Effect of EDTA on the diffusion behavior of 99TcO4 − and ReO4 − in GMZ bentonite

Polyaminopolycarboxylate EDTA with powerful metal-binding property, which often presents in low and intermediate-level waste, can enhance the radionuclide migration. The effect of EDTA on the diffusion behavior of ⁹⁹TcO₄ ^? and ReO₄ ^? in Gaomiaozi (GMZ) bentonite was investigated by using through-diffusion method. For ⁹⁹TcO₄ ^? in present of EDTA, the D _e values was (1.2 ± 0.1) × 10^?11 m²/s, which was 4 times higher than that in absent of EDTA. It can be explained that the complexation between ⁹⁹TcO₄ ^? and EDTA might be formed. By contrast, the D _e values of ReO₄ ^? remained unchanged in present or absent of EDTA, indicating that ReO₄ ^? could not complex with EDTA. However, the diffusion of ReO₄ ^? could be increased in present of EDTA, the D _a value was found to be increased from 1.8 × 10^?10 to 5.4 × 10^?10 m²/s. It demonstrated that ReO₄ ^? need more drastic conditions to form the Re(VII)–EDTA complexes than those used for ⁹⁹TcO₄ ^?. For both ReO₄ ^? and ⁹⁹TcO₄ ^?, the rock capacity factor α is less than the total porosity ε _tot, indicating that they has little retention/sorption on the surface of bentonite.     

99TcO4 − diffusion and sorption in compacted GMZ bentonite studied by capillary method

Sorption and diffusion of ⁹⁹TcO₄ ^? in compacted bentonite from Gaomiaozi county (Inner Mongolia, China) (denoted as GMZ bentonite) was studied by capillary method. The distribution coefficient (K _d) and diffusion coefficient (D _a) were calculated from diffusion curves of ⁹⁹TcO₄ ^? in compacted GMZ bentonite. The D _a and K _d values decreased with the increasing of the bulk dry density of the compacted bentonite. With increasing pH values, the D _a values increased whereas the K _d values decreased, which is attributed to the ion exchange and electrostatic repulsion between the negative surface charged bentonite and negative charged ⁹⁹TcO₄ ^? ions at high pH values. The diffusion and relative concentration distributions of ⁹⁹TcO₄ ^? in compacted bentonite after long aging time were simulated from the distribution and diffusion coefficients. Effect of aging time on the diffusion of ⁹⁹TcO₄ ^? in compacted bentonite was also calculated using the theoretical equation. The results indicated that ⁹⁹TcO₄ ^? was an easily mobile radionuclide in environment and the release of ⁹⁹TcO₄ ^? from the radioactive waste repository was dangerous to the environmental pollution.     

Effect of γ-radiation on radionuclide retention in compacted bentonite

Compacted bentonite is proposed as an engineered barrier in many concepts for disposal of high level nuclear waste. After the initial deposition however, the bentonite barrier will inevitably be exposed to ionizing radiation (mainly γ) under anoxic conditions. Because of this, the effects of γ-radiation on the apparent diffusivity values and sorption coefficients in bentonite for Cs⁺ and Co²⁺ were tested under different experimental conditions. Radiation induced effects on sorption were in general more noticeable for Co²⁺ than for Cs⁺, which generally showed no significant differences between irradiated and unirradiated clay samples. For Co²⁺ however, the sorption to irradiated MX80 was significantly lower than to the unirradiated clay samples regardless of the experimental conditions. This implies that γ-radiation may alter the surface characteristics contributing to surface complexation of Co²⁺. With the experimental conditions used, however, the effect of decreasing sorption was not large enough to be reflected on the obtained D_a values.     

Experimental and numerical investigations of 99TcO4− diffusion in compacted SPV 200 bentonite

Journal of Radioanalytical and Nuclear Chemistry - Diffusion characteristics in bentonite are essential to quantify the transport of radionuclides through buffer/backfill materials in waste...     

Effect of pH on the reactivity of dipeptides and α-amino acids in the N-acylation

The reaction kinetics of Gly, L-??-Ala, Gly-Gly, L-??-Ala-L-??-Ala and ??-Ala-??-Ala with picryl benzoate in water (40 wt %)-2-propanol was investigated. At pH = 4?C8 the rate constants of N-acylation of the anionic form of dipeptides are less than those of the corresponding amino acid anions, in agreement with their basicity, whereas the relative effective rate constants of reactions depend on pH: in acidic, neutral and slightly alkaline media the k _ef values are higher for the dipeptides, and in a strongly alkaline medium, for the amino acids. These differences are due to the changes in the concentrations of reactive forms of amino acids and dipeptides in the system at varying the medium pH.     

Effect of Ionic Strength and Temperature on the Protonation of Oxidized Glutathione

The protonation constants for oxidized glutathione, H _i−1L^(4−i+1)−, K _i ^H=[H _i L⁽⁴⁻ⁱ⁾⁻]/[H _i−1L^(4−i+1)−][H⁺] i=1,2,…,6 have been measured at 5, 25 and 45 °C as a function of the ionic strength (0.1 to 5.4 mol⋅[kg(H₂O)]⁻¹) in NaCl solutions. The effect of ionic strength on the measured protonation constants has been used to determine the thermodynamic values (K _i ^H0) and the enthalpy (ΔH _i ) for the dissociation reaction using the SIT model and Pitzer equations. The SIT (ε) and Pitzer parameters (β ⁽⁰⁾, β ⁽¹⁾ and C) for the dissociation products (L⁴⁻, HL³⁻, H₂L²⁻, H₃L⁻, H₄L, H₅L⁺, H₆L²⁺) have been determined as a function of temperature. These results can be used to examine the effect of ionic strength and temperature on glutathione in aqueous solutions with NaCl as the major component (body fluids, seawater and brines).     

Effect of temperature and pH on the aggregation and the surface hydrophobicity of bovine κ-casein

κ-Casein (κ-CN) aggregation by heating has been studied at pH 7.2 and 5.2 using UV-visible spectrophotometry, sodium dodecyl sulfate polyacrylamide gel electrophoresis, spectrofluorometric study of the 1–8 aniline naphtalene sulfonate (ANS)–κ-CN binding and circular dichroism (CD) spectroscopy. The aggregation process to form aggregates like micelles or submicelles and the structural characteristics of these aggregates were pH dependent. Far-UV CD showed that the aggregates obtained by heating presented changes in the κ-CN secondary structure. Near-UV CD spectra showed a certain degree of tertiary organization in the Tyr environment for the protein heated or unheated, only at pH 5.2. ANS binding at both pH was quite different and depends on the self-association process. Heating produced exposition of hydrophobic binding sites only at pH 7.2, including those in the neighborhood of the κ-CN Trp residue.     

Effect of Temperature on the Solubility of Short-Chain Carboxylic Acids in Water

The aqueous solubilities of pentanoic and hexanoic acids were measured between 298.15 and 333.15 K at intervals of 5.00 K. Nonlinear dependences were found for the variation of solubility with temperature. The temperature dependences of the solubility of the acids in water are described by nonlinear van’t Hoff plots. Experimental data were fitted by the method of least-squares to a second-order polynomial equation, which was then used to determine the differential solution enthalpies at selected temperatures. The values for the apparent Gibbs energy and the apparent entropy of solution are calculated.     

Effect of pH on the Hydrothermal Synthesis of BN Nanocrystals

Boron nitride (BN) has been synthesized using hydrothermal synthesis method. The experimental results showed that the pH value of the reaction solution has an important effect on the yield and phases of BN samples. As the pH value decreased, the content of cBN increased and the yield improved. The increase in cBN content is resulted from the conversion of oBN into cBN under hydrothermal condition, and the growth of cBN nanocrystals may due to the decrease in the reaction speed, thus the crystalline perfection of BN improved when the pH value decreased.     

Effect of the porosity of PS–DVB-copolymers on ion chromatographic behavior in inverse size-exclusion and ion chromatography

Small and highly pressure-stable PS-DVB copolymers of different porosity had been prepared by a two-step swelling procedure which enabled variation of diluent composition, an important characteristic affecting the porosity. The polymers were characterized by inverse size-exclusion chromatography and scanning electron microscopy. Subsequent chloromethylation and amination resulted in anion exchangers suitable for ion chromatography.The pore volume and the pore-size distribution is substantially affected by the fraction of the solvens component in the diluent. It was apparent from scanning electron microscopy that surface structure and the size of the polymer particles was not affected by diluent composition. The functionalization process led to a decrease in pore volume. The pore-size distribution remained unchanged during functionalization, which can be explained in terms of partial closing of all pore sizes. The chromatographic efficiency of the functionalized polymers in ion chromatography was highly dependent on diluent composition and the extent of functionalization was determined by the total pore volume.The composition of the diluent is an excellent tool for optimization of polymers used for the synthesis of surface-functionalized anion exchangers.     

Effect of electrolyte and agitation on the anomalous behavior and morphology of electrodeposited Co–Ni alloys

This study continues previous work which showed that the anomalous behavior of Co–Ni deposition could be alleviated or eliminated through use of cyclic voltammetry (CV) or pulse reverse (PR) plating. The research focuses on aspects not considered in this previous work: the effects of the anion and agitation in the plating bath. A comparison is made of Co–Ni electrodeposition using the CV and PR techniques in sulfate and chloride baths at pH 3 containing equimolar Co(II) and Ni(II) concentrations under both stirred and unstirred conditions. The anomalous behavior can be significantly suppressed and even eliminated with current efficiencies above 90 % through use of PR plating, in particular, but only if carried out in a chloride solution under quiescent conditions. Both metal ion reduction during the cathodic portion and oxidation of the coating during anodic polarization are accelerated in the chloride solution relative to that in the sulfate solution. Electrolyte agitation exacerbates anomalous deposition and reduces the current efficiency by enhancing mass transport of Co(II) and H⁺ to and from the electrode. The origin of anomalous deposition and effects of the chloride ion are examined in terms of coordination chemistry and ligand field theory. This analysis suggests that oxidation of the Co–Ni coating in the chloride solution during anodic polarization of the PR and CV cycles when cobalt preferentially dissolves is crucial to suppressing the anomalous behavior. Examination of the coatings shows that the anion type, degree of agitation of the electrolyte, and electroplating technique significantly affects their microstructure and roughness.     

Effect of pH on the Final Connectivity Distribution of the Silicon Atoms in the Stöber Particles

Using ²⁹Si MAS-NMR we investigate the effect of pH on the final connectivity distribution of the silicon atoms in the Stöber particles. Our data suggest that the fraction of the silicon atoms that are ully-connected decreases as the ammonia concentration is increased. This suggests a more negative first shell substitution effect in the precipitated phase (liquid droplet) if condensation reactions are irreversible. A simple model is developed to describe the condensation kinetics in the precipitated phase, and the results support the negative first shell substitution effect. These findings challenge the notion of a positive first shell substitution effect in alkaline conditions.     

Study on the Synergism Effect of Lomefloxacin and Ofloxacin for Bovine Serum Albumin in Solution by Spectroscopic Techniques

Both lomefloxacin (LOM) and ofloxacin (OFL) have a powerful ability to quench the fluorescence of bovine serum albumin (BSA). The fluorescence quenching action is much stronger when the two drugs coexist. The synergism between LOM and OFL was studied using fluorescence and ultraviolet spectroscopy under imitated physiological conditions. The results show that static quenching and non-radiation energy transfer are the main reasons for the fluorescence quenching. The synergism results in both the reduction of the binding stability between drugs and BSA and an increase of the free drug concentration, which will increase the efficacy of drugs. The thermodynamic parameters at different temperatures were calculated and the binding distances r between the drugs and BSA were obtained based on Försters theory of non-radiation energy transfer. The synchronous fluorescence spectra indicated that the effect of synergism affected the conformation of BSA.     

Effect of the Charge and the Nature of Both Cations and Anions on the Solubility of Zwitterionic Amino Acids,Measurements and Modeling

The effect of the charge and the nature of both the cations and the anions of some electrolytic salts: sodium fluoride (NaF), potassium fluoride (KF), sodium bromide (NaBr), potassium bromide (KBr), sodium iodide (NaI), potassium iodide (KI), sodium sulfate (Na₂SO₄), potassium sulfate (K₂SO₄), calcium chloride (CaCl₂), and barium chloride (BaCl₂), on the solubility of zwitterionic amino acids (glycine, DL-alanine, DL-valine, and DL-serine) in aqueous solutions at 298.15 K are studied and discussed. A salting-in effect is observed for all amino acids under investigation with all electrolytes used in the present study, except for DL-alanine and DL-valine in aqueous solutions containing sodium fluoride where a salting-out effect was observed. The orders of the effect of the nature and the charge of both the anions and the cations are: F^- < Cl^- < Br^- < I^- < NO₃^- < SO₄^2-\mathrm{F}^{-}<{}\mathrm{Cl}^{-}<{}\mathrm{Br}^{-}<{}\mathrm{I}^{-}<\mathrm{NO}_{3}^{-}<{}\mathrm{SO}_{4}^{2-} with both sodium and potassium cations; Na⁺<K⁺<Ca²⁺<Ba²⁺ with chloride anion.     

Influence of lanthanum concentration on acid and catalytic properties of H-pentasil in the μ-xylene isomerization reaction

Russian Journal of Applied Chemistry - Acid and catalytic properties of pentasil-type lanthanum-containing zeolites in the μ-xylene isomerization reaction were studied.     

Effect of Amines on the Surface Charge Properties of Iron Oxides

Specific studies detailing the effects of amines, used as pH control agents for corrosion inhibition in power plants, on the surface charge of iron oxides provide data to assess the mechanism of how these amines impact deposition rate. The current study was undertaken in order to determine accurately the dissociation constants of the relevant amines at Pressurized Water Reactor (PWR) operating conditions and to investigate the effect of sorption of two of these amines (morpholine and dimethylamine) by magnetite. The acid-dissociation equilibria of morpholine (MOR), dimethylamine (DMA) and ethanolamine (ETA) were measured potentiometrically with a hydrogen-electrode concentration cell (HECC) from 0 to 290 °C in sodium trifluoromethanesulfonate (NaTr) solutions at ionic strengths up to 1 mol⋅kg⁻¹. Magnetite surface titrations were performed at an ionic strength of 0.03 mol⋅kg⁻¹ (NaTr medium) in the presence or absence of morpholine and dimethylamine buffers over a wide range of pH and total amine concentrations at 150–250 °C. D.A. Palmer is retired.     

Effect of Solvent Characteristics on the Photophysics of Hydroxyl Aromatic Compounds

The effect of solvent characteristics on the absorption and emission properties of 1- and 2-naphthols have been studied and the results interpreted in terms of the general and specific solute-solvent interactions. Measurements were performed in several solvents and analysis of the absorption and emission wavelengths were made using Lippert’s model for general solvent effects. A near linear relationship between the Stokes shift (D[`(n)]\Delta\bar{\nu}) and the orientation polarizability (Δf) were observed for both 1- and 2-naphthols in most of the alkanols, thus showing evidence of a general solvent effect. However, in 1,4-dioxane–water mixtures the plots deviate from linearity indicating the dominance of specific solvent effects that are not included in Lippert’s equation. In the case of interactions between the fluorophores and dioxane–water mixtures, excess Stokes’ shifts are observed in the order of dioxane composition 10%>20%>30%>50%>60%>80%. This may be due to excited state proton transfer (ESPT) and the involvement of hydrogen bonding between the protic group of the fluorophore and the solvents.     

Effect of Temperature and Composition on the Density and Viscosity of Binary Mixtures of Ionic Liquid with Alcohols

Density and viscosity were determined for the binary mixtures containing the ionic liquid 1-butyl-3-methylimidazolium thiocyanate ([BMIM][SCN]) and 1-alcohols (1-butanol, 1-pentanol and 1-hexanol) at six temperatures (298.15, 308.15, 318.15, 328.15, 338.15 and 348.15) K and ambient pressure. The density and viscosity correlation for these systems was tested by an empirical second-order polynomial and by the Vogel-Fucher-Tammann equation in wide ranges of temperatures. Excess molar volumes were described by the Redlich-Kister polynomial expansions. The density and viscosity variations with composition were described by polynomials. A qualitative analysis of the trend of the properties with solvent and temperature was performed. The obtained results indicate that ionic liquid interactions with 1-alcohols are strongly dependent on the special trend of packing of this ionic liquid into hydroxylic solvents. As previously observed, an increase of the 1-alcohol carbon-chain length leads to lower interactions on mixing. Electronic Supplementary Material  The online version of this article () contains supplementary material, which is available to authorized users.     

Effect of sol–gel derived in situ silica on the morphology and mechanical behavior of natural rubber and acrylonitrile butadiene rubber blends

Silica particles were generated and grown in situ by sol–gel method into rubber blends comprised of natural rubber (NR) and acrylonitrile butadiene rubber (NBR) at various blend ratios. Silica formed into rubber matrix was amorphous in nature. Amount of in situ silica increased with increase in natural rubber proportion in the blends during the sol–gel process. Morphology studies showed that the generated in situ silica were nanoparticles of different shapes and sizes mostly grown into the NR phase of the blends. In situ silica filled NR/NBR blend composites showed improvement in the mechanical and dynamic mechanical behaviors in comparison to those of the unfilled and externally filled NR/NBR blend composites. For the NR/NBR blend at 40/60 composition, in particular, the improvement was appreciable where size and dispersion of the silica particles into the rubber matrix were found to be more uniform. Dynamic mechanical analysis revealed a strong rubber–in situ silica interaction as indicated by a positive shift of the glass transition temperature of both the rubber phases in the blends.