction of fabricated and high burnup spent UO2 fuel with saline brines. Final report

International Nuclear Information System (INIS)

Grambow, B.; Casas, I.; Pablo, J. de; Gimenez, J.; Torrero, M.E.

1996-03-01

This is the final report of a large EU-research project on spent fuel stability in saline repository environments. Static dissolution experiments with high burnup spent fuel samples and unirradiated UO 2 were performed for about two years in anaerobic NaCl solutions and deionized water with and without container material (iron) being present. Experiments performed at 25 and 150 C gave similar results. Dissolution rates were similar to those measured in the Swedish, or Canadian program for granite media. Rates are strongly influenced by the specific sample surface area, probably related to the mass balance of consumption and production of radiolytic oxidants. In the competition between the oxidizing effect of radiolysis and the reducing effect of iron, the metal corrosion process dominates. Processes controlling radionuclide release are matrix dissolution, solubility, coprecipitation sorption phenomena and colloid formation. In the absence of iron release rates of Sr90, Tc99, Np237, Sb125 and at low reaction progress Ru106 were controlled by matrix dissolution whereas concentrations of tetra-, hexa-, and trivalent actinides (U, Pu, Am, Cm) were controlled by solubility or coprecipitation. The presence of iron did effectively reduce the rates of fuel dissolution and the concentration of many, though not all radionuclides. Solubilities of U were similar for uniradiated UO 2 and for spent fuel both in the case of oxidizing and reducing conditions. In contrast, due to the effect of radiolysis, reaction rates of spent fuel were higher than UO 2 dissolution rates. (orig.) [de

Determination of the Dissolution Slowness Surface by Study of Etched Shapes: II. Comparison of 2D Experimental and Theoretical Etching Shapes

Science.gov (United States)

Leblois, T.; Tellier, C. R.; Messaoudi, T.

1997-03-01

The anisotropic etching behavior of quartz crystal in concentrated ammonium bifluoride solution is studied and analyzed in the framework of a tensorial model. This model allows to simulate bi- or three-dimensional etching shapes from the equation for the representative surface of the dissolution slowness. In this paper, we present experimental results such as surface profile and initially circular cross-sectional profiles of differently singly- or doubly-rotated cuts. The polar diagrams of the dissolution slowness vector in several planes are deduced from experimental data. The comparison between predicted surface and cross-sectional profiles and experimental results is detailed and shows a good agreement. In particular, several examples give evidence that the final etched shapes are correlated to the extrema of the dissolution slowness. However, in several cases, experimental shapes cannot be simply correlated to the presence of extrema. Simulation gives effectively evidence for an important role played by more progressive changes in the curvature of the slowness surface. Consequently, analysis of data merits to be treated carefully. Nous nous proposons d'étudier et d'analyser à l'aide du modèle tensoriel de la dissolution l'attaque chimique anisotrope du cristal de quartz dans une solution concentrée de bifluorure d'ammonium. Ce modèle permet de simuler des formes usinées à deux ou trois dimensions à partir de l'équation de la surface représentative de la lenteur de dissolution du cristal de quartz. Dans cet article, nous présentons des résultats expérimentaux concernant des profils de surface et des sections initialement cylindriques de coupes à simple et double rotation. Les diagrammes polaires du vecteur lenteur de dissolution dans différents plans sont déduits de données expérimentales. La comparaison entre les profils de surface et de section théoriques et les résultats expérimentaux est détaillée et montre un bon accord. En

Examining the Conservatisms in Dissolution Rates of Commercial Spent Nuclear Fuel

International Nuclear Information System (INIS)

Hanson, Brady D.

2008-01-01

Most models for commercial spent nuclear fuel dissolution are based on data obtained from single-pass flow-through tests. These tests are designed to have a high water volume to fuel surface area ratio so that the concentration of radionuclides in solution are below solubility limits and thus back reactions and the formation of alteration products are minimized. While this method is ideal for determining the dependence of the dissolution rate on various parameters, it is important to examine the differences between these tests and the realistic scenarios that will exist in a geologic repository. Many of the inherent conservatisms that are part of the models are examined. These conservatisms include: limited water, short-term vs. long-term rates, groundwater effects, non-congruent release, radiolysis, and fuel chemistry effects. Each of these conservatisms has the potential to decrease the currently modeled dissolution rates by between a factor of 2 and 200. The combined effects are unknown, but, if quantified, could significantly improve the waste form performance relative to current models.

Mechanical stability of surface architecture--consequences for superhydrophobicity.

Science.gov (United States)

Dyett, Brendan P; Wu, Alex H; Lamb, Robert N

2014-11-12

Wet chemistry methods such as sol-gel provide a facile means of preparing coatings with controlled surface chemistry and architecture. The manipulation of colloidal "building blocks," film constituents, and reaction conditions makes it a promising method for simple, scalable, and routine production of superhydrophobic coatings. Despite all of this, the practical application of superhydrophobic coatings remains limited by low mechanical durability. The translation of chemistry to mechanical strength within superhydrophobic films is severely hindered by the requisite physical structure. More specifically, porosity and the surface architecture of roughness in sol-gel-derived films contribute significantly to poor mechanical properties. These physical effects emphasize that collective structure and chemistry-based strategies are required. This challenge is not unique to superhydrophobics, and there are many principles that can be drawn upon to greatly improve performance. The delicate interplay between chemistry and physical structure has been highlighted through theory and characterization of porous and rough interfaces within and outside the framework of superhydrophobics. Insights can further be drawn from biology. Nature's capacity for self-repair remains extremely challenging to mimic in materials. However, nature does demonstrate strategies for structuring nano- and microbuilding blocks to achieve generally mutually exclusive properties. Difficulties with characterization and example mechanical characterization methods have also been emphasized.

A Reaction-Diffusion-Based Coding Rate Control Mechanism for Camera Sensor Networks

Directory of Open Access Journals (Sweden)

Naoki Wakamiya

2010-08-01

Full Text Available A wireless camera sensor network is useful for surveillance and monitoring for its visibility and easy deployment. However, it suffers from the limited capacity of wireless communication and a network is easily overflown with a considerable amount of video traffic. In this paper, we propose an autonomous video coding rate control mechanism where each camera sensor node can autonomously determine its coding rate in accordance with the location and velocity of target objects. For this purpose, we adopted a biological model, i.e., reaction-diffusion model, inspired by the similarity of biological spatial patterns and the spatial distribution of video coding rate. Through simulation and practical experiments, we verify the effectiveness of our proposal.

A reaction-diffusion-based coding rate control mechanism for camera sensor networks.

Science.gov (United States)

Yamamoto, Hiroshi; Hyodo, Katsuya; Wakamiya, Naoki; Murata, Masayuki

2010-01-01

A wireless camera sensor network is useful for surveillance and monitoring for its visibility and easy deployment. However, it suffers from the limited capacity of wireless communication and a network is easily overflown with a considerable amount of video traffic. In this paper, we propose an autonomous video coding rate control mechanism where each camera sensor node can autonomously determine its coding rate in accordance with the location and velocity of target objects. For this purpose, we adopted a biological model, i.e., reaction-diffusion model, inspired by the similarity of biological spatial patterns and the spatial distribution of video coding rate. Through simulation and practical experiments, we verify the effectiveness of our proposal.

The mechanisms of drug release from solid dispersions in water-soluble polymers.

Science.gov (United States)

Craig, Duncan Q M

2002-01-14

Solid dispersions in water-soluble carriers have attracted considerable interest as a means of improving the dissolution rate, and hence possibly bioavailability, of a range of hydrophobic drugs. However, despite the publication of numerous original papers and reviews on the subject, the mechanisms underpinning the observed improvements in dissolution rate are not yet understood. In this review the current consensus with regard to the solid-state structure and dissolution properties of solid dispersions is critically assessed. In particular the theories of carrier- and drug-controlled dissolution are highlighted. A model is proposed whereby the release behaviour from the dispersions may be understood in terms of the dissolution or otherwise of the drug into the concentrated aqueous polymer layer adjacent to the solid surface, including a derivation of an expression to describe the release of intact particles from the dispersions. The implications of a deeper understanding of the dissolution mechanisms are discussed, with particular emphasis on optimising the choice of carrier and manufacturing method and the prediction of stability problems.

Kinetics of ikaite precipitation and dissolution in seawater-derived brines at sub-zero temperatures to 265 K

Science.gov (United States)

Papadimitriou, Stathys; Kennedy, Hilary; Kennedy, Paul; Thomas, David N.

2014-09-01

The kinetics of calcium carbonate hexahydrate (ikaite) precipitation and dissolution were investigated in seawater and seawater-derived brines at sub-zero temperatures using the constant addition experimental technique. The steady state rate of these two processes was found to be a function of the deviation of the solution from equilibrium with respect to ikaite and conformed to the same empirical rate law as the anhydrous CaCO3 polymorphs, calcite and aragonite. In addition to the saturation state of the brine with respect to ikaite, the salinity of the brine and the temperature of the reaction evidently exerted some control on the ikaite precipitation kinetics, while the dissolution kinetics of the polymorph were not noticeably influenced by these two parameters. The experimental salinity and temperature conditions were equivalent to those at thermal equilibrium between brine and ice in the sea ice cover of polar seas. Simple modelling of the CO2 system by extrapolation of the oceanic equivalent to sea ice brines showed that the physical concentration of seawater ions and the changes in ikaite solubility as a function of salinity and temperature, both inherent in the sea ice system, would be insufficient to drive the emergent brines to ikaite supersaturation and precipitation in sea ice down to -8 °C. The loss of dissolved inorganic carbon to the gas phase of sea ice and to sympagic autotrophs are two independent mechanisms which, in nature, could prompt the brine CO2 system towards ikaite supersaturation and precipitation. Under these conditions, the steady state precipitation rate of ikaite was found to be fast enough for rapid formation within short time scales (days to weeks) in sea ice. The observed ikaite dissolution kinetics were also found conducive to short turn-over time scales of a few hours to a few days in corrosive solutions, such as surface seawater.

Dissolution of morphology-controlled Th1-xUxO2 model dioxides

International Nuclear Information System (INIS)

Hingant, N.; Hubert, S.; Barre, N.; Clavier, N.; Dacheux, N.

2008-01-01

The influence of the morphology of Th 1-x U x O 2 solid solutions on their chemical durability was evaluated considering two routes of preparation, involving either direct precipitation of a precursor or hydrothermal conditions. The great differences in terms of morphology and crystallization state of the so-obtained samples were correlated to an important variation of the specific surface area of the final dioxides then to the density of the sintered pellets fired at 1500 deg. C. In order to evaluate the chemical durability of such materials, leaching tests were undertaken. The dissolution of the samples was associated to low normalized dissolution rates typically ranging from 3.10 -6 g.m -2 .day -1 (HNO 3 10 -4 M) to 2 10 -5 g.m -2 .day -1 (HNO 3 10 -1 M) at 25 deg. C for x equals 0.25. The influence of the x value on the normalized dissolution rate was found to be limited due to the homogenization of the cationic distribution obtained through the precipitation process. Moreover, the good crystallization state initially obtained from hydrothermal conditions led to a higher chemical durability. (authors)

Dissolution behaviour of silicon nitride coatings for joint replacements

Energy Technology Data Exchange (ETDEWEB)

Pettersson, Maria [Materials in Medicine Group, Div. of Applied Materials Science, Dept. of Engineering Sciences, Uppsala University, Uppsala (Sweden); Bryant, Michael [Institute of Functional Surfaces (iFS), School of Mechanical Engineering, University of Leeds, Leeds (United Kingdom); Schmidt, Susann [Thin Film Physics, Department of Physics, Chemistry and Biology (IFM), Linköping University, Linköping (Sweden); Engqvist, Håkan [Materials in Medicine Group, Div. of Applied Materials Science, Dept. of Engineering Sciences, Uppsala University, Uppsala (Sweden); Hall, Richard M. [Institute of Medical and Biological Engineering (iMBE), School of Mechanical Engineering, University of Leeds, Leeds (United Kingdom); Neville, Anne [Institute of Functional Surfaces (iFS), School of Mechanical Engineering, University of Leeds, Leeds (United Kingdom); Persson, Cecilia, E-mail: cecilia.persson@angstrom.uu.se [Materials in Medicine Group, Div. of Applied Materials Science, Dept. of Engineering Sciences, Uppsala University, Uppsala (Sweden)

2016-05-01

In this study, the dissolution rate of SiN{sub x} coatings was investigated as a function of coating composition, in comparison to a cobalt chromium molybdenum alloy (CoCrMo) reference. SiN{sub x} coatings with N/Si ratios of 0.3, 0.8 and 1.1 were investigated. Electrochemical measurements were complemented with solution (inductively coupled plasma techniques) and surface analysis (vertical scanning interferometry and x-ray photoelectron spectroscopy). The dissolution rate of the SiN{sub x} coatings was evaluated to 0.2–1.4 nm/day, with a trend of lower dissolution rate with higher N/Si atomic ratio in the coating. The dissolution rates of the coatings were similar to or lower than that of CoCrMo (0.7–1.2 nm/day). The highest nitrogen containing coating showed mainly Si–N bonds in the bulk as well as at the surface and in the dissolution area. The lower nitrogen containing coatings showed Si–N and/or Si–Si bonds in the bulk and an increased formation of Si–O bonds at the surface as well as in the dissolution area. The SiN{sub x} coatings reduced the metal ion release from the substrate. The possibility to tune the dissolution rate and the ability to prevent release of metal ions encourage further studies on SiN{sub x} coatings for joint replacements. - Graphical abstract: Dissolution rates of SiN{sub 0.3}, SiN{sub 0.8}, and SiN{sub 1.1} coatings on CoCrMo compared to uncoated CoCrMo. Dissolution rates were obtained from i) electrochemical measurements of I{sub corr}, ii) the step height between covered and solution-exposed surfaces, measured using VSI, and iii) the ion concentration in the solution, measured with ICP. - Highlights: • The dissolution of SiN{sub x} coatings was investigated in comparison to (bulk) CoCrMo. • The coatings gave a lower or similar dissolution rate to CoCrMo, of 0.2–1.2 nm/day. • An increased nitrogen content in the coatings gave lower dissolution rates. • SiN{sub x} coatings on CoCrMo reduced the metal ion release

Adsorption of water, sulfates and chloride on arsenopyrite surface

Science.gov (United States)

Silva, Juliana C. M.; dos Santos, Egon C.; de Oliveira, Aline; Heine, Thomas; De Abreu, Heitor A.; Duarte, Hélio A.

2018-03-01

Arsenopyrite is one of the sulfide minerals responsible for acid rock drainage (ARD) and is one of the most hazardous in regions affected by mining activities. This phenomenon involves complex reaction mechanism. Although it is intensely investigated, there is a lack of consensus concerning the reaction mechanisms and more information is still necessary. In this work, the adsorption of water, hydrochloric acid, and sulfuric acid on arsenopyrite (001) surface was investigated by means of Density Functional calculations and the results compared to other sulfides aiming to understand the mineral/water interface. The interaction of the chemical species with the (001) FeAsS surface is the first step to understand the intricate oxidation mechanism of arsenopyrite. Molecular water adsorption on (001) FeAsS is more favored than the adsorption of sulfate favoring the dissolution of sulfates and enhancing its oxidation. The estimated adsorption energies of water, sulfates and chloride on other sulfide minerals are compared with the estimated values for arsenopyrite and the chemical reactivity differences discussed in detail.

Microstructure and mechanical properties of 2024-T3 and 7075-T6 aluminum alloys and austenitic stainless steel 304 after being exposed to hydrogen peroxide

Science.gov (United States)

Sofyan, Nofrijon Bin Imam

The effect of hydrogen peroxide used as a decontaminant agent on selected aircraft metallic materials has been investigated. The work is divided into three sections; bacterial attachment behavior onto an austenitic stainless steel 304 surface; effect of decontamination process on the microstructure and mechanical properties of aircraft metallic structural materials of two aluminum alloys, i.e. 2024-T3 and 7075-T6, and an austenitic stainless steel 304 as used in galley and lavatory surfaces; and copper dissolution rate into hydrogen peroxide. With respect to bacterial attachment, the results show that surface roughness plays a role in the attachment of bacteria onto metallic surfaces at certain extent. However, when the contact angle of the liquid on a surface increased to a certain degree, detachment of bacteria on that surface became more difficult. In its relation to the decontamination process, the results show that a corrosion site, especially on the austenitic stainless steel 304 weld and its surrounding HAZ area, needs more attention because it could become a source or a harborage of bio-contaminant agent after either incidental or intentional bio-contaminant delivery. On the effect of the decontamination process on the microstructure and mechanical properties of aircraft metallic structural materials, the results show that microstructural effects are both relatively small in magnitude and confined to a region immediately adjacent to the exposed surface. No systematic effect is found on the tensile properties of the three alloys under the conditions examined. The results of this investigation are promising with respect to the application of vapor phase hydrogen peroxide as a decontaminant agent to civilian aircraft, in that even under the most severe circumstances that could occur; only very limited damage was observed. The results from the dissolution of copper by concentrated liquid hydrogen peroxide showed that the rate of copper dissolution increased for

Experimental study of kinetic and mechanism of dissolution of apatite structured minerals. Application to the prediction of the long term behavior of an actinides storage host matrix

International Nuclear Information System (INIS)

Chairat, C.

2005-11-01

The motivation for this study is to assess the potential of using apatite structured ceramics as long-lived actinide storage hosts. To assess their ability to resist aqueous corrosion, the dissolution of natural fluoro-apatite and synthetic Nd-britholite (neodymium is a proxy for the trivalent actinides) was studied. Mineral surfaces were characterized using a combined spectrometric, electrokinetic and potentiometric approach and dissolution rates were measured in closed and open system reactors as a function of solution composition. Experimental results suggest apatitic minerals dissolve via distinct step sequence: 1) fluoride release, 2) release of the calcium situated in the M1, and 3) the simultaneous removal of phosphate and calcium II via the breaking of only Ca-O bonds. TST based rate equations based in this mechanism accurately describe fluoro-apatite and synthetic britholite dissolution rates as a function of solution composition. Nd release rates are limited by precipitation of Nd-rhabdophane. (author)

Study of the surface crystallization and resistance to dissolution of niobium phosphate glasses for nuclear waste immobilization

International Nuclear Information System (INIS)

Vieira, Heveline

2008-01-01

The surface crystallization and the dissolution rate of three phosphate glass compositions containing different amounts of niobium oxide were studied. The glasses were named Nb30, Nb37, and Nb44 according to the nominal content of niobium oxide in the glass composition. The three compositions were evaluated keeping the P 2 O 5 /K 2 O ratio constant and varying the amount of Nb 2 O 5 . These glasses were produced by melting appropriate chemical compounds at 1500 deg C for 0.5 hour. The crystalline phases which were nucleated on the glass surface after heat treatment were determined by X-ray diffraction. The crystalline structures depend on the amount of niobium oxide in the glass composition. The crystal morphologies were observed by using an optical microscope, and their characteristics are specific for each kind of crystalline phase. The crystal growth rate and the surface nuclei density were determined for each glass composition, and they depend on each crystalline phase nucleated on the surface. From the differential thermal analysis curves it was determined that the Nb44 glass containing 46.5 mol por cent of niobium oxide is the most thermally stable against crystallization when compared to the Nb30 and Nb37 glasses. According to the activation energies determined for crystal growth on the surface of each glass type, the Nb44 glass can also be considered the most resistant one against crystallization. The dissolution rate for the Nb44 glass after 14 days immersed in an aqueous solution with pH equals to 7 at 90 deg C is the lowest (9.0 x 10 -7 g. cm -2 . day -1 ) when compared to the other two glass compositions. The dissolution rates in acidic and neutral solutions of all studied glasses meet the international standards for materials which can be used in the immobilization of nuclear wastes. (author)

Chemistry of proposed calcination/dissolution processing of Hanford Site tank wastes

International Nuclear Information System (INIS)

Delegard, C.H.

1995-01-01

Plans exist to separate radioactive waste stored in underground tanks at the US Department of Energy's Hanford Site in south central Washington State into low-level and high-level fractions, and to immobilize the separate fractions in high-integrity vitrified forms for long-term disposal. Calcination with water dissolution has been proposed as a possible treatment for achieving low/high-level separation. Chemistry development activities conducted since 1992 with simulated and genuine tank waste show that calcination/dissolution destroys organic carbon and converts nitrate and nitrite to hydroxide and benign offgases. The process also dissolves significant quantities of bulk chemicals (aluminum, chromium, and phosphate), allowing their redistribution from the high-level to the low-level fraction. Present studies of the chemistry of calcination/dissolution processing of genuine wastes, conducted in the period October 1993 to September 1994, show the importance of sodium fluoride phosphate double salt in controlling phosphate dissolution. Peptization of waste solids is of concern if extensive washing occurs. Strongly oxidizing conditions imposed by calcination reactions were found to convert transition metals to soluble anions in the order chromate > manganate > > ferrate. In analogy with manganese behavior, plutonium dissolution, presumably by oxidation to more soluble anionic species, also occurs by calcination/dissolution. Methods to remove plutonium from the product low-level solution stream must be developed

Free Energy Landscape of the Dissolution of Gibbsite at High pH

Energy Technology Data Exchange (ETDEWEB)

Shen, Zhizhang; Kerisit, Sebastien N.; Stack, Andrew G.; Rosso, Kevin M.

2018-03-26

The individual elementary reactions involved in the dissolution of a solid into solution remain mostly speculative due to a lack of suitable, direct experimental probes. In this regard, we have applied atomistic simulations to map the free energy landscape of the dissolution of gibbsite from a step edge, as a model of metal hydroxide dissolution. The overall reaction combines kink site formation and kink site propagation. Two individual reactions were found to be rate-limiting for kink site formation, that is, the displacement of Al from a step site to a ledge adatom site and its detachment from ledge/terrace adatom sites into the solution. As a result, a pool of mobile and labile Al adsorbed species, or adatoms, exists before the release of Al into solution. Because of the quasi-hexagonal symmetry of gibbsite, kink site propagation can occur in multiple directions. Overall, the simulation results will enable the development of microscopic mechanistic models of metal oxide dissolution.

Controlling Chemical Reactions in Confined Environments: Water Dissociation in MOF-74

Directory of Open Access Journals (Sweden)

Erika M. A. Fuentes-Fernandez

2018-02-01

Full Text Available The confined porous environment of metal organic frameworks (MOFs is an attractive system for studying reaction mechanisms. Compared to flat oxide surfaces, MOFs have the key advantage that they exhibit a well-defined structure and present significantly fewer challenges in experimental characterization. As an example of an important reaction, we study here the dissociation of water—which plays a critical role in biology, chemistry, and materials science—in MOFs and show how the knowledge of the structure in this confined environment allows for an unprecedented level of understanding and control. In particular, combining in-situ infrared spectroscopy and first-principles calculations, we show that the water dissociation reaction can be selectively controlled inside Zn-MOF-74 by alcohol, through both chemical and physical interactions. Methanol is observed to speed up water dissociation by 25% to 100%, depending on the alcohol partial pressure. On the other hand, co-adsorption of isopropanol reduces the speed of the water reaction, due mostly to steric interactions. In addition, we also investigate the stability of the product state after the water dissociation has occurred and find that the presence of additional water significantly stabilizes the dissociated state. Our results show that precise control of reactions within nano-porous materials is possible, opening the way for advances in fields ranging from catalysis to electrochemistry and sensors.

Dissolution characteristics of chalcedony under alkaline condition. Study for changes in mineral composition of engineered barrier composed by bentonite

International Nuclear Information System (INIS)

Watanabe, Yasutaka; Yokoyama, Shingo

2016-01-01

In the engineered barrier of radioactive waste disposal facilities, it is expected that bentonite is exposed to alkaline groundwater which arise from leaching of cementations materials. Minerals contained in the bentonite will be dissolved by reactions of the alkaline groundwater. Some bentonite contains silica such as quartz and chalcedony. Chalcedony is categorized in intermediate silica which is microcrystalline. It is known that dissolution of silica influences to the dissolution of smectite by means of solubility. However, dissolution kinetics of chalcedony in the alkaline condition has not been investigated, which is an uncertainty in geochemical simulations to evaluate a long-term stability of the engineered barrier. Therefore, this study performed flow-through experiments in alkaline conditions using chalcedony in order to obtain the dissolution rate of the chalcedony. The flow-through experiments was performed using NaOH-NaCl solution adjusted to 0.3 mol/L of ionic strength. Initial pH of the solution was from 8.9 to 13.5. As a result, higher pH and higher temperature showed higher Si ion concentrations of reacted solutions. The dissolution rate of the samples was calculated using Si ion concentrations at steady state of the experiment. Note that, the dissolution rate of the chalcedony was almost same as that of quartz at same temperature. After the experiments, SEM observation showed that rough surface of the chalcedony partly changed to smooth surface like quartz. It is supposed that rough surface of chalcedony was rapidly dissolved because of low degree of crystallization. The dissolution rate obtained is supposedly applicable to highly crystalline SiO 2 of chalcedony. (author)

Aqueous Dissolution of Silver Iodide and Associated Iodine Release Under Reducing Conditions with Sulfide

International Nuclear Information System (INIS)

Yaohiro Inagaki; Toshitaka Imamura; Kazuya Idemitsu; Tatsumi Arima; Osamu Kato; Hidekazu Asano; Tsutomu Nishimura

2007-01-01

Aqueous dissolution tests of silver iodide (AgI) were performed in Na 2 S solutions in order to evaluate, empirically, dissolution of AgI to release iodine under reducing conditions with sulfide. The results indicated that AgI dissolves to release iodine being controlled by mainly precipitation of Ag 2 S. However, the dissolution of AgI can be depressed to proceed, and the thermodynamic equilibrium cannot be attained easily. Solid phase analysis for the reacted AgI suggested that a thin layer of solid silver forming at AgI surface may evolve to be protective against transportation of reactant species, which can lead to the depression in the dissolution of AgI. (authors)

Probable leaching mechanisms for spent fuel

International Nuclear Information System (INIS)

Wang, R.; Katayama, Y.B.

1981-01-01

At the Pacific Northwest Laboratory, researchers in the Waste/Rock Interaction Technology Program are studying spent fuel as a possible waste form for the Office of Nuclear Waste Isolation. This paper presents probable leaching mechanisms for spent fuel and discusses current progress in identifying and understanding the leaching process. During the past year, experiments were begun to study the complex leaching mechanism of spent fuel. The initial work in this investigation was done with UO 2 , which provided the most information possible on the behavior of the spent-fuel matrix without encountering the very high radiation levels associated with spent fuel. Both single-crystal and polycrystalline UO 2 samples were used for this study, and techniques applicable to remote experimentation in a hot cell are being developed. The effects of radiation are being studied in terms of radiolysis of water and surface activation of the UO 2 . Dissolution behavior and kinetics of UO 2 were also investigated by electrochemical measurement techniques. These data will be correlated with those acquired when spent fuel is tested in a hot cell. Oxidation effects represent a major area of concern in evaluating the stability of spent fuel. Dissolution of UO 2 is greatly increased in an oxidizing solution because the dissolution is then controlled by the formation of hexavalent uranium. In solutions containing very low oxygen levels (i.e., reducing solutions), oxidation-induced dissolution may be possible via a previously oxidized surface, through exposure to air during storage, or by local oxidants such as O 2 and H 2 O 2 produced from radiolysis of water and radiation-activated UO 2 surfaces. The effects of oxidation not only increase the dissolution rate, but could lead to the disintegration of spent fuel into fine fragments

The energetic conditions determining the active dissolution of carbon steel during electrocoagulation in sulfate media

International Nuclear Information System (INIS)

Gerónimo-López, Carlos; Vazquez-Arenas, Jorge; Picquart, Michel; González, Ignacio

2014-01-01

This study aims to investigate the active dissolution of carbon steel under rotating conditions, necessary for continuous dosing of metal cation in electrocoagulation. A reaction mechanism is proposed for its dissolution in 0.1, 0.3 and 0.5 M Na 2 SO 4 , using electrochemical and chemical techniques (Raman, SEM). A continuous dissolution region was obtained from the potentiodynamic study, as a result of the competition between the rate of electrochemical reactions and the rate at which energetic conditions are imposed on the electrode. On the other hand, the dissolution of carbon steel underwent active, transition and passivation regions in potentiostatic and galvanostatic techniques, which respectively shifted to higher current densities and more positive potentials as the electrolyte concentration (Na 2 SO 4 ) was increased. In general, the increase of Na 2 SO 4 concentration promotes the iron dissolution and tightens the active region. The results revealed that the Na 2 SO 4 concentration, the Fe(II)/Fe(III) interface concentration, and the time of perturbation influence the occurrence and evolution of the Green Rust Sulphate (NaFe 6 II Fe 3 III (OH) 18 (SO 4 ) 2 ) intermediary, a precursor which hinders electrocoagulation through passive film formation. Scanning Electronic Microscopy and Raman spectroscopy showed that in the active dissolution region, the films grown potentiostatically are porous and contain α-FeOOH, δ-FeOOH, and Fe 3 O 4 as the dominant species. In the transition region, these films become less porous and include α-FeOOH, Fe 3 O 4 , α-Fe 2 O 3 , γ-Fe 2 O 3 , while γ-FeOOH was identified in the passive region

Quantifying Silica Reactivity in Subsurface Environments: Reaction Affinity and Solute Matrix Controls on Quartz and SiO2 Glass Dissolution Kinetics

International Nuclear Information System (INIS)

Dove, Patricia M.

2000-01-01

During the three years of this project, Professor Dove's laboratory made tremendous progress in understanding controls on amorphous silica dissolution kinetics in aqueous solutions. Our findings have already received considerable attention. In hydrothermal and low temperature studies, the work focused on determining quantitative and mechanistic controls on the most abundant silica polymorphs in Earth environments--quartz and amorphous silica. Our studies achieved goals set forth in the original proposal to establish a new quantitative understanding of amorphous silica dissolution. This support has resulted in 10 journal, 12 abstracts and 2 thesis publications. The PI and students were also recognized with 6 awards during this period. The 1998 EMSP conference in Chicago was an important meeting for our project. The symposium, enabled P.I. Dove to establish valuable contacts with ''users'' having specific needs for the findings of our EMSP project related to the urgency of problems in the Tanks Focus Area (TFA). Since that time, our working relations developed as Dove interacted with TFA scientists and engineers on the problems of waste glass properties. These interactions refined our experimental objectives to better meet their needs. Dove presented the results of EMSP research findings to a TFA subgroup at a Product Acceptance Workshop held in Salt Lake City during December 1998. The travel costs to attend this unanticipated opportunity were paid from EMSP project funds. In January 2000, Dove also attended a similar meeting in Atlanta with PNNL, SRL and BNF scientists/engineers to discuss new issues and make another level of decisions on the Product Acceptance goals. Our EMSP-funded research interfaced very well with the ongoing studies of Dr. Pete McGrail and colleagues in the Applied Geochemistry Group at PNNL. The value of our work to ''users'' was further demonstrated when Dove's EMSP-funded Postdoc, Dr. Jonathan Icenhower was hired by the same PNNL group. With

Reaction kinetic model of the surface-mediated formation of PCDD/F from pyrolysis of 2-chlorophenol on a CuP/Silica suface

Energy Technology Data Exchange (ETDEWEB)

Lomnicki, S.; Khachatryan, L.; Dellinger, B. [Louisiana State Univ., Baton Rouge (United States). Dept. of Chemistry

2004-09-15

One of the major challenges in developing predictive models of the surface mediated pollutant formation and fuel combustion is the construction of reliable reaction kinetic mechanisms and models. While the homogeneous, gas-phase chemistry of various light fuels such as hydrogen and methane is relatively well-known large uncertainties exist in the reaction paths of surface mediated reaction mechanisms for even these very simple species. To date, no detailed kinetic consideration of the surface mechanisms of formation of complex organics such as PCDD/F have been developed. In addition to the complexity of the mechanism, a major difficulty is the lack of reaction kinetic parameters (pre-exponential factor and activation energy) of surface reactions, Consequently, numerical studies of the surface-mediated formation of PCDD/F have often been incorporated only a few reactions. We report the development of a numerical multiple-step surface model based on experimental data of surface mediated (5% CuO/SiO2) conversion of 2-monochlorphenol (2-MCP) to PCDD/F under pyrolytic or oxidative conditions. A reaction kinetic model of the catalytic conversion of 2-MCP on the copper oxide catalyst under pyrolytic conditions was developed based on a detailed multistep surface reaction mechanism developed in our laboratory. The performance of the chemical model is assessed by comparing the numerical predictions with experimental measurements. SURFACE CHEMKIN (version 3.7.1) software was used for modeling. Our results confirm the validity of previously published mechanism of the reaction and provides new insight concerning the formation of PCDD/F formation in combustion processes. This model successfully explains the high yields of PCDD/F at low temperatures that cannot be explained using a purely gas-phase mode.

The dissolution rate constant of magnetite in water at different temperatures and pH conditions

International Nuclear Information System (INIS)

Mohajery, Khatereh; Deydier de Pierrefeu, Laurent; Lister, Derek H.

2012-09-01

Under the nominal conditions of power system coolants, the corrosion of components made of carbon steel is limited by the magnetite films that develop on surfaces. In some situations, the magnetite film loses much of its protective ability and corrosion and loss of iron to the system are exacerbated. Common examples of such situations occur when the system is non-isothermal so that temperature gradients cause differences in magnetite solubility around the circuit; the resulting areas of under-saturation in iron give rise to dissolution of normally protective films. Condensing steam in two-phase systems may also promote oxide dissolution. When the turbulence in the system is high, oxide degradation is aggravated and flow-accelerated corrosion (FAC) results. The subsequent increased loading of systems with iron leads to fouling of flow passages and heat transfer surfaces and in reactor primary coolants to rising radiation fields, while FAC can have disastrous results in terms of pipe wall thinning and eventual rupture. Magnetite dissolution is clearly a key contributor to these processes. Thus, the conventional mechanistic description of FAC postulates magnetite dissolution in series with mass transfer of iron from the film to the bulk coolant. In the resulting equations, if the dissolution rate constant is considerably less than the mass transfer coefficient for a particular situation, dissolution will control and flow should have no effect. This is clearly untenable for FAC, so it is often assumed that mass transfer controls and the contribution from oxide dissolution is ignored - on occasion when data on dissolution kinetics are available and sometimes when those data show that dissolution should control. In most cases, however, dissolution rate constants for magnetite are not available. At UNB Nuclear we have a research program using a high-temperature loop to measure dissolution rates of magnetite in water under various conditions of flow, temperature and

The oxygen reduction reaction mechanism on Pt(111) from density functional theory calculations

DEFF Research Database (Denmark)

Tripkovic, Vladimir; Skulason, Egill; Siahrostami, Samira

2010-01-01

We study the oxygen reduction reaction (ORR) mechanism on a Pt(1 1 1) surface using density functional theory calculations We find that at low overpotentials the surface is covered with a half dissociated water layer We estimate the barrier for proton transfer to this surface and the barrier...

Vibrational Mode-Specific Reaction of Methane on a Nickel Surface

Science.gov (United States)

Beck, Rainer D.; Maroni, Plinio; Papageorgopoulos, Dimitrios C.; Dang, Tung T.; Schmid, Mathieu P.; Rizzo, Thomas R.

2003-10-01

The dissociation of methane on a nickel catalyst is a key step in steam reforming of natural gas for hydrogen production. Despite substantial effort in both experiment and theory, there is still no atomic-scale description of this important gas-surface reaction. We report quantum state-resolved studies, using pulsed laser and molecular beam techniques, of vibrationally excited methane reacting on the nickel (100) surface. For doubly deuterated methane (CD2H2), we observed that the reaction probability with two quanta of excitation in one C-H bond was greater (by as much as a factor of 5) than with one quantum in each of two C-H bonds. These results clearly exclude the possibility of statistical models correctly describing the mechanism of this process and attest to the importance of full-dimensional calculations of the reaction dynamics.

Dissolution process analysis using model-free Noyes-Whitney integral equation.

Science.gov (United States)

Hattori, Yusuke; Haruna, Yoshimasa; Otsuka, Makoto

2013-02-01

Drug dissolution process of solid dosages is theoretically described by Noyes-Whitney-Nernst equation. However, the analysis of the process is demonstrated assuming some models. Normally, the model-dependent methods are idealized and require some limitations. In this study, Noyes-Whitney integral equation was proposed and applied to represent the drug dissolution profiles of a solid formulation via the non-linear least squares (NLLS) method. The integral equation is a model-free formula involving the dissolution rate constant as a parameter. In the present study, several solid formulations were prepared via changing the blending time of magnesium stearate (MgSt) with theophylline monohydrate, α-lactose monohydrate, and crystalline cellulose. The formula could excellently represent the dissolution profile, and thereby the rate constant and specific surface area could be obtained by NLLS method. Since the long time blending coated the particle surface with MgSt, it was found that the water permeation was disturbed by its layer dissociating into disintegrant particles. In the end, the solid formulations were not disintegrated; however, the specific surface area gradually increased during the process of dissolution. The X-ray CT observation supported this result and demonstrated that the rough surface was dominant as compared to dissolution, and thus, specific surface area of the solid formulation gradually increased. Copyright © 2012 Elsevier B.V. All rights reserved.

Field and laboratory emission cell automation and control system for investigating surface chemistry reactions

Science.gov (United States)

Flemmer, Michael M.; Ham, Jason E.; Wells, J. R.

2007-01-01

A novel system [field and laboratory emission cell (FLEC) automation and control system] has been developed to deliver ozone to a surface utilizing the FLEC to simulate indoor surface chemistry. Ozone, humidity, and air flow rate to the surface were continuously monitored using an ultraviolet ozone monitor, humidity, and flow sensors. Data from these sensors were used as feedback for system control to maintain predetermined experimental parameters. The system was used to investigate the chemistry of ozone with α-terpineol on a vinyl surface over 72h. Keeping all other experimental parameters the same, volatile organic compound emissions from the vinyl tile with α-terpineol were collected from both zero and 100ppb(partsper109) ozone exposures. System stability profiles collected from sensor data indicated experimental parameters were maintained to within a few percent of initial settings. Ozone data from eight experiments at 100ppb (over 339h) provided a pooled standard deviation of 1.65ppb and a 95% tolerance of 3.3ppb. Humidity data from 17 experiments at 50% relative humidity (over 664h) provided a pooled standard deviation of 1.38% and a 95% tolerance of 2.77%. Data of the flow rate of air flowing through the FLEC from 14 experiments at 300ml/min (over 548h) provided a pooled standard deviation of 3.02ml/min and a 95% tolerance range of 6.03ml/min. Initial experimental results yielded long term emissions of ozone/α-terpineol reaction products, suggesting that surface chemistry could play an important role in indoor environments.

Investigation of the gas formation in dissolution process of nuclear reactor fuel

International Nuclear Information System (INIS)

Zhang Qinfen; Liao Yuanzhong; Chen Yongqing; Sun Shuyun; Fan Yincheng

1987-12-01

The gas formation in dissolution process of two kinds of nuclear fuels was studied. The results shows that the maximum volume flow released from dissolution system is composed of two parts. One of them is air remained in dissolver and pushed out by acid vapor. The other is produced in dissolution reaction. The procedure of calculating the gas amount produced in dissolution process has been given. It is based on variation of components of dissolution solution. The gas amount produced in dissolution process of spent UO 2 fuel elements was calculated. The condenser system and loading volume of disposal system of tail gas of dissolution of spent fuel were discussed

Reaction mechanisms

International Nuclear Information System (INIS)

Nguyen Trong Anh

1988-01-01

The 1988 progress report of the Reaction Mechanisms laboratory (Polytechnic School, France), is presented. The research topics are: the valence bond methods, the radical chemistry, the modelling of the transition states by applying geometric constraints, the long range interactions (ion - molecule) in gaseous phase, the reaction sites in gaseous phase and the mass spectroscopy applications. The points of convergence between the investigations of the mass spectroscopy and the theoretical chemistry teams, as well as the purposes guiding the research programs, are discussed. The published papers, the conferences, the congress communications and the thesis, are also reported [fr

Fabrication of calcite blocks from gypsum blocks by compositional transformation based on dissolution-precipitation reactions in sodium carbonate solution.

Science.gov (United States)

Ishikawa, Kunio; Kawachi, Giichiro; Tsuru, Kanji; Yoshimoto, Ayami

2017-03-01

Calcium carbonate (CaCO 3 ) has been used as a bone substitute, and is a precursor for carbonate apatite, which is also a promising bone substitute. However, limited studies have been reported on the fabrication of artificial calcite blocks. In the present study, cylindrical calcite blocks (ϕ6×3mm) were fabricated by compositional transformation based on dissolution-precipitation reactions using different calcium sulfate blocks as a precursor. In the dissolution-precipitation reactions, both CaSO 4 ·2H 2 O and CaSO 4 transformed into calcite, a polymorph of CaCO 3 , while maintaining their macroscopic structure when immersed in 1mol/L Na 2 CO 3 solution at 80°C for 1week. The diametral tensile strengths of the calcite blocks formed using CaSO 4 ·2H 2 O and CaSO 4 were 1.0±0.3 and 2.3±0.7MPa, respectively. The fabrication of calcite blocks using CaSO 4 ·2H 2 O and CaSO 4 proposed in this investigation may be a useful method to produce calcite blocks because of the self-setting ability and high temperature stability of gypsum precursors. Copyright © 2016 Elsevier B.V. All rights reserved.

Adsorption and surface reaction of bis-diethylaminosilane as a Si precursor on an OH-terminated Si (0 0 1) surface

International Nuclear Information System (INIS)

Baek, Seung-Bin; Kim, Dae-Hee; Kim, Yeong-Cheol

2012-01-01

The adsorption and the surface reaction of bis-diethylaminosilane (SiH 2 [N(C 2 H 5 ) 2 ] 2 , BDEAS) as a Si precursor on an OH-terminated Si (0 0 1) surface were investigated to understand the initial reaction mechanism of the atomic layer deposition (ALD) process using density functional theory. The bond dissociation energies between two atoms in BDEAS increased in the order of Si-H, Si-N, and the rest of the bonds. Therefore, the relatively weak Si-H and Si-N bonds were considered for bond breaking during the surface reaction. Optimum locations of BDEAS for the Si-H and Si-N bond breaking were determined on the surface, and adsorption energies of 0.43 and 0.60 eV, respectively, were obtained. The Si-H bond dissociation energy of the adsorbed BDEAS on the surface did not decrease, so that a high reaction energy barrier of 1.60 eV was required. On the other hand, the Si-N bond dissociation energy did decrease, so that a relatively low reaction energy barrier of 0.52 eV was required. When the surface reaction energy barrier was higher than the adsorption energy, BDEAS would be desorbed from the surface instead of being reacted. Therefore, the Si-N bond breaking would be dominantly involved during the surface reaction, and the result is in good agreement with the experimental data in the literature.

Synthesis of Spongy-Like Mesoporous Hydroxyapatite from Raw Waste Eggshells for Enhanced Dissolution of Ibuprofen Loaded via Supercritical CO2

Directory of Open Access Journals (Sweden)

Abdul-Rauf Ibrahim

2015-04-01

Full Text Available The use of cheaper and recyclable biomaterials (like eggshells to synthesize high purity hydroxyapatite (HAp with better properties (small particle size, large surface area and pore volume for applications (in environmental remediation, bone augmentation and replacement, and drug delivery systems is vital since high-purity synthetic calcium sources are expensive. In this work, pure and mesoporous HAp nanopowder with large pore volume (1.4 cm3/g and surface area (284.1 m2/g was produced from raw eggshells at room temperature using a simple two-step procedure. The control of precursor droplets could stabilize the pH value of the reaction solution, because of the size of the needle (of the syringe pump used for precursor additions leading to production of HAp with high surface area and pore size. The as-produced HAp revealed high ibuprofen (as a model drug loading (1.38 g/g HAp, enhanced dissolution and controllable release of the drug via solute-saturated supercritical carbon dioxide.

Synthesis of Spongy-Like Mesoporous Hydroxyapatite from Raw Waste Eggshells for Enhanced Dissolution of Ibuprofen Loaded via Supercritical CO2

Science.gov (United States)

Ibrahim, Abdul-Rauf; Li, Xiangyun; Zhou, Yulan; Huang, Yan; Chen, Wenwen; Wang, Hongtao; Li, Jun

2015-01-01

The use of cheaper and recyclable biomaterials (like eggshells) to synthesize high purity hydroxyapatite (HAp) with better properties (small particle size, large surface area and pore volume) for applications (in environmental remediation, bone augmentation and replacement, and drug delivery systems) is vital since high-purity synthetic calcium sources are expensive. In this work, pure and mesoporous HAp nanopowder with large pore volume (1.4 cm3/g) and surface area (284.1 m2/g) was produced from raw eggshells at room temperature using a simple two-step procedure. The control of precursor droplets could stabilize the pH value of the reaction solution, because of the size of the needle (of the syringe pump used for precursor additions) leading to production of HAp with high surface area and pore size. The as-produced HAp revealed high ibuprofen (as a model drug) loading (1.38 g/g HAp), enhanced dissolution and controllable release of the drug via solute-saturated supercritical carbon dioxide. PMID:25860950

Dissolution of B-doped S1(100) layers in NaOH aqueous solutions

International Nuclear Information System (INIS)

Akhter, P.; Baig, A.; Mufti, A.

1988-12-01

NaOH solution has been used to study the dissolution rates of boron doped Sl(100) wafers as a function of solution normality (0.02 N to 15 N) and temperature in the range of 30 deg. C to boiling point. For a dissolution at boiling point, two distinctive ranges of solution normalities have been observed. For N ≤ 4.5, the dissolution rate increases logarithmically and is defect dependent. For higher values of N ≥ 4.5 normal, the dissolution rate becomes a linear function of normality and reaction is defect dependent. The reaction activation energy has been measured equal to 0.65 +- 0.03 eV. (author). 7 refs, 5 figs

NATO Advanced Research Workshop on the Mechanisms of Reactions of Organometallic Compounds with Surfaces

CERN Document Server

Williams, J

1989-01-01

A NATO Advanced Research Workshop on the "Mechanisms of Reactions of Organometallic Compounds with Surfaces" was held in St. Andrews, Scotland in June 1988. Many of the leading international researchers in this area were present at the workshop and all made oral presentations of their results. In addition, significant amounts of time were set aside for Round Table discussions, in which smaller groups considered the current status of mechanistic knowledge, identified areas of dispute or disagreement, and proposed experiments that need to be carried out to resolve such disputes so as to advance our understanding of this important research area. All the papers presented at the workshop are collected in this volume, together with summaries of the conclusions reached at the Round Table discussions. The workshop could not have taken place without financial support from NATO, and donations were also received from Associated Octel, Ltd., STC Ltd., and Epichem Ltd., for which the organisers are very grateful. The orga...

Reaction mechanisms of metal complexes

CERN Document Server

Hay, R W

2000-01-01

This text provides a general background as a course module in the area of inorganic reaction mechanisms, suitable for advanced undergraduate and postgraduate study and/or research. The topic has important research applications in the metallurgical industry and is of interest in the science of biochemistry, biology, organic, inorganic and bioinorganic chemistry. In addition to coverage of substitution reactions in four-, five- and six-coordinate complexes, the book contains further chapters devoted to isomerization and racemization reactions, to the general field of redox reactions, and to the reactions of coordinated ligands. It is relevant in other fields such as organic, bioinorganic and biological chemistry, providing a bridge to organic reaction mechanisms. The book also contains a chapter on the kinetic background to the subject with many illustrative examples which should prove useful to those beginning research. Provides a general background as a course module in the area of inorganic reaction mechanis...

Evaporite dissolution relevant to the WIPP site, northern Delaware Basin, southeastern New Mexico

International Nuclear Information System (INIS)

Lambert, S.J.

1982-01-01

Evaluation of the threat of natural dissolution of host evaporites to the integrity of the Waste Isolation Pilot Plant (WIPP) in southeastern New Mexico has taken into consideration (1) the volume of missing rock salt, (2) the occurrence (or not) of characteristic dissolution brines, (3) geomorphic features, some of which are unrelated to dissolution, and (4) the time intervals over which dissolution may have been active. Even under the assumption that all missing halite was originally present and has been removed by dissolution, there is no evidence of active preferential removal of the lower Salado Formation halite by any geologically reasonable process. The geologic record contains evidence of dissolution in the Triassic and Jurassic; to constrain all removal of basinal halite to the late Cenozoic yields an unrealistically high rate of removal. Application to the lower Salado of a stratabound mechanism known to be active in Nash Draw, a near-surface feature within the Basin, allows a minimum survival time of 2,500,000 years to be predicted for the subsurface facility for storage of radioactive waste at WIPP. This calculation is based on an analysis of all known dissolution features in the Delaware Basin, and takes into account the wetter (pluvial) climate during the past 600,000 years. 2 figures, 1 table

Non-thermal desorption from interstellar dust grains via exothermic surface reactions

Science.gov (United States)

Garrod, R. T.; Wakelam, V.; Herbst, E.

2007-06-01

Aims:The gas-phase abundance of methanol in dark quiescent cores in the interstellar medium cannot be explained by gas-phase chemistry. In fact, the only possible synthesis of this species appears to be production on the surfaces of dust grains followed by desorption into the gas. Yet, evaporation is inefficient for heavy molecules such as methanol at the typical temperature of 10 K. It is necessary then to consider non-thermal mechanisms for desorption. But, if such mechanisms are considered for the production of methanol, they must be considered for all surface species. Methods: Our gas-grain network of reactions has been altered by the inclusion of a non-thermal desorption mechanism in which the exothermicity of surface addition reactions is utilized to break the bond between the product species and the surface. Our estimated rate for this process derives from a simple version of classical unimolecular rate theory with a variable parameter only loosely constrained by theoretical work. Results: Our results show that the chemistry of dark clouds is altered slightly at times up to 106 yr, mainly by the enhancement in the gas-phase abundances of hydrogen-rich species such as methanol that are formed on grain surfaces. At later times, however, there is a rather strong change. Instead of the continuing accretion of most gas-phase species onto dust particles, a steady-state is reached for both gas-phase and grain-surface species, with significant abundances for the former. Nevertheless, most of the carbon is contained in an undetermined assortment of heavy surface hydrocarbons. Conclusions: The desorption mechanism discussed here will be better constrained by observational data on pre-stellar cores, where a significant accretion of species such as CO has already occurred.

Chlorite, Biotite, Illite, Muscovite, and Feldspar Dissolution Kinetics at Variable pH and Temperatures up to 280 C

Energy Technology Data Exchange (ETDEWEB)

Carroll, S. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Smith, M. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Lammers, K. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)

2016-10-05

Summary Sheet silicates and clays are ubiquitous in geothermal environments. Their dissolution is of interest because this process contributes to scaling reactions along fluid pathways and alteration of fracture surfaces, which could affect reservoir permeability. In order to better predict the geochemical impacts on long-term performance of engineered geothermal systems, we have measured chlorite, biotite, illite, and muscovite dissolution and developed generalized kinetic rate laws that are applicable over an expanded range of solution pH and temperature for each mineral. This report summarizes the rate equations for layered silicates where data were lacking for geothermal systems.

Universal Linear Scaling of Permeability and Time for Heterogeneous Fracture Dissolution

Science.gov (United States)

Wang, L.; Cardenas, M. B.

2017-12-01

Fractures are dynamically changing over geological time scale due to mechanical deformation and chemical reactions. However, the latter mechanism remains poorly understood with respect to the expanding fracture, which leads to a positively coupled flow and reactive transport processes, i.e., as a fracture expands, so does its permeability (k) and thus flow and reactive transport processes. To unravel this coupling, we consider a self-enhancing process that leads to fracture expansion caused by acidic fluid, i.e., CO2-saturated brine dissolving calcite fracture. We rigorously derive a theory, for the first time, showing that fracture permeability increases linearly with time [Wang and Cardenas, 2017]. To validate this theory, we resort to the direct simulation that solves the Navier-Stokes and Advection-Diffusion equations with a moving mesh according to the dynamic dissolution process in two-dimensional (2D) fractures. We find that k slowly increases first until the dissolution front breakthrough the outbound when we observe a rapid k increase, i.e., the linear time-dependence of k occurs. The theory agrees well with numerical observations across a broad range of Peclet and Damkohler numbers through homogeneous and heterogeneous 2D fractures. Moreover, the theory of linear scaling relationship between k and time matches well with experimental observations of three-dimensional (3D) fractures' dissolution. To further attest to our theory's universality for 3D heterogeneous fractures across a broad range of roughness and correlation length of aperture field, we develop a depth-averaged model that simulates the process-based reactive transport. The simulation results show that, regardless of a wide variety of dissolution patterns such as the presence of dissolution fingers and preferential dissolution paths, the linear scaling relationship between k and time holds. Our theory sheds light on predicting permeability evolution in many geological settings when the self

Effect of surface stress state on dissolution property of Alloy 690 in simulated primary water condition

International Nuclear Information System (INIS)

Kim, Kyung Mo; Shim, Hee-Sang; Lee, Eun Hee; Seo, Myung Ji; Han, Jung Ho; Hur, Do Haeng

2014-01-01

The dissolution control of nickel is important to reduce the radioactive dose rate and deterioration of fuel performance in the operation of nuclear power plants (PWR). The corrosion properties are affected by the metal surface residual stress introduced in manufacture process such as work hardening. This work studied the effect of surface modification on the release rate of Alloy 690, nickel-base alloy for a steam generator tube, in the test condition of simulated primary water chemistry in PWRs. The surface stress modification was applied by the electro-polishing and shot peening method. Shot peening process was applied using ceramic beads with different intensities through the variation of air pressure. The corrosion release tests performed at 330degC with LiOH 2 ppm and H 3 BO 4 1200 ppm, DH(dissolved hydrogen) 35 cc/kg (STP) and about 20 ppb of DO(dissolved oxygen) condition. The corrosion release rate was evaluated by a gravimetric analysis method and the surface analysed by SEM and optical microscope. The surface residual stress was measured by an X-ray diffractometer, and the distribution of stress state was evaluated by a micro-hardness tester. The metal ion release rate of alloy 690 was evaluated from the influence of the stress state on the metal surface. The oxide property and structure was affected by the residual stress in the oxide layer. (author)

Instability of an infiltration-driven dissolution-precipitation front with a nonmonotonic porosity profile

Science.gov (United States)

Kondratiuk, Paweł; Dutka, Filip; Szymczak, Piotr

2016-04-01

. The porosity profile is not monotonic as in the case of pure dissolution, but it typically has a minimum in the vicinity of the front. Additionally, the porosity difference between the initial rock far-downstream and the well-developed secondary rock far-upstream can be either negative or positive, which either destabilizes of stabilized the front. We propose a theoretical model of a simple infiltration-driven dissolution-precipitation system and find the morphology of the resulting planar reaction front. By performing linear stability analysis of the stationary planar solutions we show that the front can be unstable for a wide range of control parameters, even if the porosity of the secondary rock is lower than the porosity of the primary rock. Next, by numerical simulations of the full nonlinear model we present the long-term evolution of the system. [1] D. Chadam et al., IMA J. Appl. Math. 36, 207-221, 1986. [2] A. Putnis, Rev. Mineral. Geochemistry, 70(1), 87-124, 2009.

Kinetics of oxidic phase dissolution in acids

International Nuclear Information System (INIS)

Gorichev, I.G.; Kipriyanov, N.A.

1981-01-01

The critical analysis of the experimental data on dissolution kinetics of metal oxides (BeO, V 2 O 5 , UO 2 , Nb 2 O 5 , Ta 2 O 5 etc.) in acid media is carried out. Kinetic peculiarities of oxide dissolution are explained on the basis of the notions of electron- proton theory. It is established that the surface nonstoichiometric ccomposition of oxide phase and potential jump, appearing on the interface of the oxide-electrolyte phase are the important factors, determining the dissolution rate of a solid phase. The dissolution rate of metal oxides is limited by the transition of protons into the solid oxide phase. Morphological models of heterogeneous kinetics are used when explaining kinetic regularities of oxide dissolution process [ru

Mechanism of the CO2-Ca(OH)2 reaction

International Nuclear Information System (INIS)

Chew, V.S.; Cheh, C.H.; Glass, R.W.

1983-01-01

Recent studies clearly showed the importance of moisture in achieving high Ca(OH) 2 absorbent utilization for removing CO 2 from gas streams at ambient temperatures. However, the role of moisture and the mechanism of the reaction was not well understood. This paper summarizes the results of a study of the mechanism of the CO 2 -Ca(OH) 2 reaction with emphasis on the role of moisture. The reaction between Ca(OH) 2 and CO 2 in moist N 2 was found to be first order with respect to the reactants with a rate constant of about 100 min -1 . At high humidities, the rate of reaction was chemically controlled, but at low humidities, the reaction rate was limited by the diffusion through the carbonate layer formed by the reaction. Calculations showed that capillary condensation could have occurred only in about 2% of the pore volume and was unlikely to have affected the reaction rate significantly by allowing the reaction to occur in the liquid phase. It was, therefore, concluded that the main role of moisture was to improve the Ca(OH) 2 utilization by lowering the resistance to diffusion through the carbonate layer

Deep water dissolution in Marine Isotope Stage 3 from the northern South China Sea

Science.gov (United States)

Huang, B.

2015-12-01

The production, transport, deposition, and dissolution of carbonate profoundly implicate the global carbon cycle affect the inventory and distribution of dissolved organic carbon (DIC) and alkalinity (ALK), which drive atmospheric CO2 change on glacial-interglacial timescale. the process may provide significant clues for improved understanding of the mechanisms that control the global climate system. In this study, we calculate and analyze the foraminiferal dissolution index (FDX) and the fragmentation ratios of planktonic foraminifera over 60-25 ka based on samples from 17924 and ODP 1144 in the northeastern South China Sea (SCS) to reconstruct the deep water carbonate dissolution during Marine Isotope Stage 3 (MIS 3). Result shows that the dissolution of carbonate increases gradually at 17924 but keeps stable at ODP 1144. The changes of FDX coincidence with that of fragmentation ratios at 17924 and ODP 1144 suggest both indexes can be used as reliable dissolving proxies of planktonic foraminifera. Comparing FDX and fragmentation ratios at both sites, we find the FDX and fragmentation ratios at 17924 are higher than those at 1144, indicating that carbonate dissolution is intenser in 17924 core during MIS 3. The increasing total percentage of both N. dutertrei and G. bulloides during MIS 3 reveals the rising primary productivity that may lead to deep water [CO32-] decrease. The slow down of thermohaline circulation may increase deep water residence time and accelerate carbonate dissolution. In addition, the covering of ice caps, iron supply and increased surface-water stratification also contribute to atmosphere CO2 depletion and [CO32-] decrease in deep water. In the meanwhile, regression result from colder temperature increases the input of ALK and DIC to the deep ocean and deepens the carbonate saturation depth, which makes the deep water [CO32-] rise. In ODP Site 1144, the decrease in [CO32-] caused by more CO2 restored in deep water is equal to the increase in

Hadron reaction mechanisms

International Nuclear Information System (INIS)

Collins, P.D.B.; Martin, A.D.

1982-01-01

The mechanism of hadron scattering at high energies are reviewed in such a way as to combine the ideas of the parton model and quantum chromodynamics (QCD) with Regge theory and phenomenology. After a brief introduction to QCD and the basic features of hadron scattering data, scaling and the dimensional counting rules, the parton structure of hadrons, and the parton model for large momentum transfer processes, including scaling violations are discussed. Hadronic jets and the use of parton ideas in soft scattering processes are examined, attention being paid to Regge theory and its applications in exclusive and inclusive reactions, the relationship to parton exchange being stressed. The mechanisms of hadron production which build up cross sections, and hence the underlying Regge singularities, and the possible overlap of Regge and scaling regions are discussed. It is concluded that the key to understanding hadron reaction mechanisms seems to lie in the marriage of Regge theory with QCD. (author)

Revealing the reaction mechanisms of Li–O2 batteries using environmental transmission electron microscopy

Energy Technology Data Exchange (ETDEWEB)

Luo, Langli; Liu, Bin; Song, Shidong; Xu, Wu; Zhang, Ji-Guang; Wang, Chongmin

2017-03-27

The capacity, Coulombic efficiency, rate, and cyclability of a Li-O2 battery critically depend on the electrode reaction mechanism and the structure/morphology of the reaction product as well as their spatial and temporal evolution1-8, which are all further complicated by the choice of different electrolyte. For the case of aprotic cell, the discharge product, Li2O2, is formed through solution and surface mechanisms9,10, but little is known on the formation mechanism of the perplexing morphology of the reaction product11-15. For the case of Li-O2 battery using solid electrolyte, neither electrode reaction mechanism nor the nature of the reaction production is known. Herein, we reveal the full cycle reaction pathway for Li-O2 batteries and its correlation with the nature of the reaction product. Using an aberration-corrected environmental TEM under oxygen environment, we captured, for the first time, the morphology and phase evolution on the carbon nanotube (CNT) cathode of a working solid-state Li-O2 nano-battery16 and directly correlated these features with electrochemical reaction. We found that the oxygen reduction reaction on CNTs initially produces LiO2, which subsequently evolves to Li2O2 and O2 through disproportionation reaction. Surprisingly it is just the releasing of O2 that inflates the particles to a hollow structure with a Li2O outer surface layer and Li2O2 inner-shell, demonstrating that, in general, accommodation of the released O2 coupled with the Li+ ion diffusion and electron transport paths across both spatial and temporal scales critically governs the morphology of the discharging/charging product in Li-O2 system. We anticipate that the direct observation of Li-O2 reaction mechanisms and their correlation with the morphology of the reaction product set foundation for quantitative understanding/modeling of the electrochemical processes in the Li-O2 system, enabling rational design of both solid-state and aprotic Li-O2 batteries.

Reaction and Aggregation Dynamics of Cell Surface Receptors

Science.gov (United States)

Wang, Michelle Dong

This dissertation is composed of both theoretical and experimental studies of cell surface receptor reaction and aggregation. Project I studies the reaction rate enhancement due to surface diffusion of a bulk dissolved ligand with its membrane embedded target, using numerical calculations. The results show that the reaction rate enhancement is determined by ligand surface adsorption and desorption kinetic rates, surface and bulk diffusion coefficients, and geometry. In particular, we demonstrate that the ligand surface adsorption and desorption kinetic rates, rather than their ratio (the equilibrium constant), are important in rate enhancement. The second and third projects are studies of acetylcholine receptor clusters on cultured rat myotubes using fluorescence techniques after labeling the receptors with tetramethylrhodamine -alpha-bungarotoxin. The second project studies when and where the clusters form by making time-lapse movies. The movies are made from overlay of the pseudocolored total internal reflection fluorescence (TIRF) images of the cluster, and the schlieren images of the cell cultures. These movies are the first movies made using TIRF, and they clearly show the cluster formation from the myoblast fusion, the first appearance of clusters, and the eventual disappearance of clusters. The third project studies the fine structural features of individual clusters observed under TIRF. The features were characterized with six parameters by developing a novel fluorescence technique: spatial fluorescence autocorrelation. These parameters were then used to study the feature variations with age, and with treatments of drugs (oligomycin and carbachol). The results show little variation with age. However, drug treatment induced significant changes in some parameters. These changes were different for oligomycin and carbachol, which indicates that the two drugs may eliminate clusters through different mechanisms.

Dissolution rates of DWPF glasses from long-term PCT

International Nuclear Information System (INIS)

Ebert, W.L.; Tam, S.W.

1996-01-01

We have characterized the corrosion behavior of several Defense Waste Processing Facility (DWPF) reference waste glasses by conducting static dissolution tests with crushed glasses. Glass dissolution rates were calculated from measured B concentrations in tests conducted for up to five years. The dissolution rates of all glasses increased significantly after certain alteration phases precipitated. Calculation of the dissolution rates was complicated by the decrease in the available surface area as the glass dissolves. We took the loss of surface area into account by modeling the particles to be spheres, then extracting from the short-term test results the dissolution rate corresponding to a linear decrease in the radius of spherical particles. The measured extent of dissolution in tests conducted for longer times was less than predicted with this linear dissolution model. This indicates that advanced stages of corrosion are affected by another process besides dissolution, which we believe to be associated with a decrease in the precipitation rate of the alteration phases. These results show that the dissolution rate measured soon after the formation of certain alteration phases provides an upper limit for the long-term dissolution rate, and can be used to determine a bounding value for the source term for radionuclide release from waste glasses. The long-term dissolution rates measured in tests at 20,000 per m at 90 degrees C in tuff groundwater at pH values near 12 for the Environmental Assessment glass and glasses made with SRL 131 and SRL 202 frits, respectively

Concerted and stepwise mechanisms in cycloaddition reactions: potential surfaces and isotope effects

International Nuclear Information System (INIS)

Houk, K.N.; Yi Li; Storer, Joey; Raimondi, Laura; Beno, Brett

1994-01-01

CASSCF/6-31G * calculations have been performed on concerted and stepwise Diels-Alder reactions of butadiene with ethene, the dimerization of butadiene, and the dimerization of cyclobutadiene. The relative energies of concerted and stepwise mechanisms are compared, and the factors influencing these ''energies of concert'' are discussed. The comparison of calculated isotope effects to experimental data provides support for theoretical results. (Author)

Oxidation mechanism and passive behaviour of nickel in molten carbonate

Energy Technology Data Exchange (ETDEWEB)

Vossen, J.P.T. (ECN Fossil Fuels, Petten (Netherlands)); Ament, P.C.H.; De Wit, J.H.W. (Div. of Corrosion, Lab. for Maaterials Sceince, Delft Univ. of Technology, Delft (Netherlands))

1994-07-01

The oxidation and passivation mechanism and the passive behaviour of nickel in molten carbonate have been investigated with impedance measurements. The oxidation of nickel proceeds according to a dissolution and reprecipitation process. The slowest steps in the reaction sequence are the dissociation reaction of the carbonate and the diffusion of the formed NiO to the metal surface. In the passive range, dissolution of Ni[sup 2+] proceeds after diffusion of Ni[sup 2+] through the oxide layer. The Ni[sup 2+] is formed at the metal/oxide interface. The slowest process is the diffusion of bivalent nickel ions through the passive scale. The formation of trivalent nickel ions probably takes place at the oxide/melt interface. This reaction is accompanied by the incorporation of an oxygen ion and a nickel vacancy in the NiO lattice. The trivalent nickel ions and the nickel vacancy diffuse to the bulk of the oxide scale. The slowest step in this sequence is the dissociation of the carbonate ions and the incorporation of the oxygen ion in the NiO lattice. 9 figs., 2 tabs., 11 refs.

Improvement of database on glass dissolution

International Nuclear Information System (INIS)

Hayashi, Maki; Sasamoto, Hiroshi; Yoshikawa, Hideki

2008-03-01

In geological disposal system, high-level radioactive waste (HLW) glass is expected to retain radionuclide for the long term as the first barrier to prevent radionuclide release. The advancement of its performance assessment technology leads to the reliability improvement of the safety assessment of entire geological disposal system. For this purpose, phenomenological studies for improvement of scientific understanding of dissolution/alteration mechanisms, and development of robust dissolution/alteration model based on the study outcomes are indispensable. The database on glass dissolution has been developed for supporting these studies. This report describes improvement of the prototype glass database. Also, this report gives an example of the application of the database for reliability assessment of glass dissolution model. (author)

Assessment of near-surface dissolution at and near the Waste Isolation Pilot Plant (WIPP), southeastern New Mexico

International Nuclear Information System (INIS)

Bachman, G.O.

1985-07-01

The area at and near the WIPP site was examined for evidence of karst development on the geomorphic surface encompassing the site. Certain surficial depressions of initial concern were identified as blowouts in sand dune fields (shallow features unrelated to karstification). An ancient stream system active more than 500,000 yr ago contained more water than any system since. During that time (Gatuna, Middle Pleistocene), many karst features such as Clayton Basin and Nash Draw began to form in the region. Halite was probably dissolved from parts of the Rustler Formation at that time. Dissolution of halite and gypsum from intervals encountered in Borehole WIPP-33 west of the WIPP site occurred during later Pleistocene time (i.e., <450,000 yr ago). However, there is no evidence of active near-surface dissolution within a belt to the east of WIPP-33 in the vicinity of the WIPP shaft. 26 refs., 11 figs., 1 tab

Interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials: A review.

Science.gov (United States)

He, Jie; Yang, Xiaofang; Men, Bin; Wang, Dongsheng

2016-01-01

The heterogeneous Fenton reaction can generate highly reactive hydroxyl radicals (OH) from reactions between recyclable solid catalysts and H2O2 at acidic or even circumneutral pH. Hence, it can effectively oxidize refractory organics in water or soils and has become a promising environmentally friendly treatment technology. Due to the complex reaction system, the mechanism behind heterogeneous Fenton reactions remains unresolved but fascinating, and is crucial for understanding Fenton chemistry and the development and application of efficient heterogeneous Fenton technologies. Iron-based materials usually possess high catalytic activity, low cost, negligible toxicity and easy recovery, and are a superior type of heterogeneous Fenton catalysts. Therefore, this article reviews the fundamental but important interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials. OH, hydroperoxyl radicals/superoxide anions (HO2/O2(-)) and high-valent iron are the three main types of reactive oxygen species (ROS), with different oxidation reactivity and selectivity. Based on the mechanisms of ROS generation, the interfacial mechanisms of heterogeneous Fenton systems can be classified as the homogeneous Fenton mechanism induced by surface-leached iron, the heterogeneous catalysis mechanism, and the heterogeneous reaction-induced homogeneous mechanism. Different heterogeneous Fenton systems catalyzed by characteristic iron-based materials are comprehensively reviewed. Finally, related future research directions are also suggested. Copyright © 2015. Published by Elsevier B.V.

On surface reactions of iron tungstate with ethane

International Nuclear Information System (INIS)

Obrubov, V.A.; Shchukin, V.P.; Averbukh, A.Ya.

1980-01-01

Results of investigation of ethane oxidation reaction upon iron tungstate are presented. It is shown that catalytic oxidation of ethane is accompanied by the surface reaction of the catalyst reduction. Maximum reduction of surface depends upon temperature and considerably affects the direction of ethane oxidation process. Activation energies of ethane oxidation reactions and surface reaction of iron tungstate reduction depend on the surface actual state and at its reduction up to 5% from monolayer change in the limits 36.0-46.0 and 53.0-66.0 kcal/mol respectively

Influence of oxalic acid on the dissolution kinetics of manganese oxide

Science.gov (United States)

Godunov, E. B.; Artamonova, I. V.; Gorichev, I. G.; Lainer, Yu. A.

2012-11-01

The kinetics and electrochemical processes of the dissolution of manganese oxides with various oxidation states in sulfuric acid solutions containing oxalate ion additives is studied under variable conditions (concentration, pH, temperature). The parameters favoring a higher degree of the dissolution of manganese oxides in acidic media are determined. The optimal conditions are found for the dissolution of manganese oxides in acidic media in the presence of oxalate ions. The mechanism proposed for the dissolution of manganese oxides in sulfuric acid solutions containing oxalic acid is based on the results of kinetic and electrochemical studies. The steps of the dissolution mechanism are discussed.

In vivo predictive dissolution: transport analysis of the CO2 , bicarbonate in vivo buffer system.

Science.gov (United States)

Krieg, Brian J; Taghavi, Seyed Mohammad; Amidon, Gordon L; Amidon, Gregory E

2014-11-01

Development of an oral in vivo predictive dissolution medium for acid drugs with a pKa in the physiological range (e.g., Biopharmaceutics Classification System Class IIa) requires transport analysis of the complex in vivo CO2 /bicarbonate buffering system. In this report, we analyze this buffer system using hydrodynamically defined rotating disk dissolution. Transport analysis of drug flux was predicted using the film model approach of Mooney et al based on equilibrium assumptions as well as accounting for the slow hydration reaction, CO2 + H2 O → H2 CO3 . The accuracy of the models was compared with experimentally determined results using the rotating disk dissolution of ibuprofen, indomethacin, and ketoprofen. The equilibrium and slow hydration reaction rate models predict significantly different dissolution rates. The experimental results are more accurately predicted by accounting for the slow hydration reaction under a variety of pH and hydrodynamic conditions. Although the complex bicarbonate buffering system requires further consideration given its dynamic nature in vivo, a simplifying irreversible reaction (IRR) transport analysis accurately predicts in vitro rotating disk dissolution rates of several carboxylic acid drugs. This IRR transport model provides further insight into bicarbonate buffer and can be useful in developing more physiologically relevant buffer systems for dissolution testing. © 2014 Wiley Periodicals, Inc. and the American Pharmacists Association.

Dissolution of FFTF vendor fuel

International Nuclear Information System (INIS)

Lerch, R.E.

1979-08-01

Dissolution experiments were performed on FFTF vendor fuel (both mechanically mixed and coprecipitated) during 1974, 1975, and 1976. A marked improvement was noted in the completeness of fuel dissolution from 1974 to 1976. The reason for this is unknown but may have been attributable to slight changes in fuel fabrication conditions. In general, the bulk of the fuel pellets tested dissolved to greater than 99.9% in nitric acid alone

Dissolution of FFTF vendor fuel

Energy Technology Data Exchange (ETDEWEB)

Lerch, R.E.

1979-08-01

Dissolution experiments were performed on FFTF vendor fuel (both mechanically mixed and coprecipitated) during 1974, 1975, and 1976. A marked improvement was noted in the completeness of fuel dissolution from 1974 to 1976. The reason for this is unknown but may have been attributable to slight changes in fuel fabrication conditions. In general, the bulk of the fuel pellets tested dissolved to greater than 99.9% in nitric acid alone.

Dissolution behavior of irradiated mixed oxide fuel with short stroke shearing for fast reactor reprocessing

International Nuclear Information System (INIS)

Ikeuchi, Hirotomo; Sano, Yuichi; Shibata, Atsuhiro; Koizumi, Tsutomu; Washiya, Tadahiro

2013-01-01

An efficient dissolution process was established for future reprocessing in which mixed-oxide (MOX) fuels with high plutonium contents and dissolver solution with high heavy-metal (HM) concentrations (more than 500 g dm -3 ) will be treated. This dissolution process involves short stroke shearing of fuels (∼10 mm in length). The dissolution kinetics of irradiated MOX fuels and the effects of the Pu content, HM concentration, and fuel form on the dissolution rate were investigated. Irradiated fuel was found to dissolve as 10 2 -10 3 times fast as non-irradiated fuel, but the rate decreased with increasing Pu content. Kinetic analysis based on the fragmentation model, which considers the penetration and diffusion of nitric acid through fuel matrices prior to chemical reaction, indicated that the dissolution rate of irradiated fuel was affected not only by the volume ratio of liquid to solid (L/S ratio) but also by the exposed surface area per unit mole of nitric acid (A/m ratio). The penetration rate of nitric acid is expected to be decreased at high HM concentrations by a reduction in the L/S ratio, but enhanced by shearing the fuel pieces with short strokes and thus enlarging the A/m ratio. (author)

Effect drug loading process on dissolution mechanism of encapsulated amoxicillin trihydrate in hydrogel semi-IPN chitosan methyl cellulose with pore forming agent KHCO3 as a floating drug delivery system

Science.gov (United States)

Fithawati, Garnis; Budianto, Emil

2018-04-01

Common treatment for Helicobacter pylori by repeated oral consumption of amoxicillin trihydrate is not effective. Amoxicillin trihydrate has a very short residence time in stomach which leads into its ineffectiveness. Residence time of amoxicillin trihydrate can be improved by encapsulating amoxicillin trihydrate into a floating drug delivery system. In this study, amoxicillin trihydrate is encapsulated into hydrogel semi-IPN chitosan methyl cellulose matrix as a floating drug delivery system and then treated with 20% KHCO3 as pore forming agent. Drug loading process used are in-situ loading and post loading. In-situ loading process has higher efficiency percentage and dissolution percentage than post loading process. In-situ loading process resulted 100% efficiency with 92,70% dissolution percentage. Post loading process resulted 98,7% efficiency with 90,42% dissolution percentage. Mechanism of drug dissolution study by kinetics approach showed both in-situ loading process and post loading process are diffusion and degradation process (n=0,4913) and (n=0,4602) respectively. These results are supported by characterization data from optical microscope and scanning electron microscopy (SEM). Data from optical microscope showed both loading process resulted in coarser hydrogel surface. Characterization using SEM showed elongated pores in both loading process after dissolution test.

Retention and reduction of uranium on pyrite surface

International Nuclear Information System (INIS)

Eglizaud, N.

2006-12-01

In the hypothesis of a storage of the spent fuel in a deep geological formation, understanding the uranium dispersion in the environment is important. Pyrite is a reducing mineral present in the Callovo-Oxfordian argilites, the geological formation actually studied for such a storage. However, pyrite impact on uranium migration has already been poorly studied. The aim of the study was to understand the mechanisms of uranium(VI) retention and reduction on the pyrite surface (FeS 2 ). Solution chemistry was therefore coupled with solid spectroscopic studies (XPS and Raman spectroscopy). All uranium-pyrite interactions experiments were performed under an anoxic atmosphere, in a glove box. Pyrite dissolution under anoxic conditions releases sulfoxy-anions and iron(II), which can then be adsorbed on the pyrite surface. This adsorption was confirmed by interaction experiments using iron(II) isotopic dilution. Uranium(VI) is retained by an exchange reaction with iron(II) adsorbed on sulphur sites, with a maximal amount of sorbed uranium at pH ≥ 5.5. Cobalt(II) and europium(III) are also adsorbed on the pyrite surface above pH 5.5 confirming then that reduction is not required for species to adsorb on pyrite. When the concentration of uranium retained is lower than 4 x 10 -9 mol g -1 , an oxidation-reduction reaction leads to the formation of a uranium (VI) (IV) mixed oxide and to solid sulphur (d.o. ≥ -I). During this reaction, iron remains mostly at the +II oxidation degree. The reaction products seem to passivate the pyrite surface: at higher amounts of retained uranium, the oxidation-reduction reaction is no longer observed. The surface is saturated by the retention of (3.4 ± 0.8) x 10 -7 mol L -1 of uranium(VI). Modelling of uranium sorption at high surface coverage (≥ 4 x 10 -9 mol g -1 ) by the Langmuir model yields an adsorption constant of 8 x 10 7 L mol -1 . Finally, a great excess of uranium(VI) above the saturation concentration allows the observation of

Performance enhanced design of chaos controller for the mechanical centrifugal flywheel governor system via adaptive dynamic surface control

Directory of Open Access Journals (Sweden)

Shaohua Luo

2016-09-01

Full Text Available This paper addresses chaos suppression of the mechanical centrifugal flywheel governor system with output constraint and fully unknown parameters via adaptive dynamic surface control. To have a certain understanding of chaotic nature of the mechanical centrifugal flywheel governor system and subsequently design its controller, the useful tools like the phase diagrams and corresponding time histories are employed. By using tangent barrier Lyapunov function, a dynamic surface control scheme with neural network and tracking differentiator is developed to transform chaos oscillation into regular motion and the output constraint rule is not broken in whole process. Plugging second-order tracking differentiator into chaos controller tackles the “explosion of complexity” of backstepping and improves the accuracy in contrast with the first-order filter. Meanwhile, Chebyshev neural network with adaptive law whose input only depends on a subset of Chebyshev polynomials is derived to learn the behavior of unknown dynamics. The boundedness of all signals of the closed-loop system is verified in stability analysis. Finally, the results of numerical simulations illustrate effectiveness and exhibit the superior performance of the proposed scheme by comparing with the existing ADSC method.

Studies of the surface of titanium dioxide. IV. The hydrogen-deuterium equilibration reaction

International Nuclear Information System (INIS)

Iwaki, T.; Katsuta, K.; Miura, M.

1981-01-01

The interaction of hydrogen with the surface of titanium dioxide has been studied in connection with the hydrogen-reduction mechanism of titanium dioxide, by means of such measurements as weight decrease, magnetic susceptibility, hydrogen uptake, and electrical conductance. It was postulated in the previous study that the rate-determining step of the hydrogen-reduction reaction may be the formation of surface hydroxyl groups, followed by the rapid removal of water molecules from the surface. In this study, the interactions between hydrogen and the surface of titanium dioxide were investigated by measuring the hydrogen-deuterium equilibration reaction, H 2 + D 2 = 2HD, at temperatures above 200 0 C on both surfaces before and after hydrogen reduction to compare the differences in the reactivities

Mechanism for calcite dissolution and its contribution to development of reservoir porosity and permeability in the Kela 2 gas field,Tarim Basin,China

Institute of Scientific and Technical Information of China (English)

2008-01-01

This study is undertaken to understand how calcite precipitation and dissolution contributes to depth-related changes in porosity and permeability of gas-bearing sandstone reservoirs in the Kela 2 gas field of the Tarim Basin, Northwestern China. Sandstone samples and pore water samples are col-lected from well KL201 in the Tarim Basin. Vertical profiles of porosity, permeability, pore water chem-istry, and the relative volume abundance of calcite/dolomite are constructed from 3600 to 4000 m below the ground surface within major oil and gas reservoir rocks. Porosity and permeability values are in-versely correlated with the calcite abundance, indicating that calcite dissolution and precipitation may be controlling porosity and permeability of the reservoir rocks. Pore water chemistry exhibits a sys-tematic variation from the Na2SO4 type at the shallow depth (3600-3630 m), to the NaHCO3 type at the intermediate depth (3630―3695 m),and to the CaCl2 type at the greater depth (3728―3938 m). The geochemical factors that control the calcite solubility include pH, temperature, pressure, Ca2+ concen-tration, the total inorganic carbon concentration (ΣCO2), and the type of pore water. Thermodynamic phase equilibrium and mass conservation laws are applied to calculate the calcite saturation state as a function of a few key parameters. The model calculation illustrates that the calcite solubility is strongly dependent on the chemical composition of pore water, mainly the concentration difference between the total dissolved inorganic carbon and dissolved calcium concentration (i.e., [ΣCO2] -[Ca2+]). In the Na2SO4 water at the shallow depth, this index is close to 0, pore water is near the calcite solubility. Calcite does not dissolve or precipitate in significant quantities. In the NaHCO3 water at the intermedi-ate depth, this index is greater than 0, and pore water is supersaturated with respect to calcite. Massive calcite precipitation was observed at this depth

Vibrational Mode-Specific Reaction of Methane with a Nickel Surface

Science.gov (United States)

Beck, Rainer

2004-03-01

The dissociation of methane on a nickel catalyst is a key step in steam reforming of natural gas for hydrogen production. Despite substantial effort in both experiment and theory, there is still no atomic scale description of this important gas-surface reaction. To elucidate its dynamics, we have performed quantum state resolved studies of vibrationally excited methane reacting on the Ni(100) surface using pulsed laser and molecular beam techniques. We observed up to a factor of 5 greater reaction probability for methane-d2 with two quanta of excitation in one C-H bond versus a nearly isoenergetic state with one quanta in each of two C-H bonds. The observed reactivities point to a transition state structure which has one of the C-H bonds significantly elongated. Our results also clearly exclude the possibility of statistical models correctly describing the mechanism of this process and emphasize the importance of full-dimensional calculations of the reaction dynamics.