The separation of americium(III) from europium(III) by two new 6,6'-bistriazinyl-2,2'-bipyridines in different diluents

The synthesis and extraction of americium(III) and europium(III) from aqueous nitric acid solutions by the new BTBP ligands 6,6’-bis(5,5,7,7- tetramethyl-5,7-dihydrofuro[3,4-e]-1,2,4-triazin-3-yl)-2,2’-bipyridine (Cy5-O-Me4-BTBP), and 6,6’-bis(5,5,7,7-tetramethyl-5,7-dihydrothieno[3,4-e]-1,2,4-triazin-3-yl)- 2,2’-bipyridine (Cy5-S-Me4-BTBP) is described. The affinity for Am(III) and the selectivity for Am(III) over Eu(III) of Cy5-S-Me4-BTBP were generally higher than for Cy5-O-Me4-BTBP. For both ligands, the extraction of Am(III) and Eu(III) from 3 M HNO3 into 3 mM organic solutions varied with the diluent used. The highest distribution ratios and separation factors observed were in cyclohexanone and 2-methylcyclohexanone, respectively. For Cy5-S-Me4-BTBP, there is a strong correlation between the distribution ratio for Am(III) and the permittivity of the diluent used. With 1-octanol as the diluent, low distribution ratios (D(Am) < 1) were observed for Cy5-S-Me4-BTBP although this ligand extracts Am(III) selectively (SFAm/Eu = 16-46 from 1-4 M HNO3). For Cy5-S-Me4-BTBP, Am(III) is extracted as the disolvate. The distribution ratios for Am(III), and the separation factors for Am(III) over Eu(III) are both significantly higher for CyMe4-BTBP than they are for Cy5-O-Me4-BTBP and Cy5-S-Me4-BTBP in cyclohexanone. Changing the diluent from cyclohexanone to 2-methylcyclohexanone leads to a decrease in D(Am) but an increase in SFAm/Eu for Cy5-S-Me4-BTBP.

Complexation of lanthanides, actinides and transition metal cations with a 6-(1,2,4-triazin-3-yl)-2,2′:6′,2′′-terpyridine ligand: implications for actinide(III)/lanthanide(III) partitioning

The quadridentate N-heterocyclic ligand 6-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydro-1,2,4-benzotriazin- 3-yl)-2,2′ : 6′,2′′-terpyridine (CyMe4-hemi-BTBP) has been synthesized and its interactions with Am(III),U(VI), Ln(III) and some transition metal cations have been evaluated by X-ray crystallographic analysis, Am(III)/Eu(III) solvent extraction experiments, UVabsorption spectrophotometry, NMR studies and ESI-MS. Structures of 1 : 1 complexes with Eu(III), Ce(III) and the linear uranyl (UO2 2+) ion were obtained by X-ray crystallographic analysis, and they showed similar coordination behavior to related BTBP complexes. In methanol, the stability constants of the Ln(III) complexes are slightly lower than those of the analogous quadridentate bis-triazine BTBP ligands, while the stability constant for the Yb(III)complex is higher. 1H NMR titrations and ESI-MS with lanthanide nitrates showed that the ligand forms only 1 : 1 complexes with Eu(III), Ce(III) and Yb(III), while both 1 : 1 and 1 : 2 complexes were formed with La(III) and Y(III) in acetonitrile. A mixture of isomeric chiral 2 : 2 helical complexes was formed with Cu(I), with a slight preference (1.4 : 1) for a single directional isomer. In contrast, a 1 : 1 complex was observed with the larger Ag(I) ion. The ligand was unable to extract Am(III) or Eu(III) from nitric acid solutions into 1-octanol, except in the presence of a synergist at low acidity. The results show that the presence of two outer 1,2,4-triazine rings is required for the efficient extraction and separation of An(III)from Ln(III) by quadridentate N-donor ligands.

Influence of diluent alkyl substitution on the extraction of Am(III) and Eu(III) by a 6,6'-bis(1,2,4-triazinyl)-2,2'-bipyridine ligand dissolved in alkylated cyclohexanone diluents

Several alkylated cyclohexanones were investigated as potential diluents for the selective extraction of Am(III) and Eu(III) from nitric acid solutions by the CyMe4-BTBP ligand. No significant extraction of either of the metal ions was observed for these diluents themselves. In the extractions from 1 M HNO3, 3-methylcyclohexanone and 4-methylcyclohexanone gave comparable results to cyclohexanone whereas in the extractions from 4 M HNO3, 2-methylcyclohexanone, 3-methylcyclohexanone and 4-methylcyclohexanone all gave superior results. For the monomethylated diluents, DAm and SFAm/Eu decreased in the order of alkyl substitution 2 > 4 ~ 3. However, alkyl substitution of cyclohexanone significantly slows down the extraction kinetics compared to cyclohexanone, and the position of alkyl substitution was found to play an important role in the solvents properties. 3-Methylcyclohexanone was identified as the most promising of the diluents.

From BTBPs to BTPhens: the effect of ligand pre-organization on the extraction properties of quadridentate bis-triazine ligands

The synthesis, lanthanide complexation and solvent extraction of An(III) and Ln(III) radiotracers from nitric acid solutions by a pre-organized, phenanthroline-derived bis-triazine ligand CyMe4-BTPhen are described. It was found that the ligand separated Am(III) and Cm(III) from the lanthanides with remarkably high efficiency, high selectivity, and faster extraction kinetics compared to its 2,2’-bipyridine counterpart CyMe4-BTBP. The origins of the ligands extraction properties were established by a combination of solvent extraction experiments, X-ray crystallography, kinetics and surface tension measurements and lanthanide NMR spectroscopy.

Evaluation of sample preparation procedures and krypton as an interference standard probe for arsenic speciation by HPLC-ICP-QMS

Different conditions of extraction using water, a methanol-water mixture and nitric acid solutions were evaluated for speciation of As(iii), As(v), DMA and MMA in plant samples that previously received As(v) after being sown and emergence was investigated. Microwave-assisted extraction (MAE) using diluted nitric acid solutions was also performed for arsenic extraction from chicken feed samples. The separation and determination of arsenic species were performed using HPLC-ICP-MS. The interference standard method (IFS) using 83Kr+ as the IFS probe was employed to minimize spectral interferences caused by polyatomic species, such as 40Ar 35Cl+. The extraction procedures tested presented adequate extraction efficiencies (90%), and the four arsenic species evaluated were found in plant samples. Extractions with diluted nitric acid solution at 90 °C were the most efficient strategy, with quantitative recoveries for all four As species in plant tissues. On the other hand, the methanol-water mixture was the solvent with the lowest extraction efficiency (50-60%). For chicken feed samples, MAE at 100 °C for 30 min resulted in an extraction efficiency of 97% and only As(v) was found, without any species interconversion. The IFS method contributed to improving precision and limits of detection and quantification for all tested extraction procedures. Significant improvements on accuracy were obtained by applying the IFS method and recoveries between 77 and 94%, and 82 and 93% were obtained for plant extracts and chicken feed samples, respectively. This journal is © 2013 The Royal Society of Chemistry.

Ammonium diuranate precipitation with anhydrous ammonia /

Ammonium diuranate has been precipitated from nitric acid solutions by the addition of anhydrous ammonia on both laboratory and production scales. This process produced more dense and more rapidly filtered precipitates than those formed by the addition of aqueous ammonia or slurried calcium hydroxide. The filtrates from the anhydrous ammonia process were lower in uranium content than those obtained by the addition of the other reagents. Processing equipment and precipitate characteristics are discussed.

Thermal reactivity of ammonium perchlorate crystallised from solutions having different pH

The thermal reactivity of ammonium perchlorate was found to be dependent on the pH of the solution from which it had been crystallised. A nitric acid-crystallised sample reacted faster than an ammonium hydroxide-crystallised one.

The equivalent conductance of solutions of picric acid

Picric acid possesses the property, which is rare among strong electrolytes, of having a convenient distribution ratio between water and certain organic solvents such as benzene, chloroform, etc. Because of this property, picric acid offers peculiar advantages for studying the well known deviations of strong electrolytes from the law of mass action, for; by means of distribution experiments, the activities of picric acid in various aqueous solutions may be compared.

In order to interpret the results of such distribution experiments, it is necessary to know the degree of ionization of picric acid in aqueous solutions.

At least three series of determinations of the equivalent conductance of picric acid have been published, but the results are not concordant; and therefore, the degree of ionization cannot be calculated with any degree of certainty.

The object of the present investigation was to redetermine the conductance of picric acid solutions in order to obtain satisfactory data from which the degrees of ionization of its solutions might be calculated.

Non-spectral interferences due to the presence of sulfuric acid in inductively coupled plasma mass spectrometry

Results of a systematic study concerning non-spectral interferences from sulfuric acid containing matrices on a large number of elements in inductively coupled plasma–mass spectrometry (ICP-MS) are presented in this work. The signals obtained with sulfuric acid solutions of different concentrations (up to 5% w w− 1) have been compared with the corresponding signals for a 1% w w− 1− nitric acid solution at different experimental conditions (i.e., sample uptake rates, nebulizer gas flows and r.f. powers). The signals observed for 128Te+, 78Se+ and 75As+ were significantly higher when using sulfuric acid matrices (up to 2.2-fold for 128Te+ and 78Se+ and 1.8-fold for 75As+ in the presence of 5 w w-1 sulfuric acid) for the whole range of experimental conditions tested. This is in agreement with previously reported observations. The signal for 31P+ is also higher (1.1-fold) in the presence of sulfuric acid. The signal enhancements for 128Te+, 78Se+, 75As+ and 31P+ are explained in relation to an increase in the analyte ion population as a result of charge transfer reactions involving S+ species in the plasma. Theoretical data suggest that Os, Sb, Pt, Ir, Zn and Hg could also be involved in sulfur-based charge transfer reactions, but no experimental evidence has been found. The presence of sulfuric acid gives rise to lower ion signals (about 10–20% lower) for the other nuclides tested, thus indicating the negative matrix effect caused by changes in the amount of analyte loading of the plasma. The elemental composition of a certified low-density polyethylene sample (ERM-EC681K) was determined by ICP-MS after two different sample digestion procedures, one of them including sulfuric acid. Element concentrations were in agreement with the certified values, irrespective of the acids used for the digestion. These results demonstrate that the use of matrix-matched standards allows the accurate determination of the tested elements in a sulfuric acid matrix.

BDST modelling of sodium ion exchange column behaviour with strong acid cation resin in relation to coal seam water treatment

Reverse osmosis is the dominant technology utilized for desalination of saline water produced during the extraction of coal seam gas. Alternatively, ion exchange is of interest due to potential cost advantages. However, there is limited information regarding the column performance of strong acid cation resin for removal of sodium ions from both model and actual coal seam water samples. In particular, the impact of bed depth, flow rate, and regeneration was not clear. Consequently, this study applied Bed Depth Service Time (BDST) models to reveal that increasing sodium ion concentration and flow rates diminished the time required for breakthrough to occur. The loading of sodium ions on fresh resin was calculated to be ca. 71.1 g Na/kg resin. Difficulties in regeneration of the resin using hydrochloric acid solutions were discovered, with 86% recovery of exchange sites observed. The maximum concentration of sodium ions in the regenerant brine was found to be 47,400 mg/L under the conditions employed. The volume of regenerant waste formed was 6.2% of the total volume of water treated. A coal seam water sample was found to load the resin with only 53.5 g Na/kg resin, which was consistent with not only the co-presence of more favoured ions such as calcium, magnesium, barium and strontium, but also inefficient regeneration of the resin prior to the coal seam water test.

Studies in the polarography of metal-amino acid complexes - Part I. Cadmium

1. A detailed polarographic study of cadmium has been made employing glycine, α-alanine, β-alanine, valine, aspartic acid, glutamic acid and asparagine as complexing agents at various pH values. The effect of incorporating sodium hydroxide, sodium carbonate and ammonium nitrate + ammonium hydroxide, on the polarographic behaviour of amino acid complexes of cadmium has also been investigated. 2. The reduction process has been found to be reversible in all systems. 3. The small shifts in the half-wave potentials noticed due to increase in the concentration of sodium hydroxide and sodium carbonate in presence of amino acids have been explained on the basis of formation of mixtures of pure and mixed amino acid complexes of cadmium. Mixed complexes have also been noticed in presence of ammonium hydroxide and ammonium nitrate and amino acids. 4. Polarographic evidence has been obtained for the formation of over 30 pure and mixed complexes. The dissociation constant Kd, the Δ F° value for the dissociation, and standard potential value for the formation, of each complex have been computed. 5. It has been found that cadmium can be polarographically estimated in amino acid solutions.

Low temperature synthesis and hcaracterization of Ag2S1-x Tez(O

A low-temperature route for the synthesis of Ag2S,Ag2Te and their solid solutions Ag2S1-xTex(0 less-than-or-equal-to x less-than-or-equal-to 1) is reported. Ag2S is prepared by the direct addition of silver nitrate solution to thiourea, while Ag2Te is prepared by reacting silver nitrate solution with tellurium in nitric acid and subsequently reducing it with hydrazine hydrate. The solid solutions of Ag2S and Ag2Te are obtained by the addition of nitrate solutions of silver and tellurium to thiourea followed by its reduction with hydrazine hydrate. The method enables the synthesis of low-temperature crystalline phase of Ag2S1-xTex solid solutions. The powder X-ray diffraction studies suggest that the solid solutions of compositions x < 0.3 have a phase akin to alpha-Ag2S and those with compositions x > 0.6 are similar to alpha-Ag2Te. In the intermediate range of compositions (x = 0.4 and 0.5), the solid solutions are found to be mixtures of alpha-Ag2S and alpha-Ag2Te phases which transform totally to alpha-Ag2S phase on prolonged annealing at about 473 K.

Volume Change behaviour in Calcitic Soil influenced with Sulphuric Acid using Artificial Neural Networks

This paper elucidates the methodology of applying artificial neural network model (ANNM) to predict the percent swell of calcitic soil in sulphuric acid solutions, a complex phenomenon involving many parameters. Swell data required for modelling is experimentally obtained using conventional oedometer tests under nominal surcharge. The phases in ANN include optimal design of architecture, operation and training of architecture. The designed optimal neural model (3-5-1) is a fully connected three layer feed forward network with symmetric sigmoid activation function and trained by the back propagation algorithm to minimize a quadratic error criterion.The used model requires parameters such as duration of interaction, calcite mineral content and acid concentration for prediction of swell. The observed strong correlation coefficient (R2 = 0.9979) between the values determined by the experiment and predicted using the developed model demonstrates that the network can provide answers to complex problems in geotechnical engineering.

I. The rate and mechanism of the vapor-phase reaction between water and parts-per-million concentrations of nitrogen dioxide. II. The rate and mechanism of the air oxidation of parts-per-million concentrations of nitric oxide in the presence of water vapor.

Part I

A study of the thermal reaction of water vapor and parts-per-million concentrations of nitrogen dioxide was carried out at ambient temperature and at atmospheric pressure. Nitric oxide and nitric acid vapor were the principal products. The initial rate of disappearance of nitrogen dioxide was first order with respect to water vapor and second order with respect to nitrogen dioxide. An initial third-order rate constant of 5.5 (± 0.29) x 10⁴ liter² mole^-2 sec^-1 was found at 25˚C. The rate of reaction decreased with increasing temperature. In the temperature range of 25˚C to 50˚C, an activation energy of -978 (± 20) calories was found.

The reaction did not go to completion. From measurements as the reaction approached equilibrium, the free energy of nitric acid vapor was calculated. This value was -18.58 (± 0.04) kilocalories at 25˚C.

The initial rate of reaction was unaffected by the presence of oxygen and was retarded by the presence of nitric oxide. There were no appreciable effects due to the surface of the reactor. Nitric oxide and nitrogen dioxide were monitored by gas chromatography during the reaction.

Part II

The air oxidation of nitric oxide, and the oxidation of nitric oxide in the presence of water vapor, were studied in a glass reactor at ambient temperatures and at atmospheric pressure. The concentration of nitric oxide was less than 100 parts-per-million. The concentration of nitrogen dioxide was monitored by gas chromatography during the reaction.

For the dry oxidation, the third-order rate constant was 1.46 (± 0.03) x 10⁴ liter² mole^-2 sec^-1 at 25˚C. The activation energy, obtained from measurements between 25˚C and 50˚C, was -1.197 (±0.02) kilocalories.

The presence of water vapor during the oxidation caused the formation of nitrous acid vapor when nitric oxide, nitrogen dioxide and water vapor combined. By measuring the difference between the concentrations of nitrogen dioxide during the wet and dry oxidations, the rate of formation of nitrous acid vapor was found. The third-order rate constant for the formation of nitrous acid vapor was equal to 1.5 (± 0.5) x 10⁵ liter² mole^-2 sec^-1 at 40˚C. The reaction rate did not change measurably when the temperature was increased to 50˚C. The formation of nitric acid vapor was prevented by keeping the concentration of nitrogen dioxide low.

Surface effects were appreciable for the wet tests. Below 35˚C, the rate of appearance of nitrogen dioxide increased with increasing surface. Above 40˚C, the effect of surface was small.

Reversed micellar solubilization extraction and separation of thorium(IV) from rare earth(III) by primary amine N1923 in ionic liquid

The extraction behavior of thorium(IV) sulfate by primary amine N1923 in imidazolium-based ionic liquid (IL) namely 1-octyl-3-methylimidazolium hexafluorophosphate ([C(8)mim]PF6) was systematically studied in this paper. Results showed that the extraction behavior was quite different from that using conventional solvent as diluent. A reversed micellar solubilization extraction mechanism was proposed for the extraction of thorium(IV) by N1923/[C(8)mim]PF6 via slope analysis method and polarized optical microscopy (POM)/transmission electron microscopy (TEM) observation. The salt-out agent, Na2SO4, was demonstrated to prompt this extraction mechanism.