Effect of specific adsorbed anions on the electrode kinetics of the V(III)/V(II) and Eu(III)/Eu(II) couples

Electrochemical kinetic parameters of the V(III)/V(II) and Eu(III)/Eu(II) couples in sulfuric, perchloric, hydrochloric, and hydrobromic acids were measured by potentiostatic and double pulse galvanostatic methods. The ₂ potentials in these solutions were calculated from electrocapillary measurements and the effect of the ₂ potentials on the electrode kinetics was discussed. The kinetic data after the Frumkin correction was applied show a very good agreement in H₂SO₄, HClO₄, and HCl solutions, if we assume that the non-complexed ion, which is partially supplied by the dissociation of complex ions, participates in the electrode reaction. The corrected rate constants in the bromide solution were about ten times larger than those to be expected from the ₂ potentials in the case of the V(III)/V(II) couple and a small acceleration effect was observed for the Eu(III)/Eu(II) couple. The greater reaction rate in the bromide solution is explained by the bridging effect.     

Polarographic study of Eu(III)-succinate-ethylenediamine and Eu(III)-malonate-ethylenediamine mixed systems

The mixed complexes of Eu(III) with succinate (succ^2?) and malonate (mal^2?) and ethylenediamine (en) have been studied polarographically at 25°C and at constant ionic strength, μ = 0.1 (NaNO₃) and pH 6. The reduction of the complexes in each case is quasi-reversible and diffusion-controlled. In each system three mixed complexes are formed, viz. [Eu(succ)(en)]⁺, [Eu(succ)(en)2]⁺ and [Eu(succ)₂(en)]^? with stability constants log β₁₁ = 9.2, log β₁₂ = 17.5 and log β₂₁ = 11.7; and [Eu(mal)(en)]⁺, [Eu(mal)₂(en)₂]^? and [Eu(mal)₃(en)]^3? with stability constants log β₁₁ = 11.4, log β₂₂ = 19.08 and log β₃₁ = 13.5 respectively.     

Discrete Rh(III)/Fe(II) and Rh(III)/Fe(II)/Co(III) cyanide-bridged mixed valence compounds

The heterotrinuclear complexes trans- and cis-[{cis-VI-L(15)Rh(III)(μ-NC)}{trans-III-L(14S)Co(III)(μ-NC)}Fe(II)(CN)(4)](2+) are unprecedented examples of mixed valence complexes based on ferrocyanide bearing three different metal centers. These complexes have been assembled in a stepwise manner from their {trans-III-L(14S)Co(III)}, {cis-VI-L(15)Rh(III)}, and {Fe(II)(CN)(6)} building blocks. The preparative procedure follows that found for other known discrete assemblies of mixed valence dinuclear Cr(III)/Fe(II) and polynuclear Co(III)/Fe(II) complexes of the same family. A simple slow substitution process of [Fe(II)(CN)(6)](4-) on inert cis-VI-[Rh(III)L(15)(OH)](2+) leads to the preparation of the new dinuclear mixed valence complex [{cis-VI-L(15)Rh(III)(μ-NC)}Fe(II)(CN)(5)](-) with a redox reactivity that parallels that found for dinuclear complexes from the same family. The combination of this dinuclear precursor with mononuclear trans-III-[Co(III)L(14S)Cl](2+) enables a redox-assisted substitution on the transient {L(14S)Co(II)} unit to form [{cis-VI-L(15)Rh(III)(μ-NC)}{trans-III-L(14S)Co(III)(μ-NC)}Fe(II)(CN)(4)](2+). The structure of the final cis-[{cis-VI-L(15)Rh(III)(μ-NC)}{trans-III-L(14S)Co(III)(μ-NC)}Fe(II)(CN)(4)](2+) complex has been established via X-ray diffraction and fully agrees with its solution spectroscopy and electrochemistry data. The new species [{cis-VI-L(15)Rh(III)(μ-NC)}{trans-III-L(14S)Co(III)(μ-NC)}Fe(II)(CN)(4)](2+) and [{cis-VI-L(15)Rh(III)(μ-NC)}Fe(II)(CN)(5)](-) show the expected electronic spectra and electrochemical features typical of Class II mixed valence complexes. Interestingly, in the trinuclear complex, these features appear to be a simple addition of those for the Rh(III)/Fe(II) and Co(III)/Fe(II) moieties, despite the vast differences existent in the electronic spectra and electrochemical properties of the two isolated units.     

Solvent effects on the electrode kinetics of simple redox couples: Investigations on the electrochemical behaviour of the V(III)/V(II) system in water + acetonitrile mixtures

Parallel optical and electrochemical studies on the V(III)/V(II) system in H₂O + acetonitrile (AN) + CF₃SO₃H mixtures have been performed. It was found, on the basis of the spectra of vanadium ions in the visible range, that V(III) was totally hydrated in mixtures up to x_AN ⋍ 0.6 while V(II) was specifically solvated by AN molecules, even at a molar fraction of acetonitrile in H₂O + AN mixtures as low as 0.02. In agreement with this, the formal potentials of the V(III)/V(II) system expressed versus the ferrocene electrode move to less negative potentials with an increase in AN concentration.Straightforward correlations of the electrode kinetics of the V(III)/V(II) system at a mercury electrode in H₂O + AN mixtures with both the electrode surface coverage by AN molecules and the resolvation of vanadium ions in the bulk solution were found.     

铂电极上醋酸-醋酐溶液中Mn(III)/Mn(II)电对研究

平衡电极电势实验确定了25 ℃, 1.5 mol•L－1醋酸钾＋醋酸-醋酐(3:1体积比)溶液中Mn(III)/Mn(II)的条件电极电势为0.719 V（vs SCE）;采用电势扫描和旋转圆盘电极技术研究了醋酸-醋酐溶液中铂电极上Mn(III)/Mn(II)电对的阳极氧化动力学. 结果表明:Mn(II)阳极氧化成Mn(III)的电极反应控制步骤属电荷传递过程, 阳极传递系数β=0.347,交换电流密度i0=5.84×10－6 A•cm－2,阳极标准反应速率常数ka=1.35×10－8 m•s－1, Mn(II)和OAc－的反应级数均为一级.     

The influence of triplet energy levels of bridging ligands on energy transfer processes in Ir(III)/Eu(III) dyads

A series of N^N,O^O-bridging ligands based on substituted 1-(pyridin-2-yl)-3-methyl-5-pyrazolone and their corresponding heteroleptic iridium(III) complexes as well as Ir-Eu bimetallic complexes were synthesized and fully characterized. The influence of the triplet energy levels of the bridging ligands on the energy transfer (ET) process from the Ir(III) complexes to Eu(III) ions in solution was investigated at 77 K in Ir(III)/Eu(III) dyads. Photophysical experiment results show the bridging ligands play an important role in the ET process. Only when the triplet energy level of the bridging ligand was lower than the triplet metal-to-ligand charge transfer ((3)MLCT) energy level of the Ir moiety, was pure emission from the Eu(III) ion observed, implying complete ET took place from the Ir moiety to the Eu(III) ion.     

A fluorescence study of tetraphenylporphyrinatozinc(II)/imidazolyl-linked porphyrinatoiron(III) systems

The fluorescence spectra of porphyrinatozinc(II)/iron(III) systems which consisted of tetraphenylporphyrinatozinc(II) and three kinds of imidazolyl-linked porphyrinatoiron(III) have been studied. An efficient fluorescence quenching of tetraphenylporphyrinatozinc(II) in the system was observed. Addition of a stronger organic base, such as piperdine, to the system can displace imidazolyl-linked porphyrinatoiron(III) and the fluorescence of the system restored partly. All these indicate the formation of porphyrinatozinc(II)/iron(III) supramolecular complex and coordination bonding formed by the coordination of imidazolyl group in imidazolyl-linked porphyrinatoiron(III) to Zn(II) in tetraphenyl-porphyrinatozinc(II) is the driving force of the supramolecular self-assembly. The association constants of the supramolecular complexes were calculated from the fluorescence spectroscopic titration data, and the differences among the association constants of the supramolecular complexes are discussed on the basis of the conformations which are dependent on the length of alkoxy chain linking imidazolyl group to porphyrinatoiron(III).     

Unusual multi-step sequential Au(III)/Au(II) processes of gold(III) quinoxalinoporphyrins in acidic non-aqueous media

The electrochemistry of gold(III) mono- and bis-quinoxalinoporphyrins was examined in CH(2)Cl(2) or PhCN containing 0.1 M tetra-n-butylammonium perchlorate (TBAP) before and after the addition of trifluoroacetic acid to solution. The investigated porphyrins are represented as Au(PQ)PF(6) and Au(QPQ)PF(6), where P is the dianion of the 5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)porphyrin and Q is a quinoxaline group fused to a β,β'-pyrrolic position of the porphyrin macrocycle; in Au(QPQ)PF(6) there is a linear arrangement where the quinoxalines are fused to pyrrolic positions that are opposite each other. The porphyrin without the fused quinoxaline groups, Au(P)PF(6), was also investigated under the same solution conditions. In the absence of acid, all three gold(III) porphyrins undergo a single reversible Au(III)/Au(II) process leading to the formation of a Au(II) porphyrin which can be further reduced at more negative potentials to give stepwise the Au(II) porphyrin π-anion radical and dianion, respectively. However, in the presence of acid, the initial Au(III)/Au(II) processes of Au(PQ)PF(6) and Au(QPQ)PF(6) are followed by an internal electron transfer and protonation to regenerate new Au(III) porphyrins assigned as Au(III)(PQH)(+) and Au(III)(QPQH)(+). Both protonated gold(III) quinoxalinoporphyrins then undergo a second Au(III)/Au(II) process at more negative potentials. The electrogenerated monoprotonated monoquinoxalinoporphyrin, Au(II)(PQH), is then further reduced to its π-anion radical and dianion forms, but this is not the case for the monoprotonated bis-quinoxalinoporphyrin, Au(II)(QPQH), which accepts a second proton and is rapidly converted to Au(III)(HQPQH)(+) before undergoing a third Au(III)/Au(II) process to produce Au(II)(HQPQH) as a final product. Thus, Au(P)PF(6) undergoes one metal-centered reduction while Au(PQ)PF(6) and Au(QPQ)PF(6) exhibit two and three Au(III)/Au(II) processes, respectively. These unusual multistep sequential Au(III)/Au(II) processes were monitored by thin-layer spectroelectrochemistry and a reduction/oxidation mechanism for Au(PQ)PF(6) and Au(QPQ)PF(6) in acidic media is proposed.     

Mittels der Ston-Flow-Methode mit der Quecksilbertropfelektrode untersuchte Reaktionen Fe(III)+V(III)=V(IV)+ Fe(II) und V(II) +V(IV)=2V(III)

Ohne Zusammenfassung     

Electrode processes in the course of Cr(III) and Cr(II) reduction/oxidation in KCl melt

A hypothesis about formation of a polynuclear chromium complex is made on the basis of a voltammetric study of the processes of trivalent and divalent chromium reduction within complex chloride ions in a potassium chloride melt. The effect of the reaction of Cr₂Cl ₇ ^3? formation on deviation of theoretical dependences from the experimentally obtained dependences under the terms of linear voltammetry is shown. Models are suggested for the complex chromium ions, quantum-chemical calculations of the bond lengths in them are performed and steric energies of ions are determined. Diffusion coefficients of Cr(III) and Cr(II) are calculated, diffusion activation energies are determined.     

Determination of oxygen stoichiometry in mixed Mn(III)/Cr(III)-oxides

Summary The method and experiences with the determination of oxygen Stoichiometry in mixed manganesechromium sesquioxides are described. The decomposition is carried out in sealed glass tubes in hydrochloric acid in presence of a ferro-ferric system. The oxydation state of the analysed materials is determined by titration of Fe²⁺ ions with a solution of cerium salt, ferroin being used as indicator.

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Bestimmung der Sauerstoff-Stöchiometrie in Mn(III)/Cr(III)-Mischoxiden

Zusammenfassung Es werden ein Verfahren sowie Erfahrungen mit der Bestimmung des Sauerstoffüberschusses in Mangan(III)/Chrom(III)-Mischoxiden beschrieben. Die Proben werden in zugeschmolzenen Ampullen mit SalzsÄure in Gegenwart von Eisen(II/III)-ionen aufgelöst. Sauerstoffüberschu\ wird durch Titration von Fe(II) mit Cer(IV)-salz in Gegenwart von Ferroin als Indicator bestimmt.

     

First-principles study of the separation of Am(III)/Cm(III) from Eu(III) with Cyanex301

The experimentally observed extraction complexes of trivalent lanthanide Eu(III) and actinide Am(III)/Cm(III) cations with purified Cyanex301 [bis(2,4,4-trimethylpentyl)dithiophosphinic acid, HBTMPDTP denoted as HL], i.e., ML(3) (M = Eu, Am, Cm) as well as the postulated complexes HAmL(4) and HEuL(4)(H(2)O) have been studied by using energy-consistent 4f- and 5f-in-core pseudopotentials for trivalent f elements, combined with density functional theory and second-order M?ller-Plesset perturbation theory. Special attention was paid to explaining the high selectivity of Cyanex301 for Am(III)/Cm(III) over Eu(III). It is shown that the neutral complexes ML(3), where L acts as a bidentate ligand and the metal cation is coordinated by six S atoms, are most likely the most stable extraction complexes. The calculated metal-sulfur bond distances for ML(3) do reflect the cation employed; i.e., the larger the cation, the longer the metal-sulfur bond distances. The calculated M-S and M-P bond lengths agree very well with the available experimental data. The obtained changes of the Gibbs free energies in the extraction reactions M(3+) + 3HL → ML(3) + 3H(+) agree with the thermodynamical priority for Am(3+) and Cm(3+). Moreover, the ionic metal-ligand dissociation energies of the extraction complexes ML(3) show that, although EuL(3) is the most stable complex in the gas phase, it is the least stable in aqueous solution.     

Electrode processes and their kinetic parameters in the reduction and oxidation of Cr(III) and Cr(II) in molten CsCl

The reduction of chromium ions in the CsCl-CrCl₃ melt in wide concentration and temperature ranges is reported. It is assumed that the melt contains polynuclear chromium complexes. The reduction of Cr(III) to Cr(II) is a reversible one-electron process. The electroreduction of divalent chromium to chromium metal is an irreversible process involving dinuclear and mononuclear chromium complex ions. The electron transfer rate constant has been calculated for various temperatures and chromium chloride concentrations in the salt melt. The activation energy of electron transfer and its dependence on the CrCl₃ concentration in the electrolyte have been determined for the Cr(III) ↔ Cr(II) process.     

Formation of aquatic Th(IV) colloids and stabilization by interaction with Cm(III)/Eu(III)

The present investigation is to ascertain under what conditions actinide ions undergo aggregation via oxo-bridging to form stable colloidal species. Eu and Th are taken for this purpose as trivalent and tetravalent actinide homologue ions, respectively. For verification of the effects of impurities in chemicals on the actinide colloid generation, pH is adjusted either by a conventional acid-base titration or by coulometry without addition of NaOH. The colloid generation is monitored by highly sensitive laser-induced breakdown detection in varying pH from 3 to 7, first in dilute Eu and Th solutions separately and then in a mixture of both, all in 0.5 M HCl/NaCl. The formation of stable colloids is observed particularly in a mixed solution of Eu and Th, suggesting that aggregation via mutual oxo-bridging of trivalent and tetravalent metal ions results in surface polarization, leading to stable hydrophilic particles of 20-30 nm in diameter. When Eu is replaced by Cm in the mixed solution in favor of the high fluorescence intensity of the latter, the chemical speciation is determined on colloid-borne Cm by time-resolved laser fluorescence spectroscopy. Two different colloid-borne Cm species, oxo-bridged with Th, are identified: a minor amount at 598.0 nm (denoted as Cm-Th(1)) and a major amount at 604.8 nm (Cm-Th(2)). The former is found as a transitional state, which converts to the latter with increasing pH and prevails at pH > 5.5. Both colloid-borne species (Cm-Th) are distinctively different from hydrolyzed Cm or its carbonate complexes with respect to their fluorescence peak positions and lifetimes. In conclusion, a mixed oxo-bridging of trivalent and tetravalent actinides elicits the generation of stable colloids, whereas individual ions in their pure state form colloids under oversaturation at near neutral pH only as a transitional state for precipitation.     

Determination of stability constants of copper(II) complex of glycine in water + alcohol mixed solvents with ion selective electrode technique

The first stability constants (log beta(1)) of the copper(II) complex of glycine in water and in 13 water + alcohol (isopropanol, tert-butanol, 1,2-propylene glycol and glycerol) solvents have been determined at 25 degrees C and an ionic strength of 0.10, from pH and pCu measurements of cells containing copper(II) ion selective electrode. It has been shown that as the proportion of the alcohol increases, the stability constants become increasing positive in all of the mixed solvents examined. An almost linear relation between log beta(1) and the mole fraction of alcohol was found for the complex in aqueous solutions of isopropanol, tert-butanol and glycerol. The response of the copper(II) ion selective electrode in water and in water + alcohol mixed solvents was also investigated. The advantages of using an ion selective electrode to determine the stability constants in mixed solvents are discussed.