Protonating power of aqueous and aqueous-alcoholic solutions of HC1 in the presence of inorganic salts

The indicator method has been used to obtain a scale of protonating power of the medium H_o ^s for solutions of HCl in the solvents of constant composition H₂O-EtOH-KCl and H₂O-NH₄Cl at 25C. It is shown that in the solvents investigated the value of H_O ^s in HCl is the same as H₀ in aqueous solution for the same ratios of the concentrations of HCl and of the basic solvents H₂O and EtOH. A method is worked out for estimating the value of of an organic base in aqueous and aqueous-alcoholic solutions of HCl in the presence of inorganic salts.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 996–1000, May, 1991.     

The acidity functionsH 0 s of HCl solutions in EtOH with low water content

The acidity functionsH ₀ ^s of HCl solutions in EtOH-H₂O solvents containing 1.09, 3.0, and 5.0% water have been measured at 25 and 40 °C by the indicator method. The concentration of HCl changes from 10^–2 to 36m. Nitroanilines, for which a protonation mechanism is realized in the studied systems, were used as indicators.For each solvent,H ₀ ^s is temperature independent atm _HCl < 4, and acidity atm _HCl > 4 mol L^–1 increases more rapidly at 25 °C than at 40 °C. The acidity functions of aqueous and water-ethanol solutions of HCl were compared, and the concentrations of proton solvates of different compositions and their relative protonating ability were evaluated.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1722–1725, October, 1994.This work was financially supported by the Russian Foundation for Basic Research (Project No. 93-03-18356).     

Solubility and first hidrolysis constants of europium at different ionic strength and 303 K

The solubility of europium at 0.02M, 0.1M and 0.7M NaClO₄ ionic strength solutions was determined by a radiometric method and pEu_s-pC_H diagrams were obtained. Hydrolysis constants were also determined at the same ionic strengths by pH titration and the values found were log *₁ = -7.68±0.11, -8.07±0.10 and -8.20±0.11. The log K _sp values were -23.5±0.2, -22.7±0.2 and -21.9±0.2 for 0.02M, 0.1M and 0.7M NaClO₄ ionic strengths, respectively, at 303 K under CO₂-free conditions and the extrapolated value at zero ionic strength was log K _sp ⁰ = -24.15. The working pC_H ranges for the calculation of the hydrolysis constants were selected from the pEu_s-pC_H diagrams in the region where precipitation of europium oxide or hydroxide was less than 20%. Europium removal from aqueous solutions with zeolites was explored.     

Aquation of α-cis-chloroaquoethylenediamine-N,N'-diacetatocobalt(III) in aqueous and in mixed solvents: A mechanistic study

Summary The displacement of chloride ligands from -cis-chloro-aquoethylenediamine-N,N-diacetatocobalt(III) in nonacidic aqueous solutions was followed conductimetrically at 30–45° and the products of aquation were characterised by conductance, spectral and ion-exchange techniques. The rate constants for aquation in aqueous media and in 1 : 4 v : v mixed solvents at 25° are: 4.0 × 10^–5 s^–1 in H₂O, 2.71 × 10^–5 s^–1 in MeOH : H₂O, 2.74 × 10^–5 s^–1 in EtOH: H₂,O and 2.58 × 10^–5 s^–1 n in Me₂CO : H₂O. The corresponding H&#x002A; and S&#x002A; values have also been evaluated. Solvent polarity has a marked influence on the rate of chloride ion release. The aquation rate constants and the activation parameters have been correlated with solvent parameters,e.g. D, Y-values, Dimroth's E_T and Kosower's Z-values and, based on these correlations, a dissociative interchange (I_d) mechanism is proposed rather than dissociative as observed for some other cobalt(III) complexes.Senior author.     

Low-temperature heat capacities and standard molar enthalpy of formation of the complex

Low-temperature heat capacities of a solid complex Zn(Val)SO₄·H₂O(s) were measured by a precision automated adiabatic calorimeter over the temperature range between 78 and 373 K. The initial dehydration temperature of the coordination compound was determined to be, T _D=327.05 K, by analysis of the heat-capacity curve. The experimental values of molar heat capacities were fitted to a polynomial equation of heat capacities (C _p,m) with the reduced temperatures (x), [x=f (T)], by least square method. The polynomial fitted values of the molar heat capacities and fundamental thermodynamic functions of the complex relative to the standard reference temperature 298.15 K were given with the interval of 5 K. Enthalpies of dissolution of the [ZnSO₄·7H₂O(s)+Val(s)] (Δ_sol H _m,l ⁰) and the Zn(Val)SO₄·H₂O(s) (Δ_sol H _m,2 ⁰) in 100.00 mL of 2 mol dm^–3 HCl(aq) at T=298.15 K were determined to be, Δ_sol H _m,l ⁰=(94.588±0.025) kJ mol^–1 and Δ_sol H _m,2 ⁰=–(46.118±0.055) kJ mol^–1, by means of a homemade isoperibol solution–reaction calorimeter. The standard molar enthalpy of formation of the compound was determined as: Δ_f H _m ⁰ (Zn(Val)SO₄·H₂O(s), 298.15 K)=–(1850.97±1.92) kJ mol^–1, from the enthalpies of dissolution and other auxiliary thermodynamic data through a Hess thermochemical cycle. Furthermore, the reliability of the Hess thermochemical cycle was verified by comparing UV/Vis spectra and the refractive indexes of solution A (from dissolution of the [ZnSO₄·7H₂O(s)+Val(s)] mixture in 2 mol dm^–3 hydrochloric acid) and solution A’ (from dissolution of the complex Zn(Val)SO₄·H₂O(s) in 2 mol dm^–3 hydrochloric acid).     

Development of the diffusive gradient in thin films technique for the measurement of labile mercury species in waters

The diffusive gradients in thin films (DGT) technique, utilizing resin gel with ion-exchange resin Duolite GT73 and new ion-exchange resin Ambersep GT74, was investigated for the accumulation of four mercury species (Hg²⁺, CH₃Hg⁺, C₂H₅Hg⁺, C₆H₅Hg⁺). The diffusion coefficients of mercury species in agarose gel calculated on the basis of Fick’s Law were mercury species-specific. The diffusion coefficients of Hg²⁺ and CH₃Hg⁺ at 25 °C (9.07 ± 0.23 × 10⁻⁶ cm² s⁻¹ and 9.06 ± 0.30 × 10⁻⁶ cm² s⁻¹, respectively) were very similar, but the diffusion coefficients of C₂H₅Hg⁺ (6.87 ± 0.23 × 10⁻⁶ cm² s⁻¹) and C₆H₅Hg⁺ (3.86 ± 0.19 × 10⁻⁶ cm² s⁻¹) were significantly lower. Influence of experimental conditions (pH, selected cations, chlorides and humic substance) on mercury species accumulation by DGT was studied. The DGT technique was applied to river water spiked with mercury species.     

Artificial neural networks study of the catalytic reduction of resazurin: stopped-flow injection kinetic-spectrophotometric determination of Cu(II) and Ni(II)

An artificial neural network (ANN) procedure was used in the development of a catalytic spectrophotometric method for the determination of Cu(II) and Ni(II) employing a stopped-flow injection system. The method is based on the catalytic action of these ions on the reduction of resazurin by sulfide. ANNs trained by back-propagation of errors allowed us to model the systems in a concentration range of 0.5-6 and 1-15 mg l⁻¹ for Cu(II) and Ni(II), respectively, with a low relative error of prediction (REP) for each cation: REP_Cu(II) = 0.85% and REP_Ni(II) = 0.79%. The standard deviations of the repeatability (s_r) and of the within-laboratory reproducibility (s_w) were measured using standard solutions of Cu(II) and Ni(II) equal to 2.75 and 3.5 mg l⁻¹, respectively: s_r[Cu(II)] = 0.039 mg l⁻¹, s_r[Ni(II)] = 0.044 mg l⁻¹, s_w[Ni(II)] = 0.045 mg l⁻¹ and s_w[Ni(II)] = 0.050 mg l⁻¹. The ANNs-kinetic method has been applied to the determination of Cu(II) and Ni(II) in electroplating solutions and provided satisfactory results as compared with flame atomic absorption spectrophotometry method. The effect of resazurin, NaOH and Na₂S concentrations and the reaction temperature on the analytical sensitivity is discussed.     

Analysis of the molecular bands of D2H and H2D at 5600 Å

Spectral simulation was used to analyze the molecular rovibrational bands of D₂H and H₂D at 5600 Å. These bands were previously measured by the ion beam neutralization method. They were assigned to the electronic 3p²B₁ ? 2s²A₁ and vibrational (ν - ν″) = (0, 0, 0,-0, 0, 0) transitions. Least squares fits to the experimental line-positions were made to determine the asymmetric rotator constants A, B and C for the 2s²A₁ and 3p²B₁ ν = 0 states of D₂H and H₂D, hitherto unknown. Lorentz line-profiles were assumed for the D₂H and H₂D rotational lines, whose widths are mainly governed by the lifetimes of the lower states. The bands at 5600 Å were simulated and the 2s²A₁ state lifetimes were estimated to be σ ≥ 0.5 ± 0.2 ps for D₂H and σ ≥ 0.4 ± 0.2 ps for H₂D. Vibrational constants of D₃ and D₂H in the 2s²A₁ states are determined from the positions of the 0-0 and 0-1 vibrational bands given in respective experimental spectra previously measured. For the first time the vibrational constants ω₁ and ω₂ of the 2s²A₁ state of H₂D were estimated from the positions of the 0-0 and 0-1 band maxima. These vibrational constants are compared with the corresponding vibrational constants of their ions.     

Coordination Reaction of Alanine with Neodymium(III) and Erbium(III) Nitrate. Thermochemical study

The solid-state coordination reaction: Nd(NO₃)₃·6H₂O(s)+4Ala(s) → Nd(Ala)₄(NO₃)₃·H₂O(s)+5H₂O(_l) and Er(NO₃)₃·6H₂O(s)+4Ala(s) → Er(Ala)₄(NO₃)₃·H₂O(s)+5H₂O(l) have been studied by classical solution calorimetry. The molar dissolution enthalpies of the reactants and the products in 2 mol L^–1 HCl solvent of these two solid-solid coordination reactions have been measured using a calorimeter. From the results and other auxiliary quantities, the standard molar formation enthalpies of [Nd(Ala)₄(NO₃)₃·H₂O, s, 298.2 K] and[Er(Ala)₄(NO₃)₃·H₂O, s,298.2 K] at 298.2 K have been determined to be Δ_f H _m ⁰ [Nd(Ala)₄(NO₃)₃·H₂O,s, 298.2 K]=–3867.2 kJ mol^–1, and Δ_f H _m ⁰ [Er(Ala)₄(NO₃)₃·H₂O, s, 298.2 K]=–3821.5 kJ mol^–1. This revised version was published online in August 2006 with corrections to the Cover Date.     

Effect of the concentration of polybasic aminoanilides and aminobenzimidazoles on the acidity functionH 0 of aqueous solutions of HCl

The effect of the concentrations of the reactants and reaction products on the protonating ability of aqueous HCl is investigated in the example of the cyclization of polybasic aminoanilides to aminobenzimidazoles at 25°C and 50°C. It is established that the acidity functionH ₀ ^s of HCl solutions in organic-aqueous solvents of constant composition is equal toH ₀, the acidity function for an aqueous solution with the same concentration of HCl on the mole-ratio scale. This can be utilized for the quantitative prediction ofH ₀ ^s. The decrease in the basicity of indicators in mixed solvents is a consequence of the decrease in the activity coefficient of the unionized form of the base standardized to water _B. It is observed that not onlyH ₀ ^s but also the basicity constant of the reactant may vary during the reaction. The latter depends on the concentration of the reactant, as well as on the effect of the product concentration on the value of _B for the reactant.Deceased April 8, 1991.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 488–491, March, 1993.     

Hydrogen gas mixture separation by CVD silica membrane

In this work we investigate the performance of high flux chemical vapour deposition (CVD) silica membranes for the separation of gas mixtures containing H₂ and CO₂ at various temperatures. The membranes were prepared by a counter diffusion CVD method where tetraethyl orthosilicate (TEOS) and O₂ were used as reactants. Single gas permeation resulted in activated transport for the smaller kinetic diameter gases (H₂ and He) whilst the larger kinetic diameter gases (CO₂ and N₂) showed negative activation energy. The single gas permeation of H₂ increased from 5.1 × 10⁻⁷ to 7.0 × 10⁻⁷ mol m⁻² s⁻¹ Pa⁻¹ in the temperature range 100–400 °C, and H₂/CO₂ and H₂/N₂ selectivities reached 36 and 57 at 400 °C, respectively. The H₂ purity in the permeate stream also increased with temperature for H₂:CO₂ binary gas mixture, thus being beneficial for H₂ diffusion. H₂ competitively permeated through the membrane at a several range of gas mixtures, and a saturation level was achieved at H₂:CO₂ 60:40 feed concentration, where the diffusion of CO₂ molecules became negligible delivering ∼99% H₂ purity in the permeate stream. These results substantiate that the counter diffusion CVD method produced thin silica film membranes with a very precise pore size control, in particular suggesting a narrow pore distribution with average pore radius of about 3.1 Å.     

A system-independent correlation between the enthalpy and the entropy of dilution for polymer solutions

The second osmotic virial coefficient (A₂) and its entropic and enthalpic parts (A_2,s and A_2,H) have been determined, by means of light-scattering measurements, for solutions of polystyrene, polymethylmethacrylate and cellulose nitrate of different molecular weights in 19 solvents. A distinct qualitative correlation exists between A₂ and A_2,H and between A_2,s and A_2,H. The elimination of the “geometric” parameters of the polymer, by dividing these coefficients by suitably chosen reduction parameters, shows that the reduced coefficients obtained A₂⁰ and A_2,s⁰ are predominantly functions of the reduced enthalpy coefficient A_2,H⁰.     

Thermodynamics of ionic solid solutions: II. Discontinuous series: A new treatment of existing distribution data

A method of finding the activity coefficients of salts, anhydrous or hydrated, in binary solid solutions, described in an earlier paper as it applies to continuous series, has been applied to discontinuous series. The salts must differ with respect to only one ion. The method requires isothermal distribution data for equilibria between liquid (aqueous) and solid solutions in the ternary system consisting of the two salts and water. The following salt pairs were used for illustration: K(I/Br) at 0, 15, 25, 35, and 50°C., (NH₄/K)SCN at 0, 30, 60, and 90°C., (K/Tl)C10₃ at 10°C., and (NH₄/K)SO₃NH₂, (NH₄/K)Br, (Mg/Co)SO₄-7H₂O, and (Mn/Cu) SO₄.n H₂O-all at 25°C. Two kinds of behavior were noted and treated differently: systems in which the two series have the same, and those in which they have different crystal lattices. For two salts, A and B, which have the same lattice, and whose rational activity coefficients, f _A and f _B , can be described by 2-suffix Margules equations (regular solutions), lnf _A =B_sx _B ² and lnf _B =B_sx _A ² to be partially miscible, B_s>2, but this requirement does not apply if the lattices are different. In each series, distribution constants for the equilibria were also determined. Where possible, the calculated activities of the salts or the Gibbs excess energies of the solid solutions were compared with values reported by others who determined them by other methods. All the salt pairs studied show slight or strong positive deviations from ideality.     

Enthalpy change and mechanism of oxidation of o-phenylenediamine by hydrogen peroxide catalyzed by horseradish peroxidase

The hydrogen peroxide-oxidation of o-phenylenediamine (OPD) catalyzed by horseradish peroxidase (HRP) at 37 °C in 50 mM phosphate buffer (pH 7.0) was studied by calorimetry. The apparent molar reaction enthalpy with respect to OPD and hydrogen peroxide were −447 ± 8 kJ mol⁻¹ and −298 ± 9 kJ mol⁻¹, respectively. Oxidation of OPD by H₂O₂ catalyzed by HRP (1.25 nM) at pH 7.0 and 37 °C follows a ping-pong mechanism. The maximum rate V_max (0.91 ± 0.05 μM s⁻¹), Michaelis constant for OPD K_m,S (51 ± 3 μM), Michaelis constant for hydrogen peroxide Km,H₂O₂ (136 ± 8 μM), the catalytic constant k_cat (364 ± 18 s⁻¹) and the second-order rate constants k₊₁ = (2.7 ± 0.3) × 10⁶ M⁻¹ s⁻¹ and k₊₅ = (7.1 ± 0.8) × 10⁶ M⁻¹ s⁻¹ were obtained by the initial rate method.     

Vapor pressures and enthalpies of vaporization of a series of 1- and 2-halogenated naphthalenes

Molar enthalpies of vaporization, Δ_l^gH_m⁰, of 1-methyl-naphthalene, 1-chloro-napthalene, 2-chloro-naphthalene, 1-bromo-naphthalene, 2-bromo-naphthalene, and 1-iodo-naphthalene, as well as molar enthalpies of sublimation, Δ_s^gH_m⁰, of 2-chloro-naphthalene and 2-bromo-naphthalene have been obtained from the temperature dependence of the vapor pressure determined with the transpiration method. These values and the correlation gas-chromatography method, based on the Kovat’s index, have been used to determine Δ_l^gH_m⁰ and Δ_s^gH_m⁰ of 2-iodo-naphthalene. Results obtained in this work have been compared with those from the literature and found consistent.     

Hydrogen peroxide biosensor based on hemoglobin modified zirconia nanoparticles-grafted collagen matrix

A novel method for the immobilization of hemoglobin (Hb) and preparation of reagentless biosensor was proposed using a biocompatible non-toxic zirconia enhanced grafted collagen tri-helix scaffold. The formed membrane was characterized with UV-vis and FT-IR spectroscopy, scanning electron microscope and electrochemical methods. The Hb immobilized in the matrix showed excellent direct electrochemistry with an electron transfer rate constant of 6.46 s⁻¹ and electrocatalytic activity to the reduction of hydrogen peroxide. The apparent Michaelis-Menten constant for H₂O₂ was 0.026 mM, showing good affinity. Based on the direct electrochemistry, a new biosensor for H₂O₂ ranging from 0.8 to 132 μM was constructed. Owing to the porous structure and high enzyme loading of the matrix the biosensor exhibited low limit of detection of 0.12 μM at 3σ, fast response less than 5 s and high sensitivity of 45.6 mA M⁻¹ cm⁻². The biosensor exhibited acceptable stability and reproducibility. ZrO₂-grafted collagen provided a good matrix for protein immobilization and biosensing preparation. This method was useful for monitoring H₂O₂ in practical samples with the satisfactory results.     

Change in mechanistic pathway of hydroboration: A detailed kinetic study of H2BBr·SMe2 and HBBr2·SMe2

Hydroboration reactions of 1-octene and 1-hexyne with H₂BBr·SMe₂ in CH₂Cl₂ were studied as a function of concentration and temperature, using ¹¹B NMR spectroscopy. The reactions exhibited saturation kinetics. The rate of dissociation of dimethyl sulfide from boron at 25 °C was found to be (7.36 ± 0.59 and 7.32 ± 0.90) × 10⁻³ s⁻¹ for 1-octene and 1-hexyne, respectively. The second order rate constants, k₂, for hydroboration worked out to be 7.00 ± 0.81 M s⁻¹ and 7.03 ± 0.70 M s⁻¹, while the overall composite second order rate constants, k K, were (3.30 ± 0.43 and 3.10 ± 0.37) × 10⁻² M s⁻¹, respectively at 25 °C. The entropy and enthalpy values were found to be large and positive for k₁, whilst for k₂ these were large and negative, with small values for enthalpies. This is indicative of a limiting dissociative (D) for the dissociation of Me₂S and associative mechanism (A) for the hydroboration process. The overall activation parameters, ΔH^≠ and ΔS^≠, were found to be 98 ± 2 kJ mol⁻¹ and +56 ± 7 J K⁻¹ mol⁻¹ for 1-octene whilst, in the case of 1-hexyne these were found out to be 117 ± 7 kJ mol⁻¹ and +119 ± 24 J K⁻¹ mol⁻¹, respectively. When comparing the kinetic data between H₂BBr·SMe₂ and HBBr₂·SMe₂, the results showed that the rate of dissociation of Me₂S from H₂BBr·SMe₂ is on average 34 times faster than it is in the case of HBBr₂·SMe₂. Similarly, the rate of hydroboration with H₂BBr·SMe₂ was found to be on average 11 times faster than it is with HBBr₂·SMe₂. It is also clear that by replacing a hydrogen substituent with a bromine atom in the case of H₂BBr·SMe₂ the mechanism for the overall process changes from limiting dissociative (D) to interchange associative (I_a).     

Thermodynamic investigations on derivatives of pyrimidine nucleic acid bases: Joint use of calorimetric, volumetric and structural data for the description of properties of pyrimidine nucleic acid bases and their derivatives

The experimental enthalpies of solution Δ_solH_m^∞, van’t Hoff enthalpies of sublimation Δ_s^gH_m⁰ of solid compounds, partial molar volumes V₂⁰, and partial molar heat capacities C_p,2⁰ of aqueous solutions of pyrimidine nucleic acid bases and their derivatives, determined previously and collected here, are discussed in terms of calculated structural parameters. Relations have been established between the calorimetric and volumetric properties. Correlations have been developed to relate both the enthalpies of solvation and the partial molar heat capacities to the polar and apolar parts of the accessible molecular surface areas.     

Determination of thiomersal by flow injection coupled with microwave-assisted photochemical online oxidative decomposition of organic mercury and cold vapor atomic fluorescence spectroscopy

We developed a flow injection (FI) method for the determination of thiomersal (sodium ethylmercurithiosalicylate, C₉H₉HgNaO₂S) based on the UV/microwave (MW) photochemical, online oxidation of organic mercury, followed by cold vapor generation atomic fluorescence spectrometry (CVG-AFS) detection. Thiomersal was quantitatively converted in the MW/UV process to Hg(II), with a yield of 97 ± 3%. This reaction was followed by the reduction of Hg(II) to Hg(0) performed in a knotted reaction coil with NaBH₄ solution, and AFS detection in an Ar/H₂ miniaturized flame. The method was linear in the 0.01–2 μg mL⁻¹ range, with a LOD of 0.003 μg mL⁻¹. This method has been applied to the determination of thiomersal in ophthalmic solutions, with recoveries ranging between 97% and 101%. We found a mercury concentration in commercial ophthalmic solutions ranging between 7.5 and 59.0 μg mL⁻¹.     

Hydrogen purification using a SAPO-34 membrane

A SAPO-34 membrane separated CO₂/H₂ and H₂/CH₄ mixtures at feed pressures up to 1.7 MPa. Strong CO₂ adsorption inhibited H₂ adsorption and decreased H₂ permeances significantly, especially at low temperatures, so that CO₂ preferentially permeated and CO₂/H₂ selectivities were higher at low temperatures. At 253 K, CO₂/H₂ separation selectivities were greater than 100 with CO₂ permeances of 3 × 10⁻⁸ mol m⁻² s⁻¹ Pa⁻¹. The CO₂/H₂ separation exceeded the upper bounds (selectivity–permeability plot) for polymer membranes. The SAPO-34 membrane separated H₂ from CH₄ because CH₄ is close to the SAPO-34 pore size and has a lower diffusivity than H₂. The H₂/CH₄ separation selectivity had a small maximum with temperature, and decreased slightly with feed pressure and CH₄ feed concentration.