Kinetics of substitution of aquo ligands fromcis-diaquo-bis-(biguanide) cobalt(III) and chromium(III) ions by aspartic acid in ethanol—water mixtures

The kinetics of substitution of aqua ligands fromcis-diaqua-bis(biguanide)cobalt(III) and chromium(III) ions by aspartic acid in EtOH–H₂O media have been studied spectrophotometrically in the 30 to 45°C range. We propose the following rate law for the anation

Substitution of aqua ligands fromcis-diaqua-bis(bipyridyl) ruthenium(II) by 1, 10-phenanthroline in aqueous medium

The kinetics of aqua ligand substitution fromcis-[Ru(bipy)₂(H₂O)₂]²⁺ by 1, 10-phenanthroline (phen) have been studied spectrophotometrically in the 35 to 50°C temperature range. We propose the following rate law for the reaction within the 3.65 to 5.5 pH range:

Solvent effects on the anation ofcis-diaquo-bis-ethylenediamine cobalt(III) by L-proline

The anation kinetics of the title complex were investigated spectrophotometrically in aqueous methanol, ethanol, ipropanol, t-butanol and dioxane, and the following rate law was established:

Kinetics and mechanism of anation of hexaaquochromium(III) by 2-aminopyridine

The kinetics of substitution of aqua ligands from the hexaaquochromium(III) ion by 2-aminopyridine (2-ampyH⁺) in aqueous medium has been studied spectrophotometrically in the 40–55° C range. The rate law involving the outer sphere complex formation has been established at pH 2.7 as

Vanadium(V) oxidation of thallium(I) in hydrochloric acid

The reaction between V^V and Tl^I was studied in 4.0 mol dm^–3 HCl at an ionic strength of 4.1 mol dm^–3 at 25° C. The main active species under the reaction conditions were found to be VO _inf2 ^sup+ and TlCl _inf3 ^sup2– for the oxidant and reductant, respectively. A probable mechanism in terms of these species is given, and follows the rate law:

Kinetics and mechanism of oxidation of hydroxylamine by tetrachloroaurate(III) ion

The oxidation of H₂NOH is first-order both in [NH₃OH⁺] and [AuCl₄ ^–]. The rate is increased by the increase in [Cl^–] and decreased with increase in [H⁺]. The stoichiometry ratio, [NH₃OH⁺]/[AuCl₄ ^–], is 1. The mechanism consists of the following reactions.

Kinetic study of hydrogen peroxide reaction with hydroxonitrilotri(methylenephosphonato)iron(III) complex

The decomposition of hydrogen peroxide in the presence of hydroxonitrilotri(methylenephosphonato)iron(III), [Fe(NTMP)(OH)^4–], was studied in nitrate media (=0.10–0.26 M) over the 0.2–0.5 mM concentration range for the iron complex and the temperature range 26–40°C. The rate law;

Mechanistic aspects of ligand substitution incis-diaquabis(bipyridine)ruthenium(II) ion by acetyl acetone

The effects of pH, temperature, acetyl acetone (acacH) concentration and substrate complex concentration on the rate of aqua ligand substitution in the title complex in aqueous medium have been studied. The following rate expression is proposed for the 5.0–6.5 pH range.

Kinetics and mechanism of osmium(VIII)-catalyzed oxidation of hypophosphite by hexacyanoferrate(III) in aqueous alkali

The kinetics of osmium(VIII)-catalyzed oxidation of hypophosphite with hexacyanoferrate(III) in alkaline medium has been studied. The rate is independent of the concentration of the oxidant. The order with respect to hydroxide ion is variable. Rate law (1) conforms with the experimental observations.

Kinetics and mechanism of oxidation of the chromium(III)-DL-aspartic acid complex/periodate reaction. Evidence for iron(II) catalysis

The kinetics of oxidation of the chromium(III)-DL- aspartic acid complex, [CrIIIHL]+ by periodate have been investigated in aqueous medium. In the presence of Fe^II as a catalyst, the following rate law is obeyed:

Methionine anation of aquachromium(III)

The kinetics of anation of chromium(III) species, [Cr(H₂O)₆]³⁺ and [Cr(H₂O)₅OH]²⁺, by DL-methionine have been studied spectrophotometrically. Effects of varying [methionine]_T, [H⁺], and temperature were investigated. The results are in accord with a mechanism involving a fast 11 outer-sphere association between chromium(III) species and amino acid zwitterion, followed by transformation of the outer-into inner-sphere complex by slow interchange. The rate law consistent with the mechanism is as follows:

The Decay of Methylene Blue in Alkaline Solution

The decomposition of methylene blue in aqueous alkaline solution is described. The rate equation is of the form: , where k = 9.0 × 10^-4 mol^- [dm³s^-1 at 20°C and] = 0.5 mol dm^-3.     

Anwendung der rotierenden Scheiben-Ring-Elektrode zur Untersuchung der Reduktion von Permanganat in alkalischen L?sungen

Zusammenfassung Permanganat wird in Natriumhydroxidlösungen an der rotierenden Scheibenelektrode polarographisch reversibel zu Manganat(VI) und zu Manganat(V) reduziert. Aus der Abhängigkeit der Halbwellenpotentiale der Manganat(VI)-Manganat(V)-Welle von der Hydroxylionenaktivität wurden die Hydrolysekonstante des Manganats(V) und das Normalpotential mV bestimmt.Die irreversible Reduktion von Manganat(V) zu Oxid verläuft über ein Zwischenprodukt, das elektrochemisch wieder oxydiert werden kann. Das Zwischenprodukt, wahrscheinlich hydrolysiertes, monomeres Manganat(IV), reagiert in der Lösung zu nicht mehr oxydierbaren Produkten weiter.Geschwindigkeitsbestimmend ist eine homogene Reaktion 2. Ordnung, also die Dimersierung des Manganats(IV). Die Geschwindigkeitskonstante der Dimerisierung in 5 m Natronlauge wurde zu k₂=2 · 10⁵ Liter · Mol^–1 · sec^–1 abgeschätzt.

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Summary The reduction of permanganate to manganate(VI) and manganate(V) at the rotating disc electrode is polarographically reversible. The half-wave potentials of the manganate(VI)-manganate(V) wave depend on the hydroxyl ion activity of the solution due to the hydrolysis of manganate(V). The hydrolysis constant and the standard potential were obtained from the measurements.During the irreversible reduction of manganate(V) an intermediate is formed, probably being a hydrolysed monomer of manganate(IV). The intermediate can be reoxidized at the ring electrode. It disappears by polymerisation and precipitation as an oxide, the rate determining step being a homogeneous reaction of the second order. The rate constant of that dimerisation was estimated to be k ₂=2×10⁵ liter × mole^–1 × sec^–1.

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Herrn Prof. Dr. M. von Stackelberg zum 70. Geburtstag gewidmet.

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Der Deutschen Forschungsgemeinschaft danken wir für die Unterstützung dieser Arbeit.     

Die Bewegung eines Körpers in einem ringförmigen Potentialfeld

Zusammenfassung Es wird das quantenmechanische Problem eines Teilchens in einem ringförmigen Potential der Art gelöst.

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The motion of a body in a ring-shaped potential

The quantum mechanical problem of a particle in the torus shaped potential is solved.

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Résumé Solution du problème quantique de la particule dans un potentiel toroïdal: .

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Dem Andenken an meinen Freund Karl Heinz Hansen gewidmet.     

Radiolysis of p-benzoquinone solutions

The products of the continuous radiolysis of p-benzoquinone (Q) at different concentrations of H₂SO₄, Q and Cl^– are p-hydroquinone (H₂Q) and 2-hydroxy-p-benzoquinone (2-Q-OH). In the presence of some alcohols, a carbonyl compound is produced in addition to H₂Q and 2-Q-OH. The dependence of G values of the products on these factors is described. The material balance between G(-Q) and G(H₂Q)+G(2-Q-OH) is maintained. The experimental results indicate the occurrence of the following reaction: . By competition studies, it was possible to evaluate the rate coefficients for the following reactions: .     

Oxidation of chromium(III) by alkaline hexacyanoferrate(III)

Alkaline hexacyanoferrate(III) oxidation of freshly prepared solutions of Cr^III (pH>12) at 27°C follows the rate law, Equation 1:

Kinetics and mechanism of the oxidation of formic acid by thallium(III). Reinvestigation of hydrogen ion dependence

The rate of the oxidation of formic acid by thallium(III) in (Li, H)ClO₄ solutions is not affected by variation in hydrogen ion concentration and the experimental rate law, $$\frac{{ - d\left[ {T\left( {III} \right)} \right]}}{{d t}} = \frac{{k_1 K\left[ {T\left( {III} \right)} \right]\left[ {HCOOCH} \right]}}{{1 + K\left[ {HCOOH} \right]}}$$ is consistent with the mechanism which requires the formation of intermediate complex [HCOOHTl]³⁺ in a rapid preequilibrium followed by its slow decomposition to yield the final products. At 75°,k ₁ andK have the values of 16±1×10^?5 sec^?1 and 7.3±0.5M ^?1 resp.     

Studies on the Kinetics of the First Order Autocatalytic Decomposition Reaction of Highly Nitrated Nitrocellulose

The kinetics of the first order autocatalytic decomposition reaction of highly nitrated nitrocellulose (HNNC, 14.14%N) was studied by using thermogravimetry (TG). The results show that the TG curve for the initial 50% of mass-loss of HNNC can be described by the first order autocatalytic equation