Calculation of equilibrium in anion-exchange extractive systems

Anion-exchange extractive systems based on solutions of higher quaternary ammonium salts in the presence of solvating additives, derivatives of trifluoroacetophenone, were considered. A mathematical model of the extractive system was developed and average solvation numbers and constants of solvation of ClO ₄ ^? , SCN^?, Br^?, and NO ₃ ^? ions by variously structured derivatives of trifluoroacetophenone were calculated from experimental data.     

The kinetics of reduction of palladium (II) complexes with β-alanine at dropping mercury electrode and the complexes’ stability constants

By using dc and ac polarography, the kinetics of electroreduction of the palladium (II) complexes with β-alanine at a dropping mercury electrode was studied in solutions with the palladium (II) concentration from 2 × 10^?5 to 2 × 10^?4 M and variable β-alanine and sodium perchlorate concentrations (pH 6–12). One polarographic wave was observed in solutions with pH 9 and 10 at the β-alanine overall concentration of c _βala = 1 × 10^?3 to 5 × 10^?2 M; two waves, at lower pH or higher c _βala. It was concluded on the formation of different forms of palladium (II) complexes in the studied solutions; the complexes contained two to four β-alanine coordinated anions. Using the limiting diffusion currents for the two waves at pH 9–11 and c _βala = 0.1 and 0.5 M, the stepwise stability constant for the Pd(βala) ₄ ^2? complex was calculated. Using two ac peaks observed at pH 7–8 and c _βala = 1 × 10^?2 to 0.1 M, the stepwise stability constant for the Pd(βala) ₃ ^? . was calculated. The perchlorate ions adsorbed at the dropping mercury electrode, as well as βala^? anions at their higher concentrations, hamper the electroreduction of the palladium (II) complexes with β-alanine.     

Structural Inhomogeneity in Electrolyte Solutions: The Calcium Perchlorate–Water System

A new approach has been proposed to study the structure of aqueous electrolyte solutions. NIR, Raman and attenuated total reflectance, Fourier transform infra-red (ATR FTIR) spectra have been measured for aqueous calcium perchlorate solutions in the 0.22–4.3 mol·L^?1 (0.22–7.46 mol·kg^?1) concentration range at 25 °C. By the methods of principal component analysis (PCA) and multivariate curve resolution—alternating least squares (MCR-ALS) the number, spectra and concentration profiles have been determined for spectroscopically distinguishable forms of water and ClO ₄ ^? ion in solutions. The results have been analyzed using a phenomenological model, establishing thereby: concentration ranges for structural rearrangements of the solution, the nature of structural microirregularities and different states of the ClO ₄ ^? ion in the areas of domination of the natural water structure, and of cybotactic groups of calcium perchlorate hexa and tetra hydrates.     

Effect of silver and copper ions on the decomposition of ozone in water

Features of the kinetics of ozone decomposition in water at pH 2 are studied depending on the concentration of silver and copper ions that are present. The existence of a critical concentration of metal ions (??3?6 × 10^?6 M) is established, below which ions slow the rate of ozone decomposition and above which the accelerate the process. It is concluded that the first region is due to the capture of hydroxyl and other radicals by metal ions, inhibiting the chain of ozone decomposition in water. A further increase in the concentration of ions leads to dominance of their direct interaction with molecules of ozone. A mechanism for the process is proposed and the rate constants of reaction of ozone with silver ions and copper are calculated (0.033 and 0.06 M^?1 s^?1, respectively).     

Electrical conductivity and ionic association of lithium and sodium perchlorates in tetrahydrofuran

The total limiting molar electrical conductivities of ions and triads of ions and the association constants of ions with the formation of ion pairs and triads of ions were calculated from the concentration dependences of the electrical conductivity of solutions of lithium and sodium perchlorates in tetrahydrofuran at 278.15–318.15 K with the use of the method specially developed earlier. The experimental total limiting electrical conductivities were used to calculate the limiting molar electrical conductivities and attraction friction factors of separate ions (Li⁺, Na⁺, ClO ₄ ^? , Li₂ClO ₄ ⁺ , Na₂ClO ₄ ⁺ , Li(ClO₄) ₂ ^? , and Na(ClO₄) ₂ ^? ). The constants of ion association into ion pairs were used to calculate the Gibbs energy of non-Coulomb interionic interaction (ΔG*_+?), and the constants of association into triads of ions, to determine the a ₃ distance parameter between the centers of the ion and the dipole of the ion pair. Positive ΔG*_+?), values and deviations of the experimental a ₃ value from the distance parameter calculated theoretically (a ₃ ⁰ ) for the triad of ions (Δa ₃ = a ₃ ? a ₃ ⁰ ) were related to non-Coulomb repulsion in the region of overlap of the solvation shells of ions and the influence of temperature and ion charge density on this repulsion.     

Comparison of chemical effects of UV radiation from spark discharge in air and a low-pressure mercury lamp

The chemical effects of UV radiation from atmospheric-pressure spark discharge and a DBK-9 low-pressure mercury lamp in distilled water and aqueous solutions of hydrogen peroxide and tryptophan have been studied. Reactive species generated in water by the both radiation sources are HO ₂ ^· radicals, acid residue ions NO ₂ ^? and NO ₃ ^? , and ammonium ions. The yield of HO ₂ ^· radicals has appeared to be the same for both sources, (1.1–1.2) × 10^?6 mol L^?1 s^?1. This is confirmed by measurements of the degradation kinetics of tryptophan, which can be destroyed by HO ₂ ^· radicals. The pH of water monotonically decreases with time during the spark discharge treatment. In the case of the mercury lamp, the pH varies insignificantly because of the competition of NH ₄ ⁺ alkali ions with the acid residues. UV radiation plays the major role in the decomposition of hydrogen peroxide.     

Extraction-photometric selective determination of trace perchlorates in potable waters

A method is proposed for the selective photometry determination of perchlorates in potable water with a detection limit of 2×10^?3 mg/L is proposed based on the extraction of its ion pair with the astrafloxin cation and absorbance measurements at 540 nm. The following ratios of matrix ions are acceptable (in parentheses): ClO^?, ClO ₂ ^? , ClO ₃ ^? , BrO ₃ ^? (500); I^? (1000); IO ₃ ^? (7000); HCO ₃ ^? , Cl^?,SO ₄ ^2? , NO ₃ ^? , Br^?, Na⁺, K⁺, Ca²⁺, Mg²⁺ (10000). The relative error of determination for ClO ₄ ^? is 20% in the range 4 × 10^-3-1 × 10^?2 mg/L and 10% in the range 1 × 10^-2–5 × 10^?2 mg/L.     

Role of reactive oxygen species and effect of solution matrix in trichloroethylene degradation from aqueous solution by zeolite-supported nano iron as percarbonate activator

The role of reactive oxygen species (ROSs) and effect of solution matrix have been investigated for the degradation of trichloroethylene (TCE). Zeolite-supported nano iron (Z-nZVI) was synthesized as an activator to catalyze sodium percarbonate (SPC) with or without hydroxylamine, i.e. as reducing agent (RA). The probe tests confirmed the generation of OH^· and O ₂ ^?· in the Z-nZVI activated SPC system in absence of the RA, while the presence of RA significantly increased the generation of OH^· and O ₂ ^?· radicals. Scavenger tests demonstrated that OH^· was the main ROS responsible for TCE degradation, whereas O ₂ ^?· also participated in TCE degradation. From the solution matrix perspective, the experimental results confirmed significant scavenging effects of Cl^? (1.0, 10.0, and 100 mmol L^?1) and HCO₃ ^? (1.0 and 10.0 mmol L^?1), whereas the scavenging effects were fairly impeded at 100 mmol L^?1 concentration of HCO₃ ^?. On the other hand, a considerable decline in scavenging effect was observed in the presence of RA in tested Cl^? and HCO₃ ^? concentration ranges. In addition, negligible scavenging effects of NO₃ ^? and SO₄ ^2? anions were found in all tested concentrations. The effect of initial solution pH on catalytic activity indicated a significant increase in the TCE degradation in the presence of RA even at higher pH value of 9. The results indicated that the Z-nZVI activated SPC system in presence of RA can effectively degrade chlorinated organic solvents, but it is important to consider the intensive existence of anions in groundwater.     

ClO<Stack><Subscript>4</Subscript><Superscript>−</Superscript></Stack>/Al-MCM-41 nanoparticles as a solid acid catalyst for the synthesis of 2-amino-3-cyanopyridines

A one-pot four-component reaction of various types of aldehydes, acetophenone, malononitrile, and ammonium acetate was studied in the presence of perchlorated Al-MCM-41 (ClO ₄ ^? /Al-MCM-41) nanoparticles for the synthesis of 2-amino-3-cyanopyridines. Mesoporous Al-MCM-41 molecular sieves with the Si/Al molar ratios of 30, 40, and 50 were synthesized by the sol–gel method and ClO ₄ ^? /Al-MCM-41 with different calcination temperatures were prepared and characterized by SEM, TEM, XRD, FT-IR, potentiometric titration and, N₂ adsorption-desorption techniques. The characterization results show that ClO ₄ ^? /Al-MCM-41 with calcination temperature of 300 °C has the best catalytic activity for the synthesis of 2-amino-3-cyanopyridines. The catalyst is reusable many times with moderate loss in its activity.     

Mechanism of the oxidation of hydrazoic acid by tetrachloroaurate(III) ion

The oxidation of hydrazoic acid in perchloric acid in the absence of added chloride under pseudo first-order conditions ([HN₃] » [AuCl ₄ ^? ]) is first order in [Au(III)]. Michaelis–Menten type of dependence (linear plots of k _obs ^?1 vs [HN₃]^?1) is observed with respect to [HN₃]. The k _obs is independent of ionic strength and the plot between k _obs ^?1 and [H⁺] is linear. The inner-sphere mechanism is consistent with the formation of an axial complex (K = 25 dm³ mol^?1) between AuCl₃(HO)^? ion and HN₃ prior to its rate determining decomposition (k = 0.0182 s^?1). It is inferred that the free radicals N ₃ ^? do not oxidise Au(II). The reaction becomes outer-sphere in the presence of added Cl^? ions which are inferred to form a cage around the hydronium ion surrounding the AuCl ₄ ^? ions. The penetration of N ₃ ^? through the cage is rate controlling and within the cage, the electron transfer from N ₃ ^? ion to AuCl ₄ ^? is fast. The value of the rate determining constant k ₂ is 0.547 dm³ mol^?1 s^?1 and the equilibrium constant K _Cl for the cage formation is 5 dm³ mol^?1 at 25 °C. It is calculated that the minimum HN₃ concentration required before the reaction exhibits zero-order dependence in HN₃ is 0.31 mol dm^?3 when [H⁺] = 0.18 mol dm^?3 at 25 °C.     

Self-diffusion coefficients and structure of the trivalent transplutonium ion curium and gadolinium in aqueous solution

Self-diffusion coefficients D of the trivalent aquo ion Cm³⁺ have been determined in aqueous Nd(ClO₄)₃?HClO₄ solutions (pH 2.5) at 25°C, by the open-end capillary method (O. E. C. M.). The variation of D versus the square root of the concentration of inactive solution is an exponential form in the studied range of concentration. The limiting value D₀ at zero ionic strength is 6.0·10^?6 cm²·s^?1. The curve \(D = f(\sqrt c )\) relating to Cm³⁺ can be compared to those of²⁴¹Am³⁺ and¹⁵³Gd³⁺ obtained under similar conditions. We find a similar ionic structure of Cm³⁺ with Am³⁺ and Gd³⁺. They have the same hydration as a tripositive of 5f and 4f ions in the absence of hydrolysis, complexing, or pairing at pH 2.5. The present study contributes to show the analogy of the solvation structure of trivalent actinide ions in aqueous solution at pH 2.5 with that of the trivalent lanthanide ions as a help for predicting the thermodynamic properties.     

Stripping voltammetric determination of azide ions

A procedure is proposed for the stripping voltammetric determination of N ₃ ^? ions at a mercury film electrode. It is based on the reduction of the mercury azide formed upon the oxidation of mercury in the presence of N ₃ ^? at ?0.02 to ?0.04V (in reference to an Ag/AgCl electrode) in a 0.1 M Na₂SO₄ supporting electrolyte solution. A linear dependence of the cathodic current peak on the N ₃ ^? concentration is observed in the concentration range from 4 × 10^?9 to 1 × 10^?3 M.     

Solid-phase-spectrophotometric and test determination of simultaneously present phosphorus forms (phosphorus speciation) in water

Solid-phase-spectrophotometric and test procedures are proposed to determine phosphorus as its ion associate with a quaternary ammonium salt and molybdoantimonophosphoric acid immobilized on silica gel in the concentration range 1.9–124 μg P/L. The determination of 4 μmol of phosphorus is not affected by (in μmol) alkali and alkaline-earth metals (≤2 × 10⁴), NH ₄ ⁺ (≤1 × 10³), Co²⁺ (≤1.0), Cu²⁺ (≤100), Mn²⁺ (≤10), Fe³⁺ (≤300), NO ₃ ^? and SO ₄ ^2? (≤2 × 10⁴), CO ₃ ^2? (≤1 × 10⁴), As (≤20), and Si (≤1 × 10³). The procedure was tested in the determination of various phosphorus forms in natural waters.     

The thermodynamic characteristics of vaporization of praseodymium triiodide

The vaporization of praseodymium triiodide was studied by high-temperature mass spectrometry. Monomeric (PrI₃) and dimeric (Pr₂I₆) molecules and the PrI ₄ ^? and Pr₂I ₇ ^? negative ions were recorded in saturated vapor over the temperature range 842–1048 K. The partial pressures of neutral vapor components were determined. The enthalpies of sublimation Δ_s H ^o(298.15 K) in the form of monomers (291 ± 10 kJ/mol) and dimers (400 ± 30 kJ/mol) were calculated by the second and third laws of thermodynamics. The equilibrium constants of ion-molecular reactions were measured and the enthalpies of the reactions determined. The enthalpies of formation Δ_f H ^o(298.15 K) of molecules and ions in the gas phase were calculated (?373 ± 11, ?929 ± 31, ?865 ± 25, and ?1433 ± 48 kJ/mol for PrI₃, Pr₂I₆, PrI ₄ ^? , and Pr₂I ₇ ^? , respectively).     

Ionic association and solvation in solutions of magnesium and nickel perchlorates in acetonitrile

The paper presents the conductometric data on solutions of Mg(ClO₄)₂ and Ni(ClO₄)₂ in acetonitrile over the temperature ranges 5–55°C for Mg(ClO₄)₂ and 25–75°C for Ni(ClO₄)₂. The extended Lee-Wheaton equation for unsymmetrical electrolytes was used to determine the limiting equivalent conductivities of the Mg²⁺, Ni²⁺, and ClO ₄ ^? ions and first-step ionic association constants with the formation of [KtClO₄]⁺ ion pairs. Lower ionic association constants for Ni(ClO₄)² compared with Mg(ClO₄)₂ were a consequence of stronger non-Coulomb repulsion in the formation of [KtClO₄]⁺ ion pairs because of the formation of a firmer solvation shell by the nickel compared with magnesium cation. The structure-dynamic parameter of ionic solvation was estimated. It was found that spatial-time correlations in the nearest environment of ions increased in the series ClO ₄ ^? > Mg²⁺ > Ni²⁺.     

Contribution of Organic Acid Anions to the Alkalinity of Natural Humic Water

It was found that the correction for organic acid anions to the alkalinity of water depends on the concentration of these anions, their dissociation constant, and pH; for humic water, it is expressed by the equation [Δ HCO ₃ ^? ] = [A _org ^? ](0.094 – 9064 × 10^?pH). Based on this equation and data on the alkalinity and ion balance of water, the concentrations of hydrogen carbonates and organic acid anions can be calculated. In accordance with the found average dissociation constant of humic acids (pK = 4.0), the contribution of their anions to the alkalinity of water is no higher than 10% of their concentration.     

Radiation polymerization of methacrylates controlled by a chain transfer catalyst

The effect of γ-radiation dose and chain transfer catalyst on polymerization of methyl methacrylate (MMA) and copolymerization of MMA with hydroxyethyl methacrylate or triethylene glycol dimethacrylate has been investigated. The addition of 5 × 10^?4?10^?3 mol/L of bis[(difluoroboryl) isopropylpyridine dimethylglyoximato]cobalt(II) (Co(II)) makes it possible to produce macromonomers MM _n ⁼⁼ bearing terminal double bonds and having a degree polymerization of n = 2?40 and a polydispersity index of 1.05?1.15. It has been found that the degree polymerization of the macromonomers increases with the increasing γ-radiation dose and monomer conversion through the mechanism of the reversible β-cleavage of the terminal unit: R _k ^? + MM _n ⁼ ? MM _k+1 ⁼ + R _n-1 ^? followed by the living polymerization of both radicals. This reaction may compete with the catalytic chain transfer reaction and have a significant effect on the evolution of the molecular weight characteristics of the macromonomers during the course of MMA (co)polymerization.     

The thermodynamic characteristics of dissolution and solvation of cetyltrimethylammonium perchlorate in the water-propan-2-ol system

The solubility of cetyltrimethylammonium perchlorate (CTAP) in propan-2-ol and its mixtures with water was determined by the isothermal saturation method over the whole composition range at 278.15–308.15 K. The solubility products and total standard Gibbs energies of transfer of the n-C₁₆H₃₃N(CH₃) ₃ ⁺ and ClO ₄ ^? ions were calculated. The solubility of CTAP in the mixed solvent specified was substantially influenced by solvophilic effects and the heterosolvation of ions caused by them.     

Synthesis and crystal structure of dibenzo-18-crown-6 oxonium perchlorate

An ionized crystalline adduct of dibenzo-18-crown-6, perchloric acid, and water (H₃O)[DB 18K6](ClO₄) is synthesized and structurally studied by X-ray diffraction. The crystals are triclinic: a = 8.582 Å, b = 10.486 Å, c = 26.293 Å, α = 79.45°, β = 82.00°, γ = 79.36°, Z = 4, space group P \(\bar 1\). The structure is solved by a direct method and refined by the full-matrix least-squares method in the anisotropic approximation to R = 0.098 for 5936 independent reflections (CAD4 automated diffractometer, λMoK _α radiation). The structure contains two independent DB18C6 molecules, two independent H₃O⁺ ions, and two independent ClO ₄ ^? ions. The H₃O⁺ ions each lie in the cavity of each of the two DB18C6 molecules and are retained there by three strong hydrogen bonds. Two DB18C6 molecules have close geometric parameters and a butterfly conformation with approximate symmetry C _2v . One of the two independent ClO ₄ ^? anions is disordered over two orientations.     

The solubility and kinetics of decomposition of ozone in aqueous solutions of nitrates

The influence of the concentration of NaNO₃ on the solubility of ozone in water was studied at 20, 30, and 40°C. The solubility coefficients of ozone were calculated, and the Henry constants and Sechenov coefficients determined. The Sechenov coefficients (K _c ) were found to decrease insignificantly as the temperature increased. The kinetics of dissolved O₃ transformations was analyzed. The decomposition of ozone was described by a pseudofirst-order equation with respect to salt concentration. The rate constant (k _c ) for the decomposition of ozone in the presence of NaNO₃ was found to be 3.5 × 10^?4 l mol^?1 s^?1.