Gibbs energies of formation of rare earth oxysulfides

The standard Gibbs energy change accompanying the conversion of rare earth oxides to oxysulfides by reaction of rare earth oxides with diatomic sulfur gas has been measured in the temperature range 870 to 1300 K using the solid state cell: Pt/Cu+Cu2S/R2O2S+R2O3‖(CaO)ZrO2‖Ni+NiO, Pt where R=La, Nd, Sm, Gd, Tb, and Dy. The partial pressure of diatomic sulfur over a mixture of rare earth oxide (R2O3) and oxysulfide (R2O2S) is fixed by the dissociation of Cu2S to Cu in a closed system. The buffer mixture of Cu+Cu2S is physically separated from the rare earth oxide and oxysulfide to avoid complications arising from interaction between them. The corresponding equilibrium oxygen partial pressure is measured with an oxide solid electrolyte cell. Gibbs energy change for the conversion of oxide to the corresponding oxysulfide increases monotonically with atomic number of the rare earth element. Second law enthalpy of formation also shows a similar trend. Based on this empirical trend Gibbs energies of formation of oxysulfides of Pr, Eu, Ho, and Er are estimated as a function of temperature.

Magnetic superconductors: Model theories and experimental properties of rare-earth compounds

Superconducting and magnetically long-range ordered states were believed to be mutually exclusive phenomena. The discovery of rare-earth compounds in recent years, which exhibit both superconductivity and magnetic ordering (ferromagnetic, antiferromagnetic or sinusoidal), has led to considerable theoretical and experimental work on such systems. In the present article, we give a review of various theoretical models and important experimental results. In the theoretical sections, we start with the Abrikosov-Gorkov pair breaking theory for dilute alloys and discuss its improvement in the work of Müller-Hartmann and Zittartz. Then, in the context of magnetic superconductors, various microscopic theories that have been advanced are presented. These predict re-entrant behaviour in some systems (ferromagnetic superconductors) and coexistence regions in others (particularly antiferromagnetic superconductors). Following this, phenomenological generalized Ginzburg-Landau theories for two kinds of orders (superconducting and magnetic) are presented. A section dealing with renormalization group analysis of phase diagrams in magnetic superconductors is given. In experimental sections, the properties of each rare-earth compounds (ternary as well as some tetranery) are reviewed. These involve susceptibility, heat capacity, resistivity, upper critical field, neutron scattering and magnetic resonance measurements. The anomalous behaviour of the upper critical field of antiferromagnetic superconductors near the Néel temperature is discussed both in theory sections and experimental section for various systems.

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.

Complexes of rare earth perchlorates with di-2-pyridyl ketone

Abstract is not availabe.

Rare earth transition metal sulfides, LnMS3

Ternary rare earth transition metal sulfides LnMS3 with Ln = La, Nd, and Gd, and M = V and Cr; as well as Ln = La and M = Mn, Fe, Co, and Ni have been prepared and characterized. The vanadium and chromium sulfides crystallize in a monoclinic layer structure isotypic with LaCrS3, while the other LnMS3 sulfides crystallize in a hexagonal structure. Chemical shifts of the metal K-absorption edge and XPS binding energies of core levels indicate that the transition metal is trivalent in the V and Cr sulfides, while it is divalent in the Mn, Fe, Co, and Ni sulfides. Electrical and magnetic properties of the sulfides are discussed in terms of their structures and the electronic configurations of the transition metal ions.

2,6-Lutidine-N-oxide complexes of rare-earth bromides

2,6-Lutidine-N-oxide (LNO) complexes of rare-earth bromides of the composition $$MBr_3 .(LNO)_{4_{ - n} } .nH_2 O$$ wheren = l for M = La, Pr, Nd, Sm, Gd, Ho, Er; andn = 0 for M = Y have been prepared and characterised by analyses, conductance and infrared data. Infrared spectra of the complexes indicate that the coordination of ligand to the metal ion takes place through the oxygen of the ligand, and the water molecule in the complexes present is coordinated to the metal. A coordination number of seven has been suggested to all the rare-earth metal ions.

Topochemically controlled hydrogen reduction of scheelite-related rare-earth metal molybdates

Scheelite-related -Ln2Mo3O12(Ln = La, Pr, Nd, Sm, Gd, Tb, or Dy) oxides are reduced by hydrogen at 780–870 K yielding molybdenum (IV) oxides of formula Ln2Mo3O9. The latter crystallize in a tetragonal scheelite (ABO4) type structure where one third of the A sites and a quarter of the anion sites are vacant: Ln2/3(cat)1/3MoO3(an). The reaction Ln2Mo3O12+ 3H2 Ln2Mo3O9(an)3+ 3H2O may be regarded as topochemically controlled, since both the parent and the product phases have scheelite-related structures. Infrared spectra and electrical and magnetic properties of these metastable defect scheelite phases are reported.

Thermal decomposition of rare-earth trioxalatocobaltates

The thermal decomposition of rare-earth trioxalatocobaltates LnCo(C2O4)3 · x H2O, where Ln = La, Pr, Nd, has been studied in flowing atmospheres of air/oxygen, argon/ nitrogen, carbon dioxide and a vacuum. The compounds decompose through three major steps, viz. dehydration, decomposition of the oxalate to an intermediate carbonate, which further decomposes to yield rare-earth cobaltite as the final product. The formation of the final product is influenced by the surrounding gas atmosphere. Studies on the thermal decomposition of photodecomposed lanthanum trioxalatocobaltate and a mechanical mixture of lanthanum oxalate and cobalt oxalate in 1 : 2 molar ratio reveal that the decomposition behaviour of the two samples is different. The drawbacks of the decomposition scheme proposed earlier have been pointed out, and logical schemes based on results obtained by TG, DTA, DTG, supplemented by various physico-chemical techniques such as gas and chemical analyses, IR and mass spectroscopy, surface area and magnetic susceptibility measurements and X-ray powder diffraction methods, have been proposed for the decomposition in air of rare-earth trioxalatocobaltates as well as for the photoreduced lanthanum salt and a mechanical mixture of lanthanum and cobalt oxalates.

Lanthanide coordination in dimethyl sulphoxide and antipyrine complexes of rare earth nitrates

Abstract is not available.

Preparation, IR and nuclear magnetic resonance studies on the rare-earth perchlorate complexes of 3-methylpyridine-1-oxide

THE COMPLEXES of pyridine-l-oxide and 2- and 4-substituted pyridine-l-oxides have been investigated previously[l]. The complexes of 3-substituted pyfidine-l-oxides, however, have received little attention. The rare-earth complexes of pyridine-Ioxide[l, 2], 4-methylpyridine- l-oxide [1] and 2,6- dimethylpyfidine-l-oxide[3,4] have been reported earlier. The present paper deals with the isolation and characterisation of 3-methylpyridine-l-oxide (3-Picoline-N-oxide, 3-PicNO) complexes with rare-earth perchlorates.

3-Picoline-N-oxide complexes of rare-earth bromides

3-Picoline-N-oxide (3-PicNO) complexes of rare-earth bromides of the formulaMBr3(3-PicNO)8–n·nH2O wheren=0 forM=La, Pr, Nd, Sm Tb or Y andn=2 forM=Ho or Yb have been prepared. Infrared and proton NMR studies indicate that the coordination of the ligand is through oxygen. Conductance data in acetonitrile suggest that two bromide ions are coordinated to the metal ion. Proton NMR studies suggest a bicapped dodecahedral arrangement of the ligands around the metal ion in solution for Pr(III), Nd(III) and Tb(III) complexes.

4-Picoline-N-oxide complexes of rare-earth bromides

In continuation of our work on the effect of the anion on the coordination chemistry of the rare-earth metal ions, we have now extended our studies to 4-picoline-N-oxide (4-Pie NO) complexes of rare-earth bromides. By ohangi~ the method of preparation Harrison and Watsom (1) have prepared two types of Sm(IIl) complexes and three types of Eu(III) complexes of 4-pioollne-N-Oxide in the presence of perchlorate ions. We have isolated two types of pyridine-N-Oxide complexes of rare-earth bromides, also by changing the method of preparation (2). The effect of the change of the preparative method on the composition of the lanthanide complexes is exhibited in the case of other complexes also (3-6). But our attempts to prepare 4-picoline-N-Oxide of rare-earth bromides having different stoichiometries were unsucessful . The composition of the complexes is the same for all the complexes prepared. The results of the physico-chemical studies on these 4-Pic NO complexes of rare-earth bromides are discussed in the present paper.

Antipyrine complexes of rare-earth nitrates

Antipyrine complexes of eight rare-earth nitrates of the composition M(C11H12N2O)3 (NO3)3 where M = La, Ce, Pr, Nd, Sm, Gd, Er, and Y, have been prepared by a new, simple method and characterised. The complexes undergo exothermic decomposition at ~3oo°C. Infrared and U.V. spectral studies of the complexes indicate that antipyrine coordinates to metal through oxygen. The nature of the nitrate bonding is discussed in the light of infrared evidence, and conductivity studies in nitromethane and dimethylformamide.

Rare-earth trichloroacetates

The rare-earth trichloroacetates having the formula Ln(Cl3CCOO)3. 3H2O, where Ln = La, Pr, Nd, Sm, Gd or Y, were investigated by conductimetric, cryoscopic and infrared methods. The results suggest a structure in which the acetate anion coordinates to the metal through both the oxygen and the water molecules remain outside the coordination sphere.