Journal of Inorganic and Nuclear Chemistry最新文献

Brown ring compounds have been produced by the reaction of ferrous ion with nitric oxide and with nitrous acid in aqueous solution. Spectroscopic results have showed that the brown color is due to charge-transfer bands associated with the FeNO bond. The cyclic voltammetric experiments indicated that the oxidation of this compound was completely irreversible. The influence of light was to stimulate the charge-transfer process in which the electrons were transferred from the donor orbital into the acceptor orbital, and finally led to the formation of the ion-pair Fe(I)NO⁺ which was assumed to be more electroactive.

Potentiometric and conductometric titrations of the system Pd(II) and pyridine-2-aldehyde-2′-pyridylhydrazone in aqueous solution show that only one proton per atom of Pd is titratable; i.e. only one mole of ligand coordinates with each Pd. [PdL₂] does not form in aqueous solution. Job's method of continuous variations was applied and a computer calculation on a model system was used to estimate equilibrium constants. PMR investigations suggest the ligand in [PdL₂] undergoes isomerization about the imine bond.

Cd₃[Cr(CN)₆]₂ · 14H₂O crystallizes in a cubic unit cell, space group Fm3m(O_h⁵, No. 225), with a₀ = 10.961(2)Å. The observed density is 1.70(1) Mg-m⁻³ (calculated density, 1.690 Mg-m⁻³). A thermogravimetric analysis has yielded 13.9(2) water molecules per formula unit. X-Ray fluorescence emission energy values and infrared spectroscopic results are presented. Full-matrix least-squares refinement of 160 unique reflections has yielded R₁ = 0.0350 and R₂ = 0.0349. The disordered structure contains $\text{1}\text{1}\text{3}$ molecules in the unit cell. Linkage of the divalent Cd atoms to the Cr atoms is accomplished by cyanide bridging. A new structural model was employed and important bond distances are reported.

Equilibria of cobalt(II) perchlorate with lithium chloride in 0.1 M LiClO₄ acetone solution have been investigated by means of potentiometry and spectrophotometry at 25.0°C. By the addition of a large excess of medium salt (LiClO₄), the ionic dissociation of electrolytes are surpressed and the ion-pairs predominate in this medium. It was confirmed that AgAgCl electrode gives rise to the Nernstian response in this medium. The potentiometry reveals the formation of following chloro complexes of cobalt (II): $\text{Co(ClO}{}_4\text{)}{}_2\text{+LiCl}\text{⇌}\text{K}{}_1\text{CoCl(ClO}{}_4\text{)+LiClO}{}_4$$\text{Co(ClO}{}_4\text{)+LiCl}\text{⇌}\text{K}{}_2\text{CoCl}{}_2\text{+LiClO}{}_4$$\text{CoCl}{}_2\text{+LiCl}\text{⇌}\text{K}{}_3\text{LiCoCl}{}_3$

Successive formation constants were determined as log K₁ = 5.0 ± 0.3, log K₂ = 6.2 ± 0.3 (log β₂ = log K₁K₂ = 11.15 ± 0.03) and log K₃ = 5.97 ± 0.03. By the spectrophotometric titration at higher concentration of lithium chloride, we have the following equilibrium: $\text{LiCoCl}{}_3\text{+LiCl}\text{⇌}\text{K}{}_4\text{LiCoCl}{}_3$ with formation constant of log K₄ = 2.64 ± 0.05. Absorption spectra of these complexes are presented.

Measurements of CO pressure over the thorium dioxide, thorium dicarbide, carbon phase region were made in the range 1328–1976 K. These values were used with other consistent measurements to derive the 298 K second-law heat of formation and entropy 129±6 kJ/mol and 67.0±3 J·mol⁻¹·K⁻¹, and the third-law heat of formation −122±9 kJ/mol, for thorium dicarbide.

Mixed pentahaloantimonates(III) formulated as R₂(SbX₃Y₂) (R = substituted ammonium ion and X and YCl, Br or I) and [(C₂H₅)₄N]₂ [SbCl₃BrI] have been isolated from non-aqueous media by the interaction of the antimony trihalide and the substituted ammonium halide. The reaction stoichiometry between SbX₃ (XCl, Br) and substituted ammonium halide was determined by conductimetric titrations. These complexes were characterised by chemical analysis, melting points, conductance, TGA, far IR and electronic spectra.