Electron-stimulated desorption from ionic crystal surfaces

Inelastic interactions of electrons with surfaces of ionic crystals result in emission of various particles such as ions, atoms and molecules. We will review such electron-stimulated desorption processes for the particular class of ionic crystals, namely for alkali halides. In this case, a dominant fraction of the emission is in the form of halogen and alkali atoms characterized by a thermal (Maxwellian) spectrum of translational energies. For several alkali halides (potassium and rubidium chlorides, bromides, and iodides), however, a significant part of the halogen atoms is ejected with nonthermal energies, i.e. energies of the order of 0.1 eV. The results of recent systematic studies of angular-resolved kinetic energy distributions of the emitted particles will be reported and current views on the electronic mechanisms of desorption will be described. In particular, it will be shown that the ESD mechanism can be understood in terms of the model involving a surface localisation of the so called “hot-holes” created by electron bombardment of alkali halides. A role of hot holes in ESD processes will further be discussed in relation to very recent experimental results obtained for the KBr crystals doped with In impurities which act as efficient hole traps.     

Microsolvation of the [Ni(acac)(tmen)]+ complex

Microsolvation of the [Ni(acac)(tmen)]⁺ complex by a series of aliphatic n-alcohols (Solv) has been studied in ClCH₂CH₂Cl solutions by spectrophotometry. Based on the changes in the electronic spectrum of the afore-mentioned complex, observed under the influence of any alcohol, the equilibrium constants for the formation of the [Ni(acac)(tmen)Solv]⁺ and [Ni(acac)(tmen)Solv₂]⁺ species have been computed according to the algorithm presented in this work. It was found that, in all the systems studied, the stability of five-coordinated [Ni(acac)(tmen)Solv]⁺ is higher than that of octahedral [Ni(acac)(tmen)Solv₂]⁺. The resulting values are discussed in terms of the Lewis basicity of alcohols.     

Determination of organic carbon in water with a silver-catalyzed peroxydisulfate wet chemical oxidation method

The application of Ag(I) catalysis of S₂O₈^2? to the oxidation of organic carbon to CO₂ for determination of dissolved organic carbon in aqueous samples is described. The resulting method combines to a significant degree the speed of high-temperature combustion methods and the sensitivity of wet chemical oxidation. For some samples, a higher oxidation efficiency has been observed than with an uncatalyzed wet chemical oxidation method.     

Formation of the radical-cation of monomer in the photoinduced polymerization of isobutylene in the presence of SnCl4

Spectra of isobutylene with SnCl₄ were studied at the temperature of 113°K in the dark and under illumination. Radical-cations of isobutylene are formed by irradiation of the isobutylene–SnCl₄ mixture in n-heptane substantially more slowly than in the isobutylene–TiCl₄ mixture. Polymerization of isobutylene occurs after increasing the temperature up to the melting point of this mixture. The yield of polymer depends on the duration of preirradiation, while the molecular weight of polyisobutylene (M _η) does not depend on the preirradiation of reaction mixture.     

Indirect electrochemical methods of nitration: Novel nitroacetamidation of dienes

Solutions of nitronium tetrafluoroborate in acetonitrile prepared by anodic oxidation of nitrogen dioxide, efficiently nitrate aromatics, enolsilyethers, alkenes and conjugated dienes to afford respectively nitroaromatics, α-nitroketones, vicinal nitroamides and mixtures of nitroacetamides by 1,2- and 1,4-addition.     

The synthesis of 3,6-diamino-2,3,4,6-tetradeoxy-dl-threo-hexopyranose derivatives,substrates for the synthesis of negamycin

Three synthetic routes to derivatives of 3,6 - diamino - 2,3,4,6 - tetradeoxy - DL - threo - hexopyranose were investigated. Addition of sodium azide in acetic acid to 6 - phthalimido - 5,6 - dihydro - 2 - pyrone gave 4-azido compound (7) of the erythro configuration. From methyl 2,4 - dideoxy - β -dl- erythro - hexopyranoside threo 4 - phthalimido - 6 - phthalimidomethyl - tetrahydro - 2 - pyrone (17) was obtained in three steps in low overall yield. Addition of sodium azide in acetic acid to butyl 6 - oxo - 2 - hydroxy - hex - 4 - enoate followed by methylation, amonolysis of the ester group, and reduction gave methyl 3,6 - diacetamido - 2,3,4,6 - tetradeoxy - α - DL - threo - hexopyranoside (26).     

Electrochemical studies of Tl(I) crown-ether complexes in nonaqueous media

Summary Complexation equilibria of the Tl(I) ion with 18-crown-6 and dibenzo-18-crown-6 were studied polarographically in 10 nonaqueous solvents. The stability of the complexes is strongly influenced by the nature of solvents and varies with their Lewis basicities. It has been found that the logK _s value (K _s is the stability constant of the complex) can be well described by empirical relation logK _s=a DN+b, whereDN stands for the Gutmann donor number anda andb mark the regression coefficient. Addition of the second explanatory parameter, the acceptor number, is not statistically significant. This result is in agreement with the predominant role of Tl(I) ion solvation.

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Elektrochemische Untersuchungen von Tl(I)-Kronenetherkomplexen in nichtwäßrigen Medien

Zusammenfassung Es wurden die Komplexierungsgleichgewichte des Tl(I)-Ions mit 18-Krone-6 und Dibenzo-18-krone-6 polarographisch in 10 nichtwäßrigen Lösungsmitteln untersucht. Die Stabilität der Komplexe wird sehr stark vom Solvens beeinflußt, wobei eine starke Abhängigkeit von der Lewis-Basizität beobachtet wird. Es wurde festgestellt, daß die logK _s-Werte (K _s ist die Komplexstabilitätskonstante) gut mit der empirischen Beziehung logK _s=a DN+b beschrieben werden können, wobeiDN die Gutmann'sche Donorzahl unda undb die Regressionskonstanten bedeuten. Hinzunahme der Akzeptorzahl als zweiten Parameter bleibt statistisch insignifikant. Dieses Ergebnis stimmt mit dem dominierenden Einfluß der Tl(I)-Ionensolvatation überein.

     

Nitrate ion association with Nd3+

The overall stability constantsK ₁ andK ₂ of NdNO ₃ ²⁺ and Nd(NO₃) ₂ ⁺ complexes were determined (K ₁=1.77;K ₂=1.28) using an extraction method with tri-n-butyl phosphate as the extractant. The ratio ₁/₂ of the stepwise stability constants is discussed. It was established that the Nd(NO₃) ₂ ⁺ complex was an outer-sphere ion pair.

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Die Assoziation von Nitrat-Ion mit Nd³⁺

Zusammenfassung Mittels einer Extraktionsmethode wurden die StabilitätskonstantenK ₁ undK ₂ von NdNO ₃ ²⁺ - und Nd(NO₃)⁺-Komplexen bestimmt (K ₁=1.77;K ₂=1.28; Tri-n-butylphosphat als Extraktionsmittel). Das Verhältnis ₁/₂ der stufenweisen Stabilitätskonstanten wird diskutiert. Es stellte sich heraus, daß der Nd(NO₃)⁺-Komplex als ein Outer-Shere-Ionenpaar vorliegt.

     

Retention of anions on silica-based metalloporphyrin stationary phases.

The silica-based Fe(III)-protoporphyrin and Zn-tetraphenylporphyrin stationary phases were examined for the HPLC separation of anions. The retention of nine common inorganic anions as well as benzoate anion (BA) and its hydroxy analogues (HBA) was examined using tartrate, acetate, and succinate eluents. The retention factors of inorganic anions on the FeProP stationary phase were in the order Cl- < NO3- < ClO4- < I- < SCN- and for organic anions benzoate < p-hydroxybenzoate < m-hydoxybenzoate < o-hydroxybenzoate. The retention factors of organic anions examined for a ZnTPP column were in the order p-HBA < m-HBA < BA < o-HBA.     

Positron annihilation and1H NMR study of [Zn(1-propyltetrzole)6](BF4)2 and [Fe(Methyltetrazole)6](BF4)2 complexes

The complexes [Zn(1-propyltetraole)₆](BF₄)₂ (Zn-ptz) and [Fe(methyltetrazole)₆](BF₄)₂ (Fe-mtz) were investigated by positron annihilation and solid-state NMR spectroscopy. For Zn-ptz signs of structural rearrangements were found between 70 and 145 K. For the spin-crossover complex Fe-mtz a transition affecting the high-spin stat Fe²⁺ ions at lattice site B occurs below 15 K.