Kinetics Characterization of Ion Release under Dynamic and Batch Conditions. I. Weak Acid and Weak Base Ion Exchange Resins

The aim of the present work is concerned with a study of the kinetics of release of both Ca²⁺ and F⁻ from the corresponding loaded ion-exchange resins (weak acid and weak base character for Ca²⁺ for F⁻, respectively), using both dynamic and batch experimental conditions with an artificial saliva solution as the ion-exchange media at 293 and 310 K. The influence of resin particle size and the temperature were evaluated by the kinetics parameters for the effective rate of release (B) and diffusion coefficient (D). The rate of ion release increases with temperature and decreases with particle size. The experimental data were well fitted by models based on intraparticle diffusion-controlled processes. In dynamic studies, the linear dependence of −log ₁₀(B) with the diameter of the resin particles can be applied for the estimation of B values when resins of low particle size are considered. In batch processes, although resins of low particle size can be studied, a linear relationship was only attained for the case of slow ion-exchange kinetic systems.     

Synthesis and characterization of microstructured sheets of semiconducting Ca[TCNQ]2 via redox-driven solid-solid phase transformation of TCNQ microcrystals

Microstructured sheets of semiconducting Ca[TCNQ]₂ (TCNQ = 7,7,8,8-tetracyanoquinodimethane) have been synthesized via electrochemically driven (TCNQ)/Ca[TCNQ]₂ solid-solid phase transformation that occurs upon one-electron reduction of solid TCNQ, mechanically attached to an electrode surface, in the presence of an aqueous Ca²⁺ _(aq) electrolyte solution. Voltammetric probing of the electrochemically irreversible TCNQ/Ca[TCNQ]₂ interconversion revealed that it is highly dependent on scan rate and Ca²⁺ _(aq) electrolyte concentration. This voltammetric behavior, supported by double potential-step chronoamperometric evidence, clearly attests that formation of Ca[TCNQ]₂ takes place via a rate-determining nucleation/growth process, which involves ingress of Ca²⁺ _(aq) cations into the TCNQ^·? crystal lattice at the triple phase TCNQ/TCNQ^·? _(s)│GC_(s)│Ca²⁺ _(aq) electrolyte junction. The overall redox process associated with this chemically reversible solid-solid transformation can be described by the equation: TCNQ⁰ _(S)?+?2e^??+?Ca²⁺ _(aq) ? {Ca[TCNQ]₂}_(S). SEM characterization of the morphology of the generated Ca[TCNQ]₂ material showed the formation of microstructured sheets, which are substantially different from those of parent TCNQ crystals and the needle-shaped crystals of group I cations (M⁺?=?Li, Na, K, Rb, and Cs). The kinetic and thermodynamic implications of the ΔE _p and E _m values as a function of scan rate are discussed in terms of nucleation–growth and their relevance to those reported for the conceptually related group I cations and binary M[TCNQ]₂ (M²⁺?=?Mn, Fe, Co, and Ni)-based coordination polymers.     

Kinetics and mechanism of oxidations by metal ions. Part 16. Oxidation of 4-oxopentanoic acid by aquomanganese(III) ions

Summary The outer-sphere oxidation of 4-oxopentanoic acid (4-OPA) to MeCO₂H by aquomanganese(III) ions exhibits a first-order dependence on [4-OPA] and [Mn(III)](aq). The observed pseudo first-order rate constant k _obs ([4-OPA] [Mn^III](aq)) is independent of [Mn^II] but decreases with increasing [H⁺]. The retarding effect of [H⁺] on the observed rate could be explained by considering either the reaction between MnOH⁺(aq) and MeCOCH₂— CH₂CO₂H or between Mn³⁺(aq) and MeCOCH₂CH₂-COO^– ions. The rate constant for the latter pair of reactants is much higher than the rate constant for the reaction between the first pair. Since the activation enthalpy for the first pair is about 14 kJ mol^–1 less than that of the second pair, it is concluded that the reactive species are MnOH²⁺(aq) and MeCOCH₂CH₂CO₂H or that the preferred oxidant is MnOH²⁺(aq) ion.     

Distribution of Strontium in the System Water — Ca(NO3)2 — Nitrobenzene — Strontium Dicarbollylcobaltate — 18-crown-6

From several strontium distribution experiments with ⁸⁵Sr tracer, the extraction constant corresponding to the equilibrium Ca²⁺(aq)+SrL²⁺(nb) CaL²⁺(nb)+Sr²⁺ (aq) in the two-phase water-nitrobenzene system (L = 18-crown-6; aq = aqueous phase, nb = nitrobenzene phase) was tentatively evaluated as log K _ex (Ca²⁺,SrL²⁺) = –1.9±0.1. Furthermore, the stability constant of the calcium — 18-crown-6 complex in nitrobenzene saturated with water was calculated for a temperature of 25 °C: log _nb(Cal²⁺) = 10.1±0.1.     

Experimental and theoretical study on the complexation of Ca2+ with beauvericin

From extraction experiments and γ-activity measurements, the exchange extraction constant corresponding to the equilibrium Ca²⁺(aq) + 1·Sr²⁺(nb) ? 1·Ca²⁺(nb) + Sr²⁺(aq) taking place in the two-phase water–nitrobenzene system (1 = beauvericin; aq = aqueous phase, nb = nitrobenzene phase) was evaluated as log K _ex(Ca²⁺, 1·Sr²⁺) = 1.1 ± 0.1. Further, the stability constant of the 1·Ca²⁺ complex in nitrobenzene saturated with water was calculated for a temperature of 25 °C: log β _nb(1·Ca²⁺) = 10.1 ± 0.2. Finally, by using quantum mechanical density functional level of theory calculations, the most probable structures of the non-hydrated 1·Ca²⁺ and hydrated 1·Ca²⁺·H₂O complex species were predicted.     

Solvent extraction of lead using a nitrobenzene solution of strontium dicarbollylcobaltate in the presence of polyethylene glycol PEG 400

Summary From extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium Pb²⁺(aq)+SrL²⁺ (nb)↔PbL²⁺ (nb)+Sr²⁺ (aq) taking place in the two-phase water-nitrobenzene system (L=PEG 400; aq = aqueous phase, nb = nitrobenzene phase) was evaluated as logK_ex(Pb²⁺, SrL²⁺)=2.0±0.1. Further, the stability constant of the PEG 400 - lead complex in nitrobenzene saturated with water was calculated for a temperature of 25 °C: log β_nb(PbL²⁺)=12.9±0.1.     

Extraction of lead from water into nitrobenzene by using strontium dicarbollylcobaltate in the presence of benzo-15-crown-5

Summary From extraction experiments andg-activity measurements, the extraction constant corresponding to the equilibrium Pb²⁺(aq)+SrL(nb)?PbL(nb)+Sr²⁺(aq)taking place in the two-phase water-nitrobenzene system (L = benzo-15-crown-5; aq = aqueous phase, nb = nitrobenzene phase) was evaluated aslog K_ex(Pb²⁺,SrL)=0.1±0.1. Further, the stability constant of the benzo-15-crown-5-lead complex in nitrobenzene saturated with water was calculated for a temperature of25 °C:log b_nb(PbL)=13.2±0.1.     

Extraction of lithium with nitrobenzene solution of strontium bis-1,2-dicarbollylcobaltate in the presence of 15-crown-5

From extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium 2Li⁺(aq)+SrL₂ ²⁺(nb) 2LiL⁺(nb)+Sr²⁺(aq) taking place in the two-phase water-nitrobenzene system (L=15-crown-5; aq=aqueous phase, nb=nitrobenzene phase) was evaluated as logK _ex (2Li⁺;SrL₂ ²⁺)=−3.7. Further, the stability constant of the 15-crown-5—lithium complex in nitrobenzene saturated with water was calculated: log β_nh(LiL⁺)=7.0.     

PGSE-NMR studies of solvent diffusion in poly(N-isopropylacrylamide) colloidal microgels

The solvent self-diffusion coefficient has been studied in thermoshrinking poly(N-isopropyl acrylamide) microgel dispersions by the pulsed-gradient spin-echo PGSE-NMR technique, as a function of temperature and mass fraction. After suitable corrections for the temperature, the H₂O/D₂O ratio and the relative volume fractions, all the self-diffusion data obtained over a temperature range of approximately 40 °C and mass fraction (2–12 % wt/wt) could be superimposed with the volume fraction as the universal factor. The observed reduction in the solvent self-diffusion coefficient with volume fraction was greater than that predicted by simple obstruction theory. After correction for-, and the subsequent removal of the obstruction effect, the diffusion of the solvent through the core of the particle is elucidated. As found for other polymer-solvent systems, there were no specific binding effects. The diffusion of the solvent in these dispersions over such temperature and mass fraction ranges could be rationalised assuming a constant solvent self-diffusion coefficient in the core of the particles.     

Extraction and <Emphasis Type="Italic">ab initio</Emphasis> calculation studies on the complexation of Ca<Superscript>2+</Superscript> with valinomycin

From extraction experiments and γ-activity measurements, the exchange extraction constant corresponding to the equilibrium Ca²⁺ (aq)+1·Sr²⁺ (nb) ⇆ 1·Ca²⁺ (nb) + Sr²⁺ (aq) taking place in the two-phase water-nitrobenzene system (1 = valinomycin; aq = aqueous phase, nb = nitrobenzene phase) was evaluated as log K _ex (Ca²⁺, 1·Sr²⁺) = 2.4±0.1. Further, the stability constant of the valinomycin-calcium complex (abbrev. 1·Ca²⁺) in nitrobenzene saturated with water was calculated for a temperature of 25 °C: log β _nb (1·Ca²⁺) = 8.3±0.1. By using quantum mechanical DFT calculations, the most probable structure of the 1·Ca²⁺·2H₂O complex species was predicted. In this complex, the “central” Ca²⁺ cation is bound by strong bonds to two oxygen atoms of the respective water molecules and to four ester carbonyl oxygens of the parent valinomycin ligand 1. Finally, the calculated binding energy of the considered complex 1·Ca²⁺·2H₂O is −319.2 kcal/mol, which confirms the relatively high stability of this cationic complex species.     

Stability of the valinomycin - strontium complex in water saturated nitrobenzene

Summary From extraction experiments and<span style='font-size:12.0pt;font-family:Symbol; mso-bidi-font-family:Symbol'>g-activity measurements, the extraction constant corresponding to the equilibrium Ba²⁺(aq)+SrL²⁺(nb)?BaL²⁺(nb)+Sr²⁺(aq) taking place in the two-phase water-nitrobenzene system (L= valinomycin; aq= aqueous phase,</o:p>nb= nitrobenzene phase) was evaluated as logK_ex(Ba²⁺, SrL²⁺)=1.3. Furthermore, the stability constant of the valinomycin-strontium complex in nitrobenzene saturated with water was calculated for a temperature of 25 °C: logb_nb(SrL²⁺)=5.4.     

Stability of the 15-crown-5-sodium complex in water saturated nitrobenzene

From extraction experiments with²²Na as a tracer, the extraction constant corresponding to the equilibrium Ba²⁺(aq)+2NaL⁺(nb)⇄ ⇄BaL₂ ²⁺(nb)+2Na⁺(aq) taking place in the two-phase water-nitrobenzene system (L=15-crown-5; aq=aqueous phase, nb=nitrobenzene phase) was evaluated as logK _ex (Ba²⁺,2NaL⁺)=3.3±0.1. Further, the stability constant of the complex BaL₂ ²⁺ in nitrobenzene saturated with water was calculated: log β_nh(BaL ₂ ²⁺ )=16.4±0.1.     

Extraction of silver from water into nitrobenzene using sodium dicarbollylcobaltate in the presence of valinomycin

Summary From extraction experiments andg-activity measurements, the extraction constant corresponding to the Ag⁺(aq) + NaL⁺(nb)?AgL⁺(nb) + Na⁺(aq) equilibrium in the two-phase water-nitrobenzene system (L=valinomycin; aq=aqueous phase, nb=nitrobenzene phase) was evaluated as log K_ex(Ag⁺,NaL⁺)=-0.6±0.1. The stability constant of the valinomycin-silver complex in nitrobenzene saturated with water was calculated: log b_nb(AgL⁺)=4.6±0.1. The stability constants of complexes of some univalent cations with valinomycin were summarized and discussed.     

Solvent extraction of barium picrate by p-tert-butylcalix[4]arene-tetrakis (N,N-diethylacetamide)

Summary From extraction experiments andg-activity measurements, the extraction constant of the Ba²⁺(aq)+2A^-(aq)+L(nb)?BaL²⁺(nb)+2A^-(nb) equilibrium in the two-phase water-nitrobenzene system (L = p-tert-butylcalix[4]arene-tetrakis (N,N-diethylacetamide); aq = aqueous phase, nb = nitrobenzene phase) was evaluated as logK_ex(BaL²⁺,2A^-)=6.5±0.1. Furthermore, the stability constant of the p-tert-butylcalix[4]arene-tetrakis (N,N-diethylacetamide)̵barium complex in nitrobenzene saturated with water was calculated for at 25 °C as logb_nb(BaL²⁺)=15.4±0.1.     

Extraction of lead with nitrobenzene solution of strontium bis-1,2-dicarbollylcobaltate in the presence of 15-crown-5

From extraction experiments and γ-activity measurements, the extraction constant corresponding to the equilibrium Pb²⁺(aq)+SrL₂ ²⁺(nb)⇆PbL₂ ²⁺(nb)+Sr²⁺(aq) taking place in the two-phase water-nitrobenzene system (L=15-crown-5; aq = aqueous phase, nb = nitrobenzene phase) was evaluated: logK _ex (Pb²⁺,SrL₂ ²⁺)=3.0. Further, the stability constant of the PbL₂ ²⁺ complex in nitrobenzene saturated with water was calculated: log β_nb(PbL ₂ ²⁺ )=17.8     

Kinetic study of the isotopic exchange of Na+ and Zn2+ ions on iron and chromium titanates

Iron(III) (FeTi) and chromium (III) titanates (CrTi) were prepared as cation exchange materials in a granular form. The rate of the isotopic exchange of Na⁺/*Na⁺ and Zn²⁺/*Zn²⁺ between aqueous solution and iron(III) and chromium(III) titanates in Na⁺ or Zn²⁺form has been carried out radiometrically in the 25-60 °C temperature range. The exchange rate is controlled by a particle diffusion mechanism and experimental and theoretical approaches have been used to obtain the rate of diffusion through the spherical particles of the exchangers. The values of self diffusion () of Na⁺ and Zn²⁺ ions were measured at different operation conditions, particle size, reaction temperatures and drying temperatures of the matrix. The values of kinetic and thermodynamic parameters were calculated and their significance discussed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Studies on extraction of In(III) with 8-hydroxyquinoline

The equilibrium molalities of In³⁺ in extraction reaction: In³⁺(aq)+3HOx(org) = In(Ox)₃(org) + 3H⁺(aq) were measured at ionic strengths from 0.13 to 2.54 mol·kg^?1 in the aqueous phase containing Na₂SO₄ as the supporting electrolyte and at constant initial molality of extractant, HOx, in the organic phase at temperatures from 278.15 to 308.15 K, where HOx and Ox mean 8-hydroxy-quinoline and its anion, respectively. The standard extraction constants K at various temperatures were obtained by two methods proposed in our previous paper.     

Effective intraparticle diffusion coefficients of CoCl2 in mesoporous functionalized silica adsorbents

The scope of this work is to determine the effective intraparticle diffusion coefficient of CoCl₂ over mesoporous functionalized silica. Silica is selected as a carrier of the functionalized groups for its rigid structure which excludes troublesome swelling, often found in polymeric adsorbents. 2-(2-pyridyl)ethyl-functionalized silica is selected as a promising affinity adsorbent for the reversible adsorption of CoCl₂. The adsorption kinetics is investigated with the Zero Length Column (ZLC) method. Initially, experiments were performed at different flow rates to eliminate the effect of external mass transfer. The effect of pore size (60 Å and 90 Å), particle size (40?10^?6 m–1000?10^?6 m) and initial CoCl₂ concentration (1 mol/m³–2.0 mol/m³) on the mass transfer was investigated. A model was developed to determine the pore diffusion coefficient of CoCl₂ by fitting the experimental data to the model. The pore diffusion coefficients determined for two different pore sizes of silica are D _p (60 Å) =1.95?10^?10 [m²/s] and D _p (90 Å) =5.8?10^?10 [m²/s]. The particle size and the initial CoCl₂ concentration do not have an influence on the value of diffusion coefficient. However, particle size has an influence on the diffusion time constant. In comparison with polymer adsorbents, silica based adsorbents have higher values of diffusion coefficients, as well as a more uniform and stable pore structure.     

Solvent extraction of sodium from water into nitrobenzene by using strontium dicarbollylcobaltate in the presence of benzo-15-crown-5

Summary From extraction experiments andg-activity measurements, the extraction constant corresponding to the 2Na⁺(aq)+SrL(nb)?2NaL⁺(nb)+Sr²⁺(aq) equilibrium taking place in the two-phase water-nitrobenzene system (L=benzo-15-crown-5; aq=aqueous phase, nb=nitrobenzene phase) was evaluated as log K_ex(2Na⁺,SrL)=1.0±0.1. Further, the stability constant of the benzo-15-crown-5-sodium complex in nitrobenzene saturated with water was calculated for a temperature of 25 °C: log b_nb(NaL⁺)=7.8±0.1.     

Extraction of barium picrate into nitrobenzene in the presence of benzo-15-crown-5

From extraction experiments with ¹³³Ba as a tracer, the extraction constant corresponding to the equilibrium Ba²⁺(aq) + 2A^-(aq) + 2L(nb) BaL₂ ²⁺(nb) + 2A^-(nb) in the two-phase water-nitrobenzene system (A^- = picrate, L = benzo-15-crown-5; aq = aqueous phase, nb = nitrobenzene phase) was evaluated as log K _ex (BaL₂ ²⁺, 2A^-) = 5.7. Furthermore, the stability constant of the benzo-15-crown-5 - barium complex in nitrobenzene saturated with water was calculated: log b_nb (BaL₂ ²⁺) = 14.6.