Spectrophotometric Study of Catechol Oxidation by Aerial O2 in Alkaline Aqueous Solutions Containing Mg(II) Ions.

Electronic absorption spectroscopy was employed to study the aerial oxidation of catechol (1,2-benzenediol) in alkaline aqueous solution containing an excess of Mg(II) ions. Graphical analysis by the matrix method of UV spectra recorded at regular time intervals gave a good fit for two absorbing species in solution. Based on this result and our earlier ESR spectroscopic investigations we concluded that two main absorbing species in this system are Mg(II)-spin stabilized o-benzosemiquinone anion radical and C-C dimer formed by the nucleophilic attack of catecholate anion on o-benzoquinone. Although the formation of 1,2,4-benzenetriol during the catechol oxidation has been detected in some ESR studies its presence was not indicated by this analysis probably because of the low and/or stable steady state concentration throughout the experiment.     

Vibrational Structure of the B—X System of Isotopic Ago Molecules

Spectra of ¹⁰⁷Ag¹⁸O and ¹⁰⁷Ag¹⁶O molecules have been obtained in a low-pressure arc in oxygen atmosphere, and recorded with medium dispersion. Vibrational assignments for the bands of B ²π —X²π system were verified by the study of the oxygen isotope effect, and the vibrational constants were obtained for the states involved in transitions.     

Matrix Lax Polynomials, Geometry of Prym Varieties and Systems of Hess–Appel’rot Type

We consider a four-dimensional generalization of Hess–Appel’rot system and costruct its Lax pair. Both classical and algebro-geometric integration procedure are proceeded. The algebro-geometric integration is based on deep facts from geometry of Prym varieties such as the Mumford relation and Mumford-Dalalyan theory. The integration is similar to the integration of Lagrange bitop which has recetly been performed by the authors.     

Three Electrons in a Two-Dimensional Parabolic Trap: The Relative Motion Solution

In agreement with the Kohn theorem the relative motion (rel) of three electrons in a two-dimensional parabolic trap separates from the centre-of-mass (CM) motion. By introducing new coordinates the Hamiltonian for relative motion in the approximation of non-interacting electrons can be taken to the normal form. The eigenstates of the normalized Hamiltonian are products of the Fock-Darwin states for normal modes. The energy levels for relative motion are obtained by diagonalizing the exact Hamiltonian in the eigenbasis for the non-interacting case. In this basis the interaction matrix elements can be obtained in the analytical form. Since the rank of the Hamiltonian matrix is significantly reduced, the calculations are faster and more accurate than those for the full (CM + rel) motion. This advantage is especially important for the calculations of excited states and the analysis of energy spectra.     

Effect of atmospheric pressure pulsed discharge spatial inhomogeneity on Ar I and H I lines: Electron number density study

The spatial inhomogeneity of pulsed atmospheric pressure discharge in argon is investigated using the electron number density N_e diagnostics procedure applied to asymmetrically broadened Ar I lines. A dedicated fitting procedure is used for describing Ar I 703.0 nm line shape recorded from argon gas discharge and H I (at 486.13 and 656.28 nm) lines recorded from Ar-H₂ gas mixture discharge. The results revealed the change in N_e in both axial and radial directions. The additional Ar I lines at 614.5, 710.7, 731.2, and 731.6 nm, recorded from integral spatial radiation, are analysed as well to confirm the results from the plasma column region. The possibility of using AlO (B²∑⁺–X²∑⁺) and CN (B²∑⁺–X²∑⁺) molecular bands for gas temperature T_g measurements in this type of gas discharge source is demonstrated and T_g used as an input parameter for the N_e diagnostics procedure. For the proper identification of molecular band spectral lines, the Fortrat parabolas are constructed. The results obtained from Ar I 703.0 nm line indicate three different N_e values, with N_e1 ≈ 0.6 × 10¹⁶ cm⁻³, N_e2 ≈ 3.6 × 10¹⁶ cm⁻³, and N_e3 ≈ 19 × 10¹⁶ cm⁻³ measured from the plasma column. These N_e values increase in the cathode and anode region.     

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Excitation of adsorbed molecule vibrations in low energy electron scattering

We develop a theory of low energy electron loss spectroscopy of vibrational modes of molecules adsorbed on metal surfaces. Differential and total cross sections are calculated in the Distorted Wave Born Approximation, assuming i) strong elastic scattering on the metal surface, ii) direct electron-molecule interaction via the electric dipole field associated with the molecular vibration. The angular distributions are calculated and discussed for molecules adsorbed at various distances above the metal surface and for several electron energies and impact angles. The influence of electronic screening of dipolar oscillations is discussed and the consequences of the classical induced image dipoles are explored. It is shown that the metal surface selection rule known in IR spectroscopy is only approximately valid in electron scattering. Finally, we give numerical estimates of the inelastic scattering cross sections for the stretching vibrations of CO molecule adsorbed on transition metal surfaces, in reasonable agreement with experiments.     

The effect of ligand field on the excitation luminescence spectra of some complex compounds of manganese (II)

The excitation and emission luminescence spectra of the complex compounds of manganese (II) chloride with the hydrochlorides of pyridine, 2-methyl- and 2-ethylpiperidine have been studied. It has been established that the crystals of these complex compounds appear in tetrahedral and octahedral configurations. The excitation spectra in both configurations contain bands originating from the⁴G,⁴P,⁴D and⁴F terms, the position of which is determined by configuration. From the excitation spectra the Racah parametersB andC and the ligand field strength parameter 10Dq have been determined.The emission luminescence spectra also depend on configuration of the complex compound. The character of these spectra is expressed in terms of the following characteristic parameters: the position of the maximum of the functionG(v), the half-width of the emission luminescence band, and the constants andm. From the excitation and emission luminescence spectra it has been established that the emission in both configurations is due to the⁴T₁(G)⁶A₁ transition.     

Coagulation of silver halide sols by thorium nitrate in the presence of potassium nitrate and potassium sulfate

Summary When silver iodide, silver bromide and silver chloride solsin statu nascendi are coagulated by thorium nitrate in the presence of potassium nitrate, three coagulation maxima appear. Two of them are identical with maxima that are found in absence of KNO₃, denoted with (II) and (IV) in fig. 1. The new maximum appears in the stability region of recharged sols (III). It is believed that this maximum is also—as maximum (IV)—caused by the coagulation of recharged silver halide sols by nitrate ions. Appearance of two nitrate coagulation maxima is explained by different charge densities on sol particles at various concentrations of Th(NO₃)₄ where they are formed. The new maximum indicates a lower charge density of sol particles. The possibility that the new maximum could have been caused by ionic complex species between thorium and nitrate ions has been rejected for data are available that the equilibrium constant for such complexes is small. In the presence of K₂SO₄ the coagulation effects of thorium nitrate on silver halide sols are markedly different. In acidified solutions only one coagulation maximum appears at rather high thorium nitrate concentrations [∼ 10⁻³ N Th (NO₃)₄] and the sol remains negatively charged [up to ∼ 10⁻² N Th (NO₃)₄] This is explained by complex formation of Th-ions and sulfate ions whereby ionic species of lower charge are formed, which exert a weaker coagulation effect. In neutral solutions another maximum at lower concentration of Th (NO₃)₄ is formed which appears to be the usual coagulation maximum produced by hydrolyzed thorium ions. The antagonistic effects of the salt pair Th (NO₃)₄-K₂SO₄ upon the coagulation of silver halides has been discussed and we have concluded that the large effects repeatedly reported can be explained not by simple electrostatic effects of ions in solution but rather by the formation of complexes between Th- and SO₄-ions.

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Zusammenfassung Die Koagulationseffekte des Thoriumnitrats in Anwesenheit von Kaliumnitrat und Kaliumsulfat an Silberhalogenid-Solenin statu nascendi wurden ausführlich untersucht. Wenn Silberhalogenid-Sole durch Thoriumnitrat-L?sungen koaguliert werden, bilden sich zwei Koagulationsmaxima (II und IV, Abb. 1). Bei sehr niedrigen Konzentrationen des Thoriumnitrats koaguliert das Thorium-Ion (oder Komplex) die negativen Silberhalogenid-Sole, w?hrend bei h?heren Thoriumnitrat-Konzentrationen die ungeladenen Sole durch die NitratIonen koaguliert werden. Zwischen den zwei Maxima besteht ein weites Gebiet der stabilen umgeladenen Sole (III). Unter dem Zusatz von konstanten Mengen des Kaliumnitrats wird in diesem Gebiet ein neues (drittes) Maximum gebildet (Abb. 2–5), das auch als Koagulationsmaximum identifiziert wurde. Es wird angenommen, da? dieses Maximum wieder eine Koagulation der umgeladenen Silberhalogenid-Sole durch Nitrat-Ionen darstellt. Das Auftreten von zwei Koagulationsmaxima, verursacht durch Nitrat-Ionen, wird durch die verschiedenen Ladungsdichten an Solteilchen in Gebieten der Thoriumnitrat-Konzentrationen, in denen Maxima erscheinen, erkl?rt. Die M?glichkeit eines Koagulationseffektes der komplexen Ionen zwischen Thorium und Nitrat wurde ausgeschlossen, da die Gleichgewichtskonstante solcher Komplexe ziemlich niedrig ist. In Anwesenheit von Kaliumsulfat sieht die Koagulationskurve für Silberhalogenid Sole sehr unterschiedlich aus (Abb. 6–8). In den mit Salpeters?ure (0,001N) versetzten Solen erscheint nur ein Maximum bei ziemlich hohen Thoriumnitrat-Konzentrationen [∼ 10⁻³ N Th (NO₃)₄], wobei die Solteilchen noch immer negativ sind. Da Thorium- und Sulfat-Ionen sehr stabile Ionen-Komplexe bilden, die eine niedrigere Valenz aufweisen, kann das Maximum als Folge der Koagulationseffekte solcher Komplexe an die Silberhalogenid-Sole angesehen werden. In neutralen L?sungen zeigt sich neben dem beschriebenen Maximum noch ein anderes Maximum bei niedrigerer Thoriumnitrat-Konzentration. Dieses Maximum, hervorgerufen durch die hydrolysierten Thorium-Ionen, scheint das „normale“ Koagulationsmaximum zu sein. Dieantagonistischen Effekte des Salzpaares Th (NO₃)₄-K₂SO₄ bei der Koagulation der Silberhalogenide wurden diskutiert, und es wurde geschlossen, da? die gro?en Effekte, die wiederholt ver?ffentlicht worden waren, sehr schwer nur durch die elektrostatischen Anziehungen zwischen den Ionen erkl?rt werden k?nnen. Die Komplexbildung zwischen Thorium- und Sulfat-Ionen wird für den sogenannten antagonistischen Effekt in diesem Falle als verantwortlich angesehen.

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Supported in part by U.S. Atomic Energy Commission Contract No. AT (30-1)-1801.