Intercalation of an oxalatooxoniobate complex into layered double hydroxide and layered zinc hydroxide nitrate

A Zn/Al layered double hydroxide with molar ratio of 3 was prepared by coprecipitation in alkaline pH and used as a matrix to intercalate the ionic complex diaquadioxalatooxoniobate(V) (DDON), derived from NH₄[NbO(C₂O₄)₂(H₂O)₂]2H₂O. In a similar way, the layered zinc hydroxide nitrate, Zn₅(OH)₈(NO₃)₂2H₂O, was synthesized, preexpanded with azelate ions (⁻OOC(CH₂)₇COO⁻), and then intercalated with the niobium complex. For both layered matrices, the results from X-ray powder diffractometry, Fourier transform infrared spectroscopy, and thermal analysis (TG/s-DTA) indicate the presence of the oxalate ion. In addition, results from X-ray photoelectron and Raman spectroscopy indicate the presence of the niobium center bonded to oxygen atoms. Finally, diffuse reflectance UV–vis spectroscopy suggests that the niobium centers are coordinated to oxalate ions. This is the first report of the intercalation of niobium into a layered matrix.     

Carboncarbon bond formation using bismuth in a water medium

In the presence of bismuth and ammonium chloride, allyl halides were found to react with aldehydes in a water medium at room temperature to give the corresponding homoallylic alcohols.     

Phase formation and physicochemical properties of perovskite complex oxides based on bismuth ferrite

The effect of the cationic composition on the formation of perovskite solid solutions based on bismuth ferrite(Bi_{1 − x/3}□ _x/3)[Fe_{1 − x} Ti _x ]O₃ with x = 0.00–0.48, Δx = 0.03, has been studied. The homogeneity range of the perovskite phase under the conditions of the solid-phase synthesis of solid solutions has been determined, and the effect of the cationic composition on the physicochemical properties of solid solutions has been studied.     

Chemical modification of zinc hydroxide nitrate and Zn-Al-layered double hydroxide with dicarboxylic acids

A zinc hydroxide nitrate (ZHN), Zn5(OH)8(NO3)2.2H2O, and a layered double hydroxide (LDH), Zn/Al-NO3 were doped with 0.2 mol% of Cu2+ during alkaline chemical precipitation. Both compounds were intercalated with adipate ((-)OOC(CH2)4COO(-)), azelate ((-)OOC(CH2)7COO(-)), and benzoate (C6H5COO(-)) ions through ion exchange reactions. Solid state 13C nuclear magnetic resonance spectroscopy showed only one signal of carboxylic carbon for adipate and azelate intercalated into LDH, indicating that the carboxylic ends of both acids were equivalent, whereas the signal split when the intercalation was into the ZHN matrix. The electron paramagnetic resonance (EPR) spectrum of copper in octahedral cation sites of LDH layers showed a Hamiltonian parameter ratio g ||/A ||=170 cm and, after intercalation of adipate, the change was not significant: g ||/A ||=174 cm. This result indicates that the carboxylate ions did not coordinate with copper centers. Nonetheless, the intercalation of azelate increased the ratio to g ||/A ||=194 cm, similar to the spectra of ZHN modified with adipate, g ||/A ||=199 cm, and azelate, g ||/A ||=183 and 190 cm, which are associated with the coordination of copper by weak carboxylate anion ligands. Copper occupies octahedral or tetrahedral sites in ZHN layers, and the EPR spectra indicate that the dicarboxylate anions reacted preferentially with octahedral sites, whereas benzoate reacted with both sites.     

The preparation and characterization of guanylurea nitrate and perchlorate salts

Guanylurea nitrate (GUN) and guanylurea perchlorate (GUP) were prepared from cyanoguanidine (CG) and concentrated nitric or perchloric acid, respectively. Both compounds were fully characterized by analytical and spectroscopic methods. Crystals of GUP were grown from water, and its crystal structure was determined by single‐crystal X‐ray diffraction. GUP crystallizes in the monoclinic space group P2₁/c with four molecules in the unit cell; different unit cell parameters are a = 8.0115(2) Å, b = 9.7328(2) Å c = 9.5770(2) Å and β = 105.89(1)°. The heats of combustion of both compounds were determined using oxygen bomb calori‐metry. Finally, the EXPLO5 computer code was used to determine the detonation velocity (D = 5734 m s⁻¹) and pressure (P = 10.6 GPa) of GUN as well as those of formulations with ammonium nitrate and dinitramide. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:301–306, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20419     

Electrochemical and complexation behavior of neptunium in aqueous perchlorate and nitrate solutions

Electrochemical and complexation properties of neptunium (Np) are investigated in aqueous perchlorate and nitrate solutions by means of cyclic voltammetry, bulk electrolysis, UV-visible absorption, and Np L(III)-edge X-ray absorption spectroscopies. The redox reactions of Np(III)/Np(IV) and Np(V)/Np(VI) couples are reversible or quasi-reversible, while the electrochemical reaction between Np(III/IV) and Np(V/VI) is irreversible because they undergo structural rearrangement from spherical coordinating ions (Np(3+) and Np(4+)) to transdioxoneptunyl ions (NpO2(n+), n = 1 for Np(V) and 2 for Np(VI)). The redox reaction of the Np(V)/Np(VI) couple involves no structural rearrangement on their equatorial planes in acidic perchlorate and nitrate solutions. A detailed analysis on extended X-ray absorption fine structure (EXAFS) spectra suggests that Np(IV) forms a decaaquo complex of [Np(H2O)10](4+) in 1.0 M HClO4, while Np(V) and Np(VI) exist dominantly as pentaaquoneptunyl complexes, [NpO2(H2O)5](n+) (n = 1 for Np(V) and 2 for Np(VI)). A systematic change is observed on the Fourier transforms of the EXAFS spectra for all of the Np oxidation states as the nitrate concentration is increased in the sample, revealing that the hydrate water molecules are replaced by bidentate-coordinating nitrate ions on the primary coordination sphere of Np.     

Behaviour of bismuth nitrate spots in inorganic paper chromatography

An investigation of irregularities found when chromatographing bismuth ions with butanol-watcr-thiocyanic solutions led to the conclusion that the process is one of absorption rather than partition for the development of this ion.     

ipso-Nitration of arylboronic acids with bismuth nitrate and perdisulfate

An efficient and one pot synthetic method of ipso-nitration of arylboronic acids has been developed. The high efficiency, general applicability, and broader substrate scope including heterocycles and functional groups make this method advantageous. Due to its simplicity, we expect to find application of this method in synthesis.     

Kinetics of actinide valence transformation in alpha-radiolysis of nitrate and perchlorate solutions

This paper presents the results of systematic kinetic studies of valence transformation of U, Np, Pu, Am and Bk in nitrate- and perchlorate solutions under the effect of intensive internal alpha-radiation emitted by²⁴⁴Cm nuclides. The high dose rate of solutions (D=1–8 Gy/s) provides a sufficient yield of H₂O₂, HNO₂ and ClO₂ — the main products of alpharadiolysis of water, nitrate and perchlorate ions, respectively, which was determined by spectrophotometric methods immediately in the course of the process under study. To describe the results, a kinetic scheme considering the effect of dose rate and solution composition is proposed. The calculations have been carried out on a BESM-6 computer, a satisfactory agreement between the calculated and experimental data has been obtained.     

Kinetics of the decay of nitroxyl radicals during polymerization of a complex of acrylamide with bismuth nitrate

Kinetics of the decay of nitroxyl radicals during spontaneous polymerization of complexes of acrylamide (AAm) with Bi^III nitrate has been studied by ESR. From a comparison of the experimental and calculated kinetic curves, the initiation rate constant of polymerization has been determined. The approach proposed is suitable for determining the main kinetic characteristics of other polymerizable nonparamagnetic AAm complexes with metal nitrates.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1572–1575, September, 1994.This work was carried out with the financial support of the Russian Foundation for Basic Research (Project No93-03-4162).     

Reaction of bismuth nitrate with sodium citrate in water-glycerol solutions

The reaction in a Bi(NO₃)₃-Na₃Hcit-(H₂O + glycerol) system was studied in a wide range of component ratios by the solubility method and pH-metry in combination with chemical analysis of solid phases. Poorly soluble phases of Bi(Hcit) _x (OH)_{3(1 − x)} · mH₂O (x < 1) and sodium bismuth citrate NaBiCit · 3H₂O were obtained. The compounds synthesized were characterized, and their compositions were refined by X-ray diffraction, DTG, and IR spectroscopy.     

Preparation of magnesium hydroxide from nitrate aqueous solution

Nucleation of Mg(OH)₂ was investigated by measuring the electrical conductivity and pH of the Mg(NO₃)₂ reaction solution to which ammonia containing different amounts of NH₄NO₃ was added. NH₄NO₃ increases solubility and slows down precipitation of Mg(OH)₂ in the system. Data are presented on the influence of NH₄NO₃ on the solubility of Mg(OH)₂ at 25°C. The phenomena observed can be explained by the solvation effect of nitrate ions brought to the system with the addition of ammonium nitrate, which was proved by NMR spectroscopy. When the mass fraction of NH₄NO₃ exceeds 15 %, homogeneous nucleation does not proceed. It was found that seeding of the system with Mg(OH)₂ crystals only influenced the rate of Mg(OH)₂ crystallisation, not the size and shape of the crystals. Primary crystals are smaller than 0.1 μm. The large difference in the surface energy of individual crystal planes leads to oriented agglomeration. This process is accelerated in a pressure reactor at 130°C. The resulting polycrystals are hexagonal plates 0.2 μm thin with a diameter of 1–2 μm. Under variable reaction conditions, agglomerates as big as 30 μm can be prepared.     

Hydrolysis studies on bismuth nitrate: synthesis and crystallization of four novel polynuclear basic bismuth nitrates

Hydrolysis of Bi(NO(3))(3) in aqueous solution gave crystals of the novel compounds [Bi(6)O(4)(OH)(4)(NO(3))(5)(H(2)O)](NO(3)) (1) and [Bi(6)O(4)(OH)(4)(NO(3))(6)(H(2)O)(2)]·H(2)O (2) among the series of hexanuclear bismuth oxido nitrates. Compounds 1 and 2 both crystallize in the monoclinic space group P2(1)/n but show significant differences in their lattice parameters: 1, a = 9.2516(6) ?, b = 13.4298(9) ?, c = 17.8471(14) ?, β = 94.531(6)°, V = 2210.5(3) ?(3); 2, a = 9.0149(3) ?, b = 16.9298(4) ?, c = 15.6864(4) ?, β = 90.129(3)°, V = 2394.06(12) ?(3). Variation of the conditions for partial hydrolysis of Bi(NO(3))(3) gave bismuth oxido nitrates of even higher nuclearity, [{Bi(38)O(45)(NO(3))(24)(DMSO)(26)}·4DMSO][{Bi(38)O(45)(NO(3))(24)(DMSO)(24)}·4DMSO] (3) and [{Bi(38)O(45)(NO(3))(24)(DMSO)(26)}·2DMSO][{Bi(38)O(45)(NO(3))(24)(DMSO)(24)}·0.5DMSO] (5), upon crystallization from DMSO. Bismuth oxido clusters 3 and 5 crystallize in the triclinic space group P1? both with two crystallographically independent molecules in the asymmetric unit. The following lattice parameters are observed: 3, a = 20.3804(10) ?, b = 20.3871(9) ?, c = 34.9715(15) ?, α = 76.657(4)°, β = 73.479(4)°, γ = 60.228(5)°, V = 12021.7(9) ?(3); 5, a = 20.0329(4) ?, b = 20.0601(4) ?, c = 34.3532(6) ?, α = 90.196(1)°, β = 91.344(2)°, γ = 119.370(2)°, V = 12025.8(4) ?(3). Differences in the number of DMSO molecules (coordinated and noncoordinated) and ligand (nitrate, DMSO) coordination modes are observed.     

Dialkyl sulfoxides complexes with nickel(II) nitrate and perchlorate

Nickel(II) perchlorate and nitrate complexes containing dimethyl, di-n-propyl, di-n-butyl, di-i-butyl and di-t-butyl sulfoxides have been synthesized and characterized by IR and electronic spectroscopies, magnetic-susceptibility and electrolytic-conductance measurements. In the complexes containing perchlorate, the metal: sulfoxide molar ratio is 1:6 and the perchlorate groups are ionic. In the nitrate compounds, the molar ratio decreases from 1:6 to 1:2 according to the increase in the steric bulk of the alkyl group from methyl to t-butyl. The nitrate group may either be non-coordinating or behave as a monodentate or bidentate ligand. All the complexes contain O-bonded sulfoxide molecules and are characterized as high-spin, with an octahedral or distorted octahedral geometry. The dialkyl sulfoxides studied in this work fall in the same position as dimethyl sulfoxide in the spectrochemical and nephelauxetic series. Electrolytic conductivities suggest that the compounds containing ionic nitrate exhibit sulfoxide—nitrate exchange in nitromethane solutions.     

Conductometric titration of nitrate by formation of the silver-1,10-phenanthroline-nitrate ternary complex

Nitrate forms an insoluble ternary complex, Ag(phen)(2)NO(3), with silver in the presence of 1,10-phenanthroline (phen). A simple and direct conductometric titration of nitrate, based on the formation of this ternary complex, has been investigated. The sample solution is adjusted to pH 4.3 with acetate buffer and titrated with 0.1M Ag(phen)(+)(2) complex solution in 40% ethanol-water mixture. The relative error is less than 0.5% and relative standard deviation less than 0.4%. The effect of ammonium ion and urea has also been studied. The method has been successfully applied to determination of nitrate-nitrogen in fertilizer.     

Indirect bromometric microdetermination of nitrate and perchlorate,using nitron as reagent

Summary An indirect bromometric method for the determination of nitrate or perchlorate is described. A known excess of standard nitron acetate solution is added to the sample solution to precipitate the anion to be determined; the excess of reagent is then determined in the supernatant liquid by bromatometric titration. The relative standard deviation of the method is 0.7% for nitrate and 0.5% for perchlorate. Sulphate, phosphate and fluoride do not interfere and chloride does not interfere up to a concentration of 0.1 M. Bromide, iodide, chromate, nitrite and chlorate interfere but can be eliminated.

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Zusammenfassung Ein indirektes bromatometrisches Verfahren zur Bestimmung von Nitrat oder Perchlorat wurde beschrieben. Ein gemessener Überschuß einer Nitronacetatlösung bekannter Konzentration wird zur Fällung des Anions der Probe zugesetzt und im Überstand bromatometrisch zurücktitriert. Die rel. Standardabweichung beträgt 0,7% für Nitrat und 0,5% für Perchlorat. Sulfat, Phosphat und Fluorid stören nicht; Chlorid stört nicht bis zu 0,1-m Konzentration. Bromid, Jodid, Chromat, Nitrit und Chlorat stören zwar, können aber eliminiert werden.