Mechanism of the oxidation of L-ascorbic acid by the bis(pyridine-2,6-dicarboxylate)cobaltate(III) ion in aqueous solution

A detailed investigation of the oxidation of L-ascorbic acid (H₂A) by the title complex has been carried out using conventional spectrophotometry at 510 nm, over the ranges: 0.010 [ascorbate] _T 0.045 mol dm^–3, 3.62 pH 5.34, and 12.0 30.0 °C, 0.50 I 1.00 mol dm^–3, and at ionic strength 0.60 mol dm^–3 (NaClO₄). The main reaction products are the bis(pyridine-2,6-dicarboxylate)cobaltate(II) ion and l-dehydroascorbic acid. The reaction rate is dependent on pH and the total ascorbate concentration in a complex manner, i.e., k _obs = (k ₁ K ₁)[ascorbate] _T /(K ₁ + [H⁺]). The second order rate constant, k ₁ [rate constant for the reaction of the cobalt(III) complex and HA^–] at 25.0 °C is 2.31 ± 0.13 mol^–1 dm³ s^–1. H = 30 ± 4 kJ mol^–1 and S = –138 ± 13 J mol^–1 K^–1. K ₁, the dissociation constant for H₂A, was determined as 1.58 × 10^–4 mol dm^–3 at an ionic strength of 0.60 mol dm^–3, while the self exchange rate constant, k ₁₁ for the title complex, was determined as 1.28 × 10^–5 dm³ mol^–1 s^–1. An outer-sphere electron transfer mechanism has been proposed.     

Complex formation between nickel(II) and 2-(2-aminoethyl) benzimidazole: A kinetic and equilibrium study

Summary The reversible complex formation between 2-(2-aminoethyl) benzimidazole (AEB) and nickel(II) was studied by stopped flow spectrophotometry at I = 0.30 mol dm^–3. Both the neutral and monoprotonated form of AEB reacted to give the NiAEB²⁺ chelate. At 25 °C, the rates and activation parameters for the reactions Ni_II + AEB NiAEB²⁺ and Ni^II + AEBH⁺ NiAEB²⁺ + H⁺ are k _f ^L(dm^–3 mol^–1 s^–1) = (2.17 ± 0.24) × 10³, H (kJ mol^–1) = 40.0 ± 0.8, S (JK^–1 mol^–1) = – 47 ± 3 and k _inff ^pHL (dm³ mol^–1 s^–1) = 33 ± 10, H (kJ mol^–1) = 42.0 ±2.7, S (JK^–1 mol^–1) = – 72 ± 9. The dissociation of NiAEB²⁺ was acid catalysed and k _obs for this process increased linearly with [H⁺] in the 0.01–0.15 mol dm^–3 (10–30 °C) range with k _H(dm³ mol^–1s^–1) (25 °C) = 329 ± 6, H (kJ mol^–1) = 40 ± 2 and S (JK^–1 mol^–1) = – 61 ± 8. The results also indicated that the formation of NiAEB²⁺ involves a chelation-controlled, rate-limiting process. Analysis of the S ° data for the acid ionisation of AEBH _inf2 ^p2+ and the formation of NiAEB²⁺ showed that the bulky AEBH⁺ ion has a solvent structure breaking effect as compared to AEB [s _aqS ° (AEBH⁺) – s _aq ° (AEB) = 69 JK^–1 mol^–1], while AEBH _inf2 ^p2+ is a solvent ordering ion relative to NiAEB²⁺ [s _aq° (NiAEB²⁺) – ovS _aq ° (AEBH _inf2 ^p2+ ) = 11 JK^–1 mol^–1].Author to whom all correspondence should be directed.     

Transformations of formaldehyde and glycolaldehyde during the hydroformylation of formaldehyde in the presence of rhodium catalysts

Hydroformylation of formaldehyde to give glycolaldehyde (GA) in the presence of RhCl(PPh₃)₃, RhCl(CO)(PPh₃)₂, or the RhCl₃ + PPh₃ system inN,N-dimethylacetamide was studied. The hydroformylation is accompanied by the Cannizzaro-Tishchenko reaction, condensation of CH₂O with GA to give C₃-C₁₆ polyoxyaldehydes (POA), and dimerization of GA. The formation of POA, which probably occurs through coordination of GA with a Rh atom, predominates among the side reactions. The optimum conditions for hydroformylation of CH₂O were found to be: RhCl₃ + PPh₃ as the catalyst,T 383 K, 12MPa, [H₂O] 1.8 mol L^–1, [Rh] 2.5 · 10^–3 g-at. L^–1, and [CH₂O] 0.03 g L^–1. At a substrate conversion of 62–67 %, the selectivity of GA formation reaches 96 %, and the yield is 60–65 %.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 75–78, January, 1995.     

Kinetics of the thermal and photochemical decomposition of aquapentacyanoferrate(III) in aqueous solution

Summary The kinetics of the thermal and photochemical decomposition of aquapentacyanoferrate(III) ion in aqueous solution in the presence ofo-phenanthroline was studied spectrophotometrically. The first-order rate constant (k ) at 30° C [I=1 M(NaCl)] for the thermal reaction is (1.49±0.13)×10^–6 s^–1 with H =(158±7)kJ mol^–1 and S=(42±4) JK^–1 mol^–1. The initial quantum yield for the photochemical reaction at pH=7 is independent of the light intensity and is (1.49±0.33)×10^–2 mol einstein^–1.A communication on this subject was presented at the XVI Latinamerican Chemistry Congress held at Rio de Janeiro. Brasil, October 14–20, 1984.     

Ion-pair adsorption film colorimetry of iron (III) in water samples and human serum

The anionic chelate of iron(III)-2,2-dihydroxyazobenzene (H₂L), [FeL₂]^–, formed 1 1 ion-pair with crystal violet cation (CV⁺), CV⁺ [FeL₂]^–, and was adsorbed on a surface of transparent polyvinyl chloride (PVC) film plasticized with di-n-octyl phthalate. Enrichment of the blue violet species of the ion-pair onto the transparent PVC film has enabled a highly sensitive and simple method for the determination of iron(III). The detection limits are 1 × 10^–8 mol dm^–3 (0.6 ppb) by spectrophotometry at 592 nm, and 4 × 10^–8 mol dm^–3 (2 ppb) by visual colorimetry. The method has been successfully applied to the determination of iron in water samples and human serum. No preparatory procedures for the separation of serum protein and other coexisting substances are required, since ion-pair adsorption process provides a new method to prevent interference of serum matrix.     

Room Temperature Synthesis of Noble Metal Clusters in the Mesopores of Mechanically Strong Silica-Polymer Aerogel Composites

Clusters of Ag and Au have been formed in the bulk of mechanically strong silica-polymer aerogel composite monoliths. For that purpose, base-catalyzed silica hydrogels were washed with a 50% w/w acetone/diisocyanate (di-ISO) solution, and cured at 55°C for 3 days. Unreacted di-ISO solution was washed off with acetone, and the gels were washed with a acetone solutions of Ag⁺ or AuCl^– ₄ (3 × 10^–4 mol · L^–1), containing also 0.2 mol · L^–1 of 2-propanol as radical scavenger. Metal clusters were formed upon radiolytic reduction ( rays, 48–72 h, 7–7.5 kGy) of the precursor ions. After irradiation, the hydrogels were washed with acetone, and dried in supercritical CO₂. The resulting aerogel monoliths had a density of 0.56 g·cm^–3, a surface area of about 160 m² · g^–1, and an average pore diameter of about 200 nm. Transmission electron microscopy showed that the metal clusters are free of contamination, with a cubic face centered structure, and a narrow size distribution, centered around 10 nm. The elastic module, measured with a three-point flexural bending method, was in the 60–70 MPa range, and the load at rupture between 16 and 19 kg. Thermogravimetric analysis showed that the composites were stable up to about 300°C. These results are in excellent agreement with results obtained previously for as-grown, di-ISO cross-linked silica aerogels, and show that addition of metal clusters and gamma irradiation to a dose corresponding to a permanence of several years in low earth orbit at high inclination did not affect the chemical identity, the mechanical strength, the porosity and the bulk density of the composite aerogel monoliths.     

Time-resolved enzymatic determination of glucose using a fluorescent europium probe for hydrogen peroxide

An enzymatic assay for glucose based on the use of the fluorescent probe for hydrogen peroxide, europium(III) tetracycline (EuTc), is described. The weakly fluorescent EuTc and enzymatically generated H₂O₂ form a strongly fluorescent complex (EuTc–H₂O₂) whose fluorescence decay profile is significantly different. Since the decay time of EuTc–H₂O₂ is in the microseconds time domain, fluorescence can be detected in the time-resolved mode, thus enabling substantial reduction of background fluorescence. The scheme represents the first H₂O₂-based time-resolved fluorescence assay for glucose not requiring the presence of a peroxidase. The time-resolved assay (with a delay time of 60 s and using endpoint detection) enables glucose to be determined at levels as low as 2.2 mol L^–1, with a dynamic range of 2.2–100 mol L^–1. The method also was adapted to a kinetic assay in order to cover higher glucose levels (mmol L^–1 range). The latter was validated by analyzing spiked serum samples and gave a good linear relationship for glucose levels from 2.5 to 55.5 mmol L^–1. Noteworthy features of the assay include easy accessibility of the probe, large Stokes shift, a line-like fluorescence peaking at 616 nm, stability towards oxygen, a working pH of approximately 7, and its suitability for both kinetic and endpoint determination.     

On the characteristics and mechanism of the radiation-induced chain reaction between sulfur dioxide and molecular oxygen in acid solutions

Characteristics of the -induced chain reaction between sulfur dioxide and molecular oxygen in perchloric and sulfuric acid media in the presence of Ce(III) ions have been studied. The concentration effects of dissolved oxygen (0.2·10^–3–9.4·10^–3 mol/dm³, sulfur dioxide (0.3·10^–1–2.0·10^–1 mol/dm³ and Ce(III) (0.2·10^–3–4.8·10^–3 mol/dm³) and dose rate (0.26·10¹⁹–1.0·10¹⁹ eV/dm³·s) on the radiation — chemical yield of oxygen consumption G(–O₂) and accumulation of sulfate G(HSO ₄ ^– ), have been investigated. The reaction proceeds with G(–O₂) reaching 10²–10³ molecule/100eV in a catalytic regime. The reaction rate in perchloric acid medium is 3–4 times lower than that in the sulfuric acid medium and depends on the SO₂, O₂ and Ce(III) concentrations, the reaction order varying from 1.0 to 0 and/or in the reverse direction. The mechanism of the process involves chain propagation with 3 stages and 3 intermediates: SO₃H, HSO₅ and Ce(IV). The catalytic effect is caused by the interaction of HSO₄ with Ce(IV) ions followed by their reduction when interacting with SO₂, yielding SO₃H radicals. Chain termination may be due to one or two of the three intermediates or due to all three particles, the kinetics depending on this. Kinetic equations describing the experimental data have been obtained.     

Determination of hexavalent chromium by using speciated isotope-dilution mass spectrometry after microwave speciated extraction of environmental and other solid materials

Precise and accurate determination of hexavalent chromium in different types of solid environmental sample is regarded as a technical challenge with significant potential error if historically accepted methods are used. Microwave-assisted alkaline extraction (0.5 mol L^–1 NaOH+0.28 mol L^–1 Na₂CO₃) followed by anion-exchange chromatographic separation and inductively coupled plasma mass spectrophotometric detection has been shown to provide accurate and precise results. To obtain a better understanding of potential species conversion during and/or after extraction steps, speciated isotope-dilution mass spectrometry (SIDMS) (EPA Method 6800) metrology has been successfully applied as a diagnostic tool with the modified accompanying extraction version of EPA Method 3060A. In our study, aggregate materials distributed over a large area of a major western US state were found to contain a high concentration of total chromium (195±13 to 709±19 g g^–1) and significant amounts of Cr⁶⁺ (141±6 to 341±29 g g^–1) which are at least three orders of magnitude higher than the US EPA threshold limit (0.5 g g^–1). Sediment samples from a major western US state, studied independently, were found to contain less (1.77±0.34 g g^–1) or no Cr⁶⁺ in the presence of significant total chromium.     

Electronic structure and the unimolecular reactions of imine peroixde HNOO

Summary Electronic structure and possible unimolecular reaction paths of a linear four-atom molecule HNOO to be formed by the addition of NH(^3–) toward O₂(³ _g ^– ) are investigated by the SCF and MRD-CI calculations employing the 6–31G** basis functions. HNOO in its ground state (¹ A) is an ozone-like diradicaloid, whose N–O binding energy is only 27 kJ/mol. Geometries and excitation energies of various diradical (excited) states, both singlet and triplet, are examined. The isomerization paths of the ground-state HNOO(¹ A) are traced by a multi-configuration (MC) SCF procedure and the activation barrier heights evaluated by the CI treatment. It has proved that energetically the most favorable is the 1,3-hydrogen migration to give hydroperoxynitrene NOOH(¹ A) with the barrier height of 62 kJ/mol. The nitrene should be extremely unstable; it is liable to be decomposed to NO + OH with virtually no activation barrier.Presented at the 7th International Congress on Quantum Chemistry, Menton, July 1991     

Kinetics and mechanism of the interaction of thiourea with cis-diaquaethylene-diamineplatinum(II) perchlorate in aqueous medium

The kinetics of the interaction of thiourea with [Pt(en)(H₂O)₂]²⁺ have been studied spectrophotometrically as a function of [Pt(en)(H₂O)₂]²⁺, [thiourea] and temperature at a particular pH(4.0), where the substrate complex exists predominantly as the diaqua species and the thiourea ligand as a neutral molecule. The reaction proceeds via a rapid outer sphere association followed by two slow consecutive steps, the second step exhibiting first order dependence on the aqua ion and thiourea concentrations. The activation parameters for both the steps have been evaluated: (H ₁ = 54.8 ± 1.2 kJ mol^–1, S ₁ = –96 ± 4 J K^–1 mol^–1, H ₂ = 27.9 ± 0.8 kJ mol^–1 and, S ₂ = –183 ± 2.6 J K^–1 mol^–1). The low enthalpy of activation and large negative values of entropy of activation indicate an associative mode of activation for both consecutive steps.     

Determination of traces of vanadium with the catalytic maximum wave in differential pulse polarography

Summary A differential pulse-polarographic method has been studied for the determination of vanadium employing the catalytic maximum wave. A well-defined differential pulse polarographic peak is observed in the potential range from –0.2 to –0.7 V vs. SCE for vanadium(V) in 10 mmol 1^–1 NaCl containing 10 mmol 1^–1 acetic acid, 40 mmol 1^–1 pyrocatechol, and 2.5 mmol 1^–1 KBrO₃. The peak current is very large and proportional to the concentration of vanadium(V) between 1×10^–7 and 1×10^–6 mol 1^–1. The relative standard deviation at 0.5 mol l^–1 vanadium(V) was 2.06% (n=7). This method has been successfully applied to the determination of vanadium in standard materials such as pond sediment.

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Spurenbestimmung von Vanadium mit Hilfe der katalytischen Maximumsstufe in der Differential-Puls-Polarographie

Zusammenfassung Ein gut definierter differentialpuls-polarographischer Peak wurde für Vanadium(V) in 10 mmol/l NaCl-Lösung, die 10 mmol/l Essigsäure, 40 mmol/l Brenzcatechin und 2,5 mmol/l KBrO₃ enthielt, beobachtet (Potentialbereich –0,2 bis –0,7 V gegen SCE). Der Peakstrom ist sehr groß und die Vanadiumkonzentration im Bereich von 1×10^–7 bis 1×10^–6 mol/l proportional. Die relative Standardabweichung betrug 2,06% (n=7) bei 0,5 mol/l Vanadium(V). Das Verfahren wurde mit gutem Erfolg zur Vanadiumbestimmung in Standardproben (z.B. Teichsediment) eingesetzt.

     

Kinetic and mechanistic studies on the interaction of thymidine with the hydroxopentaaquarhodium(III) ion

The interaction of thymidine, a nucleoside, with hydroxopentaaquarhodium(III), [Rh(H₂O)₅(OH)]²⁺ ion in aqueous medium is reported and the possible mode of binding is discussed. The kinetics of interaction between thymidine and [Rh(H₂O)₅OH]²⁺ has been studied spectrophotometrically as a function of [Rh(H₂O)₅OH²⁺], [thymidine], pH and temperature. The reaction has been monitored at 298 nm, the _max of the substituted complex, and where the spectral difference between the reactant and product is a maximum. The reaction rate increases with [thymidine] and reaches a limiting value at a higher ligand concentration. From the experimental findings an associative interchange mechanism for the substitution process is suggested. The activation parameters (H=47.8 ± 5.7 kJ mol^–1, S=–173 ± 17 J K^–1 mol^–1) supports our proposition. The negative G⁰ (–13.8 kJ mol^–1) for the first equilibrium step also supports the spontaneous formation of the outer sphere association complex.     

The effect of mechanical activation on the thermal decomposition of chalcopyrite

Experimental results on the influence of preliminary mechanical activation on the thermal decomposition of chalcopyrite are presented and discussed. The following experimental facts were found:

Kinetics of enzymatic hydrolysis of sodium carboxymethylcellulose with different degrees of polymerization by cellulase

The reaction cellulase (EC 3.2.1.4)—sodium carboxymethylcellulose (Na-CMC) with different degrees of polymerization (n=140, 640 and 900) was investigated by the use of a modifiedMichaelis-Menten equation, valid for enzymatic hydrolysis of linear homopolymers. TheMichaelis-Menten constant [Km (M)=6.31·10^–2mol/dm³] and the reaction rate constant (k ₊₂=4.07·10^–6s^–1), which correspond to the enzymatic hydrolysis of a single bond in the homopolymer substrates are determined. The free energy ( =101 kJ/mol), which corresponds to the degradation and formation of a single bond in the enzyme—polymer substrate is also estimated. This energy expressed in electronvolt units is =1.39 eV. The ratio between the effective cross section of the reactive substrate bond and the active enzyme center is =1.22.

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Kinetik der enzymkatalysierten Hydrolyse von Natriumcarboxymethylcellulose mit verschiedenem Polymerisationsgrad durch Cellulase

Zusammenfassung Die modifizierte Gleichung nachMichaelis-Menten wird bei der durch Cellulase (EC 3.2.1.4) katalysierten hydrolytischen Spaltung von Natriumcarboxy-methylcellulose (Na-CMC) verschiedenen Polymerisationsgrades (n=140, 640 und 900) angewandt. Es wurde dieMichaelis-Menten-Konstante [Km (M)=6.31·10^–2mol/dm³] und die Reaktionsgeschwindigkeitskonstante (k ₊₂=4.07·10^–6s^–1), die der enzymatischen Hydrolyse einer Einfachbindung im homopolymeren Substrat entspricht, berechnet. Die freie Energie ( =101 kJ/mol), die dem Abbau und der Bildung einer Einfachbindung im Enzym—Polymer-Substrat entspricht, wurde bestimmt. Diese Energie — ausgedrückt in Elektronvolt-Einheiten — beträgt =1.39 eV. Das Verhältnis zwischen den effektiven Querschnitten der reaktiven Substratbindung ( _S ) und des aktiven Enzym-Zentrums ( _E ) beträgt =1.22.

     

Photometrische Bestimmung von Sulfid mit Jodnitrotetrazoliumchlorid

Zusammenfassung S^2– kann mit Jodnitrotetrazoliumchlorid (INT) innerhalb von 30 min photometrisch bestimmt werden. PO₄ ^3–, Cl^– und SO₄ ^2– in Konzentrationen bis zu 5 · 10^–2 mol/l, S₂O₃ ^2– bis zu 10^–4 mol/l und S₃O₆ ^2– bis zu 2 · 10^– mol/l stören nicht. Die untere Bestimmungsgrenze beträgt 3,4 · 10^–5 mol/l, entsprechend 1 g S^2–. Als relative Standardabweichung ergibt sich bei der Bestimmung von 3,2 g S²}±6,4 Rel.%.Die Untersuchungen wurden mit Hilfe eines Stipendiums der Alexander von Humboldt-Stiftung durchgeführt, der an dieser Stelle herzlich gedankt sei.     

The outersphere complex of EuCl2+ in a mixed system of methanol and water of 1.0M (H, Na) (Cl, ClO4)

The stability constans, ₁, of each monochloride complex of Eu(III) have been determined in the methanol and water mixed system with 1.0 mol·dm^–3 ionic strength using a solvent extraction technique. The values of ₁ increase with an increase in the mole fraction of methanol (X _S ) in the mixed solvent system when 0X _S 0.40. The, distance of Eu³⁺–Cl^– in the mixed solvent system was calculated using the Born-type equation and the Gibbs' free energy derived from ₁. Calculation of the Eu³⁺–Cl^– distance and the preferential solvation, of Eu³⁺ by water proposed the variation of the outersphere complex of EuCl²⁺ as follows: (1) [Eu(H₂O)₉]³⁺Cl^–, [Eu(H₂O)₈]³⁺Cl^– and [Eu(H₂O)₇(CH₃OH)³⁺Cl^– inX _S0.014, (2) [Eu(H₂O)₈]^3–Cl^– and [Eu(H₂O)₇(CH₃OH)]³⁺Cl^– in 0.014<X _S <0.25 and (3) [Eu(H₂O)₇(CH₃OH)]^3–Cl^– and [Eu(H₂O)₆(CH₃OH)[₂ ³⁺Cl^– in 0.25<X _S 0.40.     

Rapid determination of telmisartan in pharmaceuticals and serum by the parallel catalytic hydrogen wave method

The polarographic characteristics of telmisartan have been investigated in 0.8 mol L^–1 NH₃.H₂O–NH₄Cl (pH 8.9)–0.01 mol L^–1 H₂O₂ as supporting electrolyte. The results demonstrate that the polarographic reduction wave at ca. –1.30 V in the absence of H₂O₂ is a catalytic hydrogen wave, and the reduction wave enhanced by H₂O₂ is a so-called parallel catalytic hydrogen wave. The analytical sensitivity of the parallel catalytic hydrogen wave is ca. 60 times higher than that of the corresponding catalytic hydrogen wave. Based on the parallel catalytic hydrogen wave a novel method has been developed for determination of telmisartan by linear sweep polarography. The calibration curve is linear in the range 2.0×10^–8–2.0×10^–6 mol L^–1 and the detection limit is 1.0×10^–8 mol L^–1. The precision is excellent with relative standard deviations of 2.6% at a concentration of 1.0×10^–7 mol L^–1 telmisartan. The proposed method has been applied to the direct determination of the telmisartan in capsule forms and biological samples. The proposed method has been proved to be advantageous over existing CZE and MEKC methods in simplicity, rapidity, and reproducibility.     

Indirect determination of bromide by diffusion flow injection analysis with amperometric detection

Summary A rapid, indirect diffusion flow injection analysis (FIA) method with amperometric detection has been developed for the selective and sensitive determination of Br^–. The method is based on permanganate oxidation of Br^– to bromine. Bromine diffuses through a PTFE membrane and is quantified amperometrically at a platinum working electrode. Calibration graphs were linear up to the maximum concentration of Br^– investigated (10.0 mmol/l). The precision of the technique was better than a relative standard deviation of 0.7% at 10.0 mol/l, with a throughput of 30 samples per hour. The effects of temperature, acidity, working potential, composition of the reagent solution and interferents on the FIA signals were studied. The catalytic effect of Cl^– on the permanganate oxidation of the analyte was utilized to lower the detection limit to 1 mol/l (16 ng Br^–). Similar detection limits were achieved by combining the effects of higher acidity (4.0 mol/l H₂SO₄) and elevated temperatures (40°C). The method was successfully applied to the determination of Br^– in chloride and other reagents, as well as in natural waters.     

Tris(2-ethylhexyl)phosphate as an extractant for quadrivalent tin,with subsequent determination with pyrocatechol violet in alloy samples

The solvent extraction of tin(IV) from chloride media withtris(2-ethylhexyl)phosphate is presented. Tin(IV) is extracted quantitatively from 2.75–3.20 mol dm^–3 hydrochloric acid using 6.38–6.91 mol dm^–3 tris(2-ethyl-hexyl)phosphate dissolved in toluene as an extractant. After back-extraction of tin(IV) with water from thetris(2-ethylhexyl)phosphate phase, it is estimated spectrophotometrically following complexation with pyrocatechol violet. The recommended range for determination of tin(IV) is 10–100 g. The probable extracted species is SnCl₄·2TEHP. The method is applicable to the analysis of alloy samples with a detection limit of 0.4 g/ml (for 10 g of tin) and a relative standard deviation between 0.21–0.32%.