Low-temperature ortho-para conversion of hydrogen on films of rare-earth metals and their copper alloys

Kinetic data for the ortho-para conversion of H₂ at 77 k rear earth metals (REM) and their Cu alloy films are given. Conversion on the surface of Sc, Y, La, Yb and Lu has been shown previously to follow a chemical mechanism, for the others it is magnetic. When alloyed with Cu, the specific catalytic activity (K_sp) of Sc, Y, La, Yb and Lu sharply increases. A sharp increase of K_sp is also observed on Cu alloys of Ce, Sm, Nd, Pr, Eu and Gd and the chemical conversion mechanism becomes predominant. On Tb, Dy, Er, Ho and Tm, K_sp rises only slightly and the magnetic mechanism preserves.

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- H₂ 77 P3M . , Sc, Y, La, Yb Lu , . Cu () Sc, Y, La, Yb, Lu, Ce, Sm, Nd, Pr, Eu Gd, . Ha Tb, Dy, Er, Ho Tm .

     

Isotope effects in the hydrogen exchange reaction

The PODSs of the H₃ system and its isotopic derivatives are used for computing exact adiabatic barriers. We find good agreement with experimentally measured ground and vibrationally excited activation energies. The theoretical results should stimulate further measurements of activation energies of vibrationally excited species.     

Isotope exchange of molecular nitrogen on barium nitride

The activity of barium nitride in the isotope exchange of nitrogen is 2–3 orders of magnitude higher than that of Fe and Ru. In the temperature range from 373 to 673 K the activation energy of exchange is 40 kJ/mol.

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2–3 Fe Ru. 373–673 40 /.

     

Oxidation by hydrogen in the chemistry and physics of the rare-earth metals

Rare-earth metals (RE) easily react with hydrogen. For decades the bonding of hydrogen has been discussed controversially in terms of either the "proton model" or the "anion model". Detailed investigations of metal-rich compounds of the rare-earth metals provide clear evidence for the incorporation of hydrogen as a hydride anion. Several categories of compounds can be distinguished regarding their behavior towards hydrogen. Low-valence compounds with metal-metal bonding frequently provide their excess electrons to form hydride ions as found with the halide hydrides REXH(n). However, there are exceptions, such as, LaI which does not react with hydrogen as a result of special electronic and electrostatic conditions. The opposite is true with La(2)C(3) although this compound does not provide excess metal valence electrons. An amorphous phase La(2)C(3)H(1.5) forms at very low temperature, around 450 K. The presence of hydrogen strongly influences the electrical and magnetic properties, for example, spin-glass formation and colossal magneto resistance arising in the presence of 4f(n) cores with the lanthanoid elements.     

Isotope effects upon hydrogen atom loss from molecular ions

The isotope effect (T_H/T_D) upon the kinetic energy release and the isotope effect (k_H/k_D) upon ion abundance for unimolecular H· loss from molecular ions has been determined for several compounds. It is suggested that the isotope effect upon abundance might provide a convenient method of estimating the relative life-time of ions which fragment in the metastable region for different instruments or different experimental conditions. The value of k_H/k_D varies from <2 to >1000 for different molecular ions and this variation is apparently largely due to the rate of increase of the reaction rate with internal energy in the threshold region. The magnitude of the isotope effect is thus related to the entropy of activation. The isotope effect upon energy release was found to be slightly less than unity in almost every case studied; this included both reactions in which the reverse activation energy is very small and those in which it is appreciable.     

Isotope effect on the location of variational transition states: The hydrogen exchange reaction

The microcanonical variational transition states of the isotopic reactions H + T₂ and T + H₂ are shown to migrate with increasing energy in opposite directions away from the classical barrier, i.e., into the reactant and product valleys, respectively. The energy dependence of this isotopic shift is examined and excitation functions are reported, both for collinear and near-collinear reactions.     

Oxygen isotopic exchange between carbon dioxide and some molybdates or rare-earth elements

The oxygen exchange between C¹⁸O₂ and the normal molybdates of cerium, lanthanum, praseodymium and neodymium has been studied within the temperature interval 300–500°C. The specific rates and activation energies of exchange for these molybdates were found to have similar values. The reactivity of oxygen in the molybdates studied was shown to be close to the reactivity of oxygen in MoO₃     

Isotope effects in tritium exchange between liquid pyrrole, pyrrolidine and gaseous hydrogen

The overall tritium separation factor between molecular hydrogen and liquid pyrrole and pyrrolidine has been measured between 280 and 325 K. The data are comparable with values of α measured for similar exchange reactions involving ammonia and methylamine. There is a visible correlation of the isotope effect with the energy of hydrogen bond formed by NH groups of liquid ammonia, methylamine, pyrrole and pyrrolidine.     

Isotope exchange of heterocyclic compounds with D2O in the presence of transition metals

During a study of deuterium-hydrogen exchange of two-ring condensed heterocycles in the presence of a Pt catalyst it was observed that the degree of deuteration decreases in the order benzofuran naphthalene > benzothiophene. It was found that the degree of deuteration of 2-acetylbenzofuran is 80%, whereas for 2-propylbenzofuran it is only 8%. The degree of deuteration of hydrogenated derivatives decreases in the order coumarin > chromene > dihydrocoumarin; the formation of polydeuterated derivatives is observed for coumarin, whereas products of replacement of one hydrogen atom by deuterium predominate for chromene and dihydrocoumarin.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 451–453, April, 1981.     

Determination of admixtures of high-melting metals in rare-earth metals and their compounds

The study considers the possibility of using inductively coupled plasma mass spectrometry (ICP MS) for the determination of admixtures of Zr, Nb, Mo, Hf, Ta, W, and Te in rare-earth metals and their compounds using preliminary extraction or extraction-chromatographic preconcentration. The admixture elements have been separated by extraction with trioctylphosphine oxide in dichloroethane from hydrochloric acid media and back extraction with oxalic acid. Chemical separation provided a 1–4-order reduction of the lower quantification limit for these elements using ICP MS.     

Complexes of rare-earth metals with meconic acid

Two series of complexes of meconic acid (H₃ Mec) with rare-earths have been prepared by varying the preparative procedure. The compounds have the general formulae, [Ln(Mec) (H₂O)₂]·3 H₂O (whereLn=La, Ce, Pr, Nd, Sm, Ho and Y) and [Ln(HMec) (H₂ Mec) (H₂O)₂]·4 H₂O (whereLn=La, Pr, Nd and Sm). The infrared spectral data indicate that the carboxylate groups are bound to the rare-earth metal in a bidentate fashion. Thermal studies indicate that two water molecules are coordinated in each case. The complexes are probably polymeric.

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Komplexe von Seltenerd-Metallen mit Meconsäure

Zusammenfassung Es wurden zwei Reihen von Komplexen der Meconsäure (H₃ Mec) mit Seltenerd-Metallen mit den allgemeinen Formeln [Ln(Mec)(H₂O)₂]·3 H₂O (Ln=La, Ce, Pr, Nd, Sm, Ho, Y) und [Ln(HMec)₂(H₂ Mec) (H₂O)₂]·4 H₂O (Ln=La, Pr, Nd, Sm) hergestellt. Die IR-Spektren zeigen, daß die Carboxylat-Gruppen in zweizähniger Weise mit den Metallionen koordinieren; thermische Untersuchungen ergeben, daß in beiden Reihen jeweils zwei Wassermoleküle zusätzlich koordiniert sind. Die Komplexe weisen wahrscheinlich eine Polymerstruktur auf.