Ligand exchange reactions of some Cr(III) complexes investigated by cyclic voltammetry

From cyclic linear sweep voltammograms of some Cr(III) complexes it is evident that after electron transfer ligand groups are expelled relatively slowly inDMSO and the tetra coordinated complex is formed. The rate constants could be determined in some cases by the methods of cyclic voltammetry. The following compounds were examined: [Cr(en)₃]³⁺, [Cr(acac)(en)₂]²⁺, [Cr(acac)₃]. [Cr(dien)₂]³⁺, [Cr(DMSO)₆]³⁺, [Cr(ur)₆]³⁺. For [Cr(en)₃]³⁺ the energy of activation could be determined as well.The dependence of the velocity of ligand elimination on complex structure is discussed.

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Untersuchung von Ligandenaustauschreaktionen einiger Cr(III)-Komplexe mittels cyclischer Voltammetrie

Zusammenfassung Bei der Reduktion einiger der folgenden Cr(III)-Komplexe inDMSO läßt sich auf Grund der Voltammogramme auf eine Ligandenabspaltung und Bildung der vierfach koordinierten Cr(II)-Komplexe schließen: [Cr(en)₃]³⁺, [Cr(acac)(en)₂]²⁺, [Cr(acac)₃], [Cr(dien)₂]³⁺, [Cr(DMSO)₆]³⁺, [Cr(ur)₆]³⁺. Für das [Cr(en)₃]³⁺ konnten Geschwindigkeitskonstante und Aktivierungsenergie dieser nachgelagerten Reaktion bestimmt werden.Der Einfluß der Struktur des Komplexes auf die Zerfallsgeschwindigkeit wird diskutiert.

     

Untersuchungen zur Kinetik der thermischen Dissoziation von Nickel-, Kupfer- und Zinksulfat

The rates of decomposition and the energies of activation were determined for the thermal dissociation of NiSO₄, CuSO₄, Cu₂(SO₄)O, ZnSO₄and Zn₃(SO₄)₂O. Linear, parabolic and logarithmic rate laws were found. Kinetics are largely determined by the rate of energy transfer. The reasons for the formation of basic sulfate intermediates are discussed.     

Study of coherent diffractive production reactions ofp+C→[Y 0 K +]+C type and observation of narrow structures in ∑ (1385)0 K + and ∑0 K + effective mass spectra

In the experiments at the SPHINX facility in 70 GeV proton beam of the IHEP accelerator the coherent diffractive production reactions on carbon nucleip+C [(1385)⁰ K ⁺+C andp+C[⁰ K ⁺]+C were investigated. The evidences for new baryon states were obtained in the study of hyperon-kaon effective mass spectra in these two reactions:X (2050) with massM=(2052±6) MeV and width =(35 _–35 ⁺²² ) MeV inM[(1385)⁰ K ⁺] andX(2000) withM=1999±6 MeV and =91±17 MeV inM[⁰ K ⁺]. The unusual features of these massive states (small enough decay widths, anomalously large branching ratios for decays with strange particles emission) make them very serious candidates for cryptoexotic pentaquark baryons with hidden strangeness.     

Classical fluids of negative heat capacity

It is shown that new parametersX can be defined such that the heat capacity C_xT(S/T)_x is negative, even when the canonical ensemble [i.e., at fixed T=(U/S)_Y and YX] is stable. This implies an extension of the classical theory of polytropes from ideal gases to general fluids. As examples of negative heat capacity systems we treat blackbody radiation and general gas systems with nonsingular _T. For the case of a simple ideal gas we even exhibit an apparatus which enforces a constraint X(p, V)=const that makes C_x<0. We then show that it is possible to infer the statistical mechanics of canonicallyunstable systems-for which even the traditional heat capacities are negative-by imposing constraints that stabilize the associated noncanonical ensembles. Two explicit models are discussed.     

Gravitational redshift and the equivalence principle

Two problems have long been confused with each other: the gravitational redshift as discussed by the equivalence principle; and the Doppler shift observed by a detector which moves with constant proper acceleration away from a stationary source. We here distinguish these two problems and give for the first time a solution of the former which is exact within the context of the equivalence principle in a sense discussed in the paper. The equivalence principle leads to transformations between flat spacetimes. These are analyzed, and a generalized Lorentz transformation is proposed which covers transformations from inertial to uniformly accelerated frames of reference.     

Observation of ω → π0μ+μ− decay

The results of studying the mass spectrum of μ⁺μ^?γγ systems produced in π^?p collisions at 25 and 33 GeV/c presented. The wide-aperture magnetic spectrometer with a hodoscope γ-detector was used to identify muon pairs and photons. There is a clear peak in the mass spectrum which corresponds to the decay ω → π⁰μ⁺μ^? previously not observed. The branching ratio for the decay is estimated to be 9 × 10^?5 with a systematic error of 50%.