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.     

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.     

Coordination around thorium(IV) in aqueous perchlorate,chloride and nitrate solutions

The coordination around the thorium(IV) ion in aqueous perchlorate, chloride and nitrate solutions has been determined from large angle X-ray scattering measurements. In perchlorate solutions, where inner-sphere complexes are not formed, the first coordination sphere contains 8.0±0.5 water molecules with Th-H₂O bond lengths of 2.48₅ Å. In chloride solutions inner-sphere complexes are formed, which lead to an increase in the coordination number. In nitrate solutions the nitrate ions are bonded as bidentate ligands to the thorium ion. The bond lengths are similar to those found in crystalline hydrates of thorium nitrate. The coordination numbers found for thorium(IV) in solution are compared with previously reported values for lower charged ions of similar size.On leave from Department of Inorganic Chemistry Royal Institute of Technology S-10044 Stockholm Sweden     

Dibutyl N,N-dibutylcarbamoylmethylphosphonate extraction of Eu(III) from perchlorate and nitrate solutions

Dibutyl N,N,-dibutylcarbamoylmethylphosphonate (DBDBCMP) has been used in the extraction study of Eu(III) from low acidic solutions. The different parameters affecting the distribution ratio have been studied. The reaction is considered as a chelate interaction and the extracted species are Eu(OH)₂ DBDBCMP·2HDBDBCMP and Eu(NO₃)₂ DBDBCMP. HDBDBCMP from perchlorate and nitrate, respectively. The equilibrium constants corresponding to the different species formed are calculated and discussed. The effect of changing diluent on extraction capacity of the phosphonate is also studied and discussed.     

Capillary electrophoresis determination of nitrate and nitrite in high-salt perchlorate solutions for the UC dissolution study

The capillary electrophoresis method with direct UV detection is proposed for the determination of nitrite and nitrate in high-salt perchlorate solutions issued from uranium carbide dissolution. The isotachophoretic sample stacking was used to compensate for the perchlorate matrix interference. Simple electrolyte composed of 120 mM formiate buffer, pH 3.8 enabled the nitrate and nitrite determination in the presence of up to 1000-fold excess of perchlorate with 2 μM and 4 μM detection limits for nitrate and nitrite, respectively. The proposed method was applied to the determination of nitrate and nitrite in high-salt non-irradiated uranium carbide dissolution samples.     

An X-ray investigation on the structure of iron(III) perchlorate solutions

Ferric perchlorate solutions have been investigated by an X-ray scattering technique. The main features of the radial distribution functions are consistent with the presence of ClO₄⁻ ions and of hydrated Fe(H₂O)₆³⁺ complexes in octahedral configuration. Structural parameters have been derived for these two species from the outermost parts of the reduced intensity functions. An hydrogen bonded structure outside the inner coordination sphere of iron(III) is strongly suggested by the presence of a large peak at 4 Å in the radial distribution curves. In this respect a comparison between iron(III) perchlorate and nitrate solutions has made possible to evidentiate a similar structural arrangement for Fe³⁺ ions in both media. Some indications have been also obtained supporting the existence of an outer-sphere FeClO₄ complex and of hydration water around the perchlorate group.     

Intradiffusion coefficients for iron and water and shear viscosities in aqueous iron(II) perchlorate solutions at 25°C

Intradiffusion coefficients of iron(II) and water were determined in acidified solutions of iron(II) perchlorate for an iron concentration range of 0 to 2.5 mol-dm^–3 at 25°C. In addition ancillary shear viscosity and density data were measured for each solution. Results were compared with existing diffusion data for iron(III) perchlorate solutions and highlighted the differences in the solvent dynamics around the two metal ions. By use of a simple model the effective hydration of the iron(II) ion was estimated to be 12, comparable to that of other divalent, uncomplexed metal cations; the same model indicates an effective hydration of 19 for iron(III).     

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     

Small-angle neutron scattering from typical synthetic and biopolymer solutions

Small-angle neutron scattering (SANS) has been used to investigate the solution properties of four model polymers, two poly-amino acids [poly(lysine) and poly(proline)], and two water-soluble synthetic polymers [poly(acrylic acid) and poly(ethylene oxide)]. In each case, one of the two polymers is charged, while the other is neutral. SANS measurements were made in the semi-dilute concentration regime in two different solvents [d-water and d-ethylene glycol]. The scattering signals were decomposed into low-Q clustering and high-Q solvation contributions. The temperature dependence of the scattering parameters was determined for poly(lysine) and poly(ethylene oxide) solutions over the temperature range of 13 to 82 °C. Analysis of the SANS spectra revealed that with increasing temperature, the solvation intensity increased in both solvents, while the clustering intensity increased in d-water and decreased in d-ethylene glycol. Significant differences were observed between the SANS spectra of charged and neutral polymer solutions. However, biopolymers and synthetic polymers exhibited qualitatively similar behavior.     

Comparative analysis of structural parameters of the nearest surrounding of nitrate and perchlorate ions in aqueous solutions of electrolytes

Data on structural parameters of the nearest surrounding of nitrate and perchlorate ions in aqueous solutions under standard conditions have been generalized. Hydration numbers, interparticle distances, and ionic association types have been discussed and compared. The major difference between the ions is that nitrate ion tends to form ion pairs, whereas perchlorate ion does not.     

Thermolysis of hydrogen sulphate,nitrate and perchlorate salts of diphenylamine. Part LXVIII

Hydrogen sulphate, nitrate and perchlorate salts of diphenylamine have been prepared and characterized by elemental, spectral and gravimetric analyses. Thermal decomposition of these salts has been evaluated by TG (static air) and DSC (inert atmosphere). The proton transfer reaction plays a major role during thermolysis of these salts. The diphenylammonium hydrogen sulphate under thermal and microwave irradiation forms 4-(phenylamino) benzenesulphonic acid by sulphonation process, whereas nitrate and perchlorate salts do not form corresponding nitro and perchloro derivatives, rather they ignite and explode, respectively, to form gaseous products along with a residual carbon .     

Extraction kinetics of iron(III) from aqueous nitrate solutions to toluene solutions of tri-n-butylacetohydroxamic acid

The forward and reverse extraction rate of Fe³⁺ at time zero between aqueous nitrate solutions and toluene solutions of tri-n-butylacetohydroxamic acid, HX, has been studied as function of the composition of the system and the stirring speed of the two phases. Experimental information has been also obtained on the degree of aggregation of HX, its surface active properties, its solubility in the aqueous phase as well as on the equilibrium distribution of Fe(III). Rate equations have been derived. The rate determining step of the extraction reaction has been shown to be the reaction of the free and hydrolyzed iron ions, Fe³⁺ (hydrated) and FeOH⁺ (hydrated), with the HX undissociated molecules. The reactions occur simultaneously in the aqueous phase (homogeneous path) and at the interface (heterogeneous path). A correlation between the rate constants and the equilibrium constant of the extraction reaction of Fe(III) has been established.     

Small-angle X-ray scattering and rheological characterization of aqueous lignosulfonate solutions

Lignosulfonate is a colloidal polyelectrolyte widely used as a dispersant in various industrial applications and produced during chemical pulping of wood chips. Here we present a systematic small-angle X-ray scattering (SAXS) and rheological study of fractionated lignosulfonate (mass weighted molar mass M w 18 000 g/mol) dissolved in water and 0.2 M NaCl. The concentration range varied from semidilute to concentrated regime. SAXS intensity of all solutions followed the Porod law at all concentrations, which is a clear indication of a compact shape of the lignosulfonate particle. In water, below 10 mass % lignosulfonate, the average interparticle distance obtained from SAXS patterns relates to concentration via a power law with exponent -0.28. Deviation of the power law exponent from ideal -0.33 and a linear decrease in volume fraction normalized Porod constant as a function of concentration are taken as indications of self-association of lignosulfonate. In saline solutions at high lignosulfonate mass fractions the average distance between lignosulfonate particles was longer and the average particle size was larger than those in aqueous solutions. The intrinsic viscosity in saline solution also was larger than that in aqueous solution. Lignosulfonate solutions showed Newtonian viscosity, except at very high concentrations. The variation of the relative zero-shear viscosity eta(0),r) with concentration was interpreted with the Krieger-Dougherty equation. An oblate spheroid shape with an axial ratio of 3.5 describes the average shape of the lignosulfonate particles in saline solutions based on SAXS intensities, the size distribution obtained using gel permeation chromatography, and rheological characterization. The largest dimension of the particles was about 8 nm. SAXS and rheology studies as a function of temperature reveal indications of temperature-dependent self-association.     

Study of the reaction between lanthanum perchlorate and Eriochrome Cyanine R in strongly alkaline solutions

Summary The nature of the reaction product between La(III) and ECR has been investigated and an empirical formula proposed for the observed lake. Chemical analysis of the lake demonstrated it does not possess a definite structure, the composition of the isolated product being dependent on the experimental conditions and composition of the solution. X-ray studies revealed the amorphous nature of the isolated product. D. T. A. study of the product was made and a decomposition sequence is proposed for the same.

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Zusammenfassung Das Reaktionsprodukt aus La(III) und Eriochromcyanin R wurde untersucht und eine empirische Formel für diese Lackverbindung vorgeschlagen. Die chemische Analyse zeigt, daß sie keine definierte Struktur hat, sondern in ihrer Zusammensetzung von den Versuchsbedingungen und von der Konzentration der Lösung abhängt. Die Röntgenanalyse zeigt, daß das isolierte Reaktionsprodukt amorph ist. Aufgrund einer Differential-Thermoanalyse wurden die Einzelvorgänge der Zersetzung dargelegt.

     

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.     

Electronic and spatial structure of spin transition iron(II) tris(4-amino-1,2,4-triazole) nitrate and perchlorate complexes

Electronic and spatial structure of polynuclear iron(II) complexes Fe(ATr)₃(ClO₄)₂, Fe(ATr)₃(NO₃)₂, and Fe_0.34Zn_0.66(ATr)₃(NO₃)₂ (where ATr is 4-amino-1,2,4-triazole) is investigated using EXAFS and XANES spectroscopy and X-ray fluorescent spectroscopy. Changes in the distances to the first four coordination spheres of Fe and Zn atoms upon spin transitions induced by variations of the anion or temperature are analyzed. It is shown that in polynuclear complexes the spin transition (from S=2 to S=0) is accompanied by pronounced variations in the electronic and spatial structure. A mutual effect of Fe and Zn atoms was found which alters the local environment of the low-spin Fe atoms in a magnetically diluted complex as compared to the initial one. Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences. Translated fromZhurnal Strukturnoi Khimii, Vol. 35, No. 4, pp. 96–104, July–August, 1994. Translated by L. Smolina