Properties of TRPO-HNO<Subscript>3</Subscript> complex used for direct dissolution of lanthanide and actinide oxides in supercritical fluid CO<Subscript>2</Subscript>

The mixed trialkylphosphine oxide-nitric acid (TRPO-HNO₃) complex prepared by contacting pure TRPO with concentrated HNO₃ may be used as additives for direct dissolution of lanthanide and actinide oxides in the supercritical fluid carbon dioxide (SCF-CO₂). Properties of the TRPO-HNO₃ complex have been studied. Experimental results show when the initial HNO₃/TRPO volume ratio is varied from 1:7 to 5:1, the concentration of HNO₃ in the TRPO-HNO₃ complex changes from 2.12 to 6.16 mol/L, the [HNO₃]/[TRPO] ratio of the TRPO-HNO₃ complex changes from 0.93 to 3.38, and the content of H₂O in the TRPO-HNO₃ complex changes from 0.97% to 2.70%. All of the density, viscosity and surface tension of the TRPO-HNO₃ complex change with the concentration of HNO₃ in the complex. The protons of HNO₃ and H₂O in the complex undergo rapid exchange to exhibit a singlet resonance peak in NMR spectra with D₂O insert. When the TRPO-HNO₃ complex dissolves in a low dielectric constant solvent, small droplets of HNO₃ appear which can be detected by NMR. Supported by the National Natural Science Foundation of China (Grant No. 20506014)     

Extraction chemistry of uranyl nitrate and nitric acid in high concentration systems

HNO₃ is extracted in significant quantities by uranyl nitrate solvates with different extractants: TBP (tributyl phosphate), TOPO (trioctyl phosphine oxide) and TDA (tetradecyl ammonium). The effect of diluent nature is not observed on extracting HNO₃ and TBP saturated by uranium at equilibrium with its salt using the diluents (CCl₄, C₆H₅Cl, C₁₂H₂₆, CHCl₃) which are less polar than UO₂(NO₃)₂(TBP)₂. HNO₃ occurs in organic phase as undissociated form and its state is similar to pure anhydrous HNO₃. Solvates of TBP and TDA with uranyl nitrate dissolve HNO₃ without displacement of uranium from organic phase.     

Extraction liquide-liquide par des esters alkylphosphoriques. II. Extraction des nitrates de béryllium et des autres alcalino-terreux par le tri-n-butylphosphate

The solvent extraction systems Be(NO₃)₂? HNO₃? H₂O? TBP/kerosene and M(NO₃)₂? H₂O? TBP/kerosene (TBP = tri-n-butylphosphate, M = Be, Mg, Ca and Sr) have been studied. The alkaline earths elements are poorly extracted. Only very high acidities allow better extraction of beryllium. The sequence of extraction of the alkaline earths elements by the TBP depends on the concentration of the cations and is Ca > Be > Sr > Mg if the metal concentration is lower than 2 M.     

Glutarimidedioxime: A Complexing and Reducing Reagent for Plutonium Recovery from Spent Nuclear Fuel Reprocessing

Efficient separation processes for recovering uranium and plutonium from spent nuclear fuel are essential to the development of advanced nuclear fuel cycles. The performance characteristics of a new salt‐free complexing and reducing reagent, glutarimidedioxime (H₂A), are reported for recovering plutonium in a PUREX process. With a phase ratio of organic to aqueous of up to 10:1, plutonium can be effectively stripped from 30 % tributyl phosphate (TBP) in kerosene into 1 m HNO₃ with H₂A. The complexation‐reduction mechanism is illustrated with the combination of UV/Vis absorption spectra and the crystal structure of a Pu^IV complex with the reagent. The fast stripping rate and the high efficiency for stripping Pu^IV, through the complexation‐reduction mechanism, is suitable for use in centrifugal contactors with very short contact/resident times, thereby offering significant advantages over conventional processes.     

Radiolytic degradation of TBP-HNO3 system: Gas chromatographic determination of radiation chemical yields of n-Butanol and nitrobutane

Radiolytic degradation of the TBP-HNO₃ system has been studied for the radiation dose range of 19.8 to 262 kGy by the gas chromatographic method. n-Butanol and nitrobutane formed due to irradiation have been identified and estimated in pure TBP, TBP-3M HNO₃ extract and TBP-5M HNO₃ extract. The G-values (radiation chemical yields) of n-butanol are determined to be 0.28, 0.77 and 0.47 for a pure TBP, TBP-3M HNO₃ extract and TBP-5M HNO₃ extract, respectively. The G-values of nitrobutane (1-nitrobutane) are 0.55 and 1.09 for TBP-3M HNO₃ extract and TBP-5M HNO₃ extract. It is found than G(n-butanol) is less for TBP-5M HNO₃ extract than for TBP-3M HNO₃ extract, while G(nitrobutane) is grater for TBP-5M HNO₃ extract than for TBP-3M HNO₃ extract. This is explained on the basis of the formation of TBP.HNO₃ species and the role played by nitric acid in the TBP phase.     

Insights into the Mechanism of Extraction of Uranium (VI) from Nitric Acid Solution into an Ionic Liquid by using Tri‐n‐butyl phosphate

We present new results on the liquid–liquid extraction of uranium (VI) from a nitric acid aqueous phase into a tri‐n‐butyl phosphate/1‐butyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide (TBP/[C₄mim][Tf₂N]) phase. The individual solubilities of the ionic‐liquid ions in the upper part of the biphasic system are measured over the whole acidic range and as a function of the TBP concentration. New insights into the extraction mechanism are obtained through the in situ characterization of the extracted uranyl complexes by coupling UV/Vis and extended X‐ray absorption fine structure (EXAFS) spectroscopy. We propose a chemical model to explain uranium (VI) extraction that describes the data through a fit of the uranyl distribution ratio D_U. In this model, at low acid concentrations uranium (VI) is extracted as the cationic complex [UO₂(TBP)₂]²⁺, by an exchange with one proton and one C₄mim⁺. At high acid concentrations, the extraction proceeds through a cationic exchange between [UO₂(NO₃)(HNO₃)(TBP)₂]⁺ and one C₄mim⁺. As a consequence of this mechanism, the variation of D_U as a function of TBP concentration depends on the C₄mim⁺ concentration in the aqueous phase. This explains why noninteger values are often derived by analysis of D_U versus [TBP] plots to determine the number of TBP molecules involved in the extraction of uranyl in an ionic‐liquid phase.     

Microwave-assisted dissolution of ceramic uranium dioxide in TBP–HNO3 complex

Microwave-assisted dissolution of ceramic uranium dioxide in tri-n-butyl phosphate (TBP)–HNO₃ complex was investigated. The research on dissolution of ceramic uranium dioxide in TBP–HNO₃ inclusion complex under microwave heating showed the efficiency of the use of this method. Nitric acid present in the inclusion complex participates both dissolution of UO₂, and oxidation of U(IV)–U(VI), the resulting UO₂(NO₃)₂ extracted with tri-n-butyl phosphate. Dissolution rate depends on both temperature of microwave dissolution process, and concentration of nitric acid present in the inclusion complex. The most intensive dissolution process is when the concentration of nitric acid ≥2 mol/L and the temperature of 120 °C. From the experimental data obtained by two kinetic models activation energies were calculated. At the average activation energy of UO₂ dissolution in TBP–HNO₃ complex equal 70 kJ/mol, and reaction order is close to one, i.e. the reaction takes place in an area close to kinetic.     

NMR study of the interaction between water and tributyl phosphate in the TBP-CCl4-H2O system

Hydrogen bonding between water and tributyl phosphate (TBP) in TBP? CCl₄? H₂O system has been studied by ¹H NMR. A new model and an empirical equation have been established on the basis of Li's model and the parameters of hydrogen bond between water and TBP are determined by nonlinear optimization method. In TBP? CCl₄? H₂O system change of ¹H chemical shift of water can be satisfactorily explained by the new model and the empirical equation in the whole concentration range. When the concentration of water in the organic phase is very low, the main existing forms of water are H₂O · TBP and H₂O · 2TBP. When the concentration of water reaches saturation, the main existing form is associated water, but there are still about 20% of water existing in the forms of H₂O · TBP and H₂O · 2TBP.     

Dependence of primary and secondary emulsion formation on the concentration of TBP,HNO3 and additives

Model studies on TBP—diluent—aqueous HNO₃ extraction systems were performed to establish the mechanism of emulsyfying during the reprocessing of spent reactor fuel with mixtures of TBP solutions. The systems of interest were emulsified under fixed conditions. The rate of separation of the primary emulsion as well as the turbidity of each phase were determined. The experiments were performed on mixtures of pure components of the extraction systems. Emulsion stability was investigated in terms of the influence of such factors as main products of TBP decay, the type of diluents, HNO₃ concentration and concentration of TBP in different diluents.     

Nitric acid transport across TBP—Kerosene oil supported liquid membranes

HNO₃ transport across tri-n-butyl phosphate kerosene oil supported liquid membrane with or without uranyl ion transport has been studied. Parameters studied are the effect of TBP in the membrane, nitric acid in the feed solution and nitrate ion concentration in the feed solution. The flux of protons for 1 to 10 mol·dm^–3 HNO₃ solution is in the range of (0–25)·10^–4 mol·m^–2·s^–1 and for the TBP concentration range of 0.359 to 3.59 mol·dm^–3, the flux determined is (8.9 to 22)·10^–4 mol·m^–2·s^–1. From the experimental data and using theoretical equations the complex under transport through the membrane appears to be 2TBP·HNO₃ both in the presence and absence of uranyl ions. The diffusion coefficient for H⁺ ions through the membrane as a function of TBP concentration varies from (53 to 6)·10^–12 m²·s^–1, based on experimental flux and permeability data. The values of this coefficient supposing 2TBP·HNO₃ as diffusing species, based on viscosity data and theoretical estimation varies from (82.50 to 3.30)·10^–12 m²·s^–1. The value of distribution coefficient varies in the reverse direction from 0.06 to 1.46 at the same TBP concentration.     

Controlled surface functionalization of carbon nanotubes by nitric acid vapors generated from sub‐azeotropic solution

Controlled surface modification of nanocarbons is crucial for their use in applications. The paper deals with the functionalization of carbon nanotubes (CNTs) with HNO₃ vapors. Sub‐azeotropic HNO₃ + H₂O + Mg(NO₃)₂ solution is used for the generation of nitric acid vapors. Because this approach allows tuning the HNO₃ concentration in the vapor phase, the effect of its variation on the surface chemistry and structural properties of the CNTs is investigated. A combination of analytical techniques is applied to evaluate oxidation extent of the CNT surface, selectivity towards the formation of carboxyl groups compared with other oxygenated functionalities, and CNT integrity. The comparison with liquid‐phase functionalization in H₂SO₄ + HNO₃ mixture (1 : 3–3 : 1 v/v), conventionally utilized for oxidizing CNTs, shows that vapor‐phase functionalization affords greater surface oxygen uptakes and higher selectivity towards the formation of carboxyl groups, with smaller tube damage; more importantly, it evidences that, regardless of the method and conditions chosen, the selectivity towards carboxyl groups increases linearly with the surface oxygen concentration. The presented results prove that the product of HNO₃ concentration in the vapor‐phase (25–93 wt%) and vapor‐phase functionalization duration (0.5–5 h) controls the surface oxygen concentration. A simple rate model is proposed to account for its increase. Copyright © 2015 John Wiley & Sons, Ltd.     

Radiation-induced decomposition of the tributyl phosphate-nitric acid system: Role of nitric acid

Radiation-induced decomposition of tributyl phosphate-nitric acid as a two-component system has been studied. Degradation products, dibutylphosphoric acid (DBP) and monobutylphosphoric acid (MBP), were determined by separation-extraction method. 0.59, 0.78 and 1.38 are the G (DBP) values and 0.15, 0.17 and 0.13 are the G (MBP) values obtained for pure TBP, TBP-3M HNO₃ extract and TBP-5M HNO₃ extract, respectively. G (–HNO₃) values are 5.19 and 6.15 for 3M HNO₃ and 5M HNO₃ extracts. It is shown that nitric acid plays a significant role in enhancing the decomposition of TBP.     

Effects of water on the activity of Tri-n-butylphosphate in the H2O-diluent system

This paper presents a model of the formation of hydrated and solvated ionic pair, nonhydrated monosolvate HNO₃ · TBP (tri-n-butylphosphate), hydrated disolvate HNO₃ · 2TBP, and semisolvate 2HNO₃ · TBP, to which an unlimited number of HNO₃ molecules can be added. The equilibrium was calculated using mole fractions. To calculate the mole fraction of free (not bonded to solvates) water, we suggested an equation containing four parameters, three of which are determined from the data for the independent TBP-H₂O-diluent system.     

Effect of L64 on the Phase Behavior of 1-Dodecyl-3-methylimidazolium Chloride/Water System

Phase behavior of ternary system involving surfactant‐like ionic liquid 1‐dodecyl‐3‐methylimidazolium chloride ([C₁₂mim]Cl), water, and nonionic surfactant PEO‐PPO‐PEO block copolymer (Pluronic L64) is investigated at 25°C. Hexagonal (H₁) and lamellar liquid crystal phase (Lα) are found in [C₁₂mim]Cl/H₂O/L64 system by using polarized optical microscopy (POM), small‐angle X‐ray scattering (SAXS) techniques and ²H NMR spectra. The phase structure (H₁ phase), which is formed in [C₁₂mim]Cl/H₂O binary system, is not changed when L64 with a low concentration is added. However, phase transitions will occur from hexagonal to multiphases of H₁ and cubic phases (C), then to Lα+C phases with constant [C₁₂mim]Cl/H₂O ratio and increasing L64 concentration. Moreover, at given L64 (5%, 20%) concentration, the lattice parameter of H₁ or Lα phase decreases with increasing [C₁₂mim]Cl/H₂O ratio. Fourier transform infrared (FTIR) spectra indicate that the H‐bonded network comprising an imidazolium ring, chloride ion and water formed in [C₁₂mim]Cl/H₂O binary system is disrupted upon addition of L64. This is helpful to the phase transition, due to the decreasing of interfacial curvature induced by dehydration of hydrated layer after the addition of PEO block of L64.     

Determination of plutonium in environmental samples by controlled valence in aniion exchange

The title method was successfully used for collecting^239,249Pu from 200 litres of seawater by coprecipitation with 16 g FeSO₄·7H₂O under redcing conditions witout filtering. The plutonium is leached by concentrate HNO₃+HCl from the coprecipitate and the solid particles. The precipitate is heated at 400°C and digested in aqua regia. Na₂SO₃ and NaNO₂ have been applied to obtain the Pu⁴⁺ valence state in 0.5–1N HNO₃ for different samples. Plutonium and thorium are coadsorbed on anionic resin from 8N HNO₃. The column is eluted with 8N HNO₃ containing fresh NaNO₂ to keep the Pu⁴⁺ state for uranium decontaination. The system of the column is changed from 8N HNO₃ to concentrated HCl with 50 ml concentrated HCl containing a few milligrams of NaNO₂. Furtheer decontaimination of torium was achieved by elution with concentrated HCl instead of 9N HCl. The plutonium is successfully stripped by H₂O, NaOH, 2N HNO₃ and 0.5N HNO₃ containign 0.01M NaNO₃. The chemica yield of plutonium for a 2001 seawate sample is 60–80%. The resolution of the electroplated thin source is very good.     

Complexation of uranium(VI) with acetohydroxamic acid

The advanced separation extraction process based on tri-n-butyl phosphate organic phase called UREX is being developed to separate uranium from fission products and other actinides, and the acetohydroxamic acid (AHA) is employed to reduce and complex plutonium and neptunium in order to decrease their distribution to the TBP-organic phase. In this study, the extraction of uranium was performed from various aqueous matrices with different concentrations of HNO₃, LiNO₃, and AHA. Extraction of uranium increases with increasing both initial HNO₃ and total nitrate concentration. UV-VIS spectrophotometry confirmed that AHA is involved in the complex of uranium with TBP.     

Cation chromatography on stannic tungstate papers: Quantitative separation of vanadium from iron,titanium, zirconium and thorium

Summary A systematic study of the chromatography of metal ions on stannic tungstate papers has been performed using acetone-HNO₃–H₂O systems. The effect of mole fractions of acetone, HNO₃ and H₂O on the R_f values of the metal ions has been discussed in detail and a relationship between R_f and mole fraction (X) of the solvent has been obtained as R_f=mX+C. The usefulness of the study has been demonstrated by the specific extraction of titanium and thorium in HNO₃H₂O (12) and HNO₃:acetone:H₂O (161) systems. In addition, some binary and ternary separations of metal ions have also been achieved on these papers.     

Investigation of foam properties in some extraction systems with TBP in kerosene and in carbon tetrachloride

Using the nephelometric sedimentation analytical method, the emulsions dispersity was investigated. These emulsions were formed in a centrifugal extractor mixing chamber with different extraction systems: TBP in kerosene—HNO₃ and TBP in CCl₄−HNO₃. The TBP and HNO₃ concentration, the speed of rotation and the supply of the mixing chamber with the phases stream influence on the histeresis loop of the emulsion type and the emulsion dispersity was described. The foaminess of extraction systems was investigated, and the stabilizing influence of w/o emulsions on the foaminess was confirmed.     

Kinetic studies on the extraction of U(IV) by TBP in kerosene from nitrate medium

The kinetics of extraction of U(IV) by TBP in kerosene was investigated using a stirred Lewis cell. The effect of the different parameters affecting the extraction rate as well as temperature were separately investigated. The rate equation deduced from the experimental results show that the extraction of U(IV) is first order dependent on TBP concentration while it is of zero order with respect to U(IV), H⁺, NO ₃ ^– and HNO₃ concentrations. The data obtained show that the extraction process is governed by chemical reactions taking place at teh interface.     

Monotonic transfer annealing kinetics associated with an oscillatory phenomenon in51Cr(III)-doped potassium chromate

Infrared absorption spectra of HNO₃ solutions in UO₂(NO₃)₂(TBP)₂ have been taken. The formation of a hydrogen bond between HNO₃ and nitrate or phosphoryl group in UO₂(NO₃)₂(TBP)₂ has been established. On extracting Pu(IV) and Np(IV) by 30% TBP-dodecane, dependence of the distribution coefficients on concentration has been found at UO₂(NO₃)₂ concentrations in the aqueous phase upwards from 0.4M. This dependence appeared in the temperature interval 0–60°C. Such effects may be caused by ordered structure of saturated uranyl nitrate solutions in TBP.