The thermal degradation of some alkali metal salts of poly(itaconic acid)

The Li-, Na- and K salts of poly(itaconic acid) (PIA) were prepared by treating the polyacid with the corresponding aqueous hydroxide.The resulting polysalts were analyzed by elemental analysis, FTIR spectroscopy and thermogravimetry. The results indicate that the polysalts are thermally more stable than the parent PIA, they all degrade in a similar manner and somewhat more complexly than the poly(methacrylic acid) salts.     

The intensity of spontaneous surface convection in di-(2-ethylhexyl)phosphoric acid systems

The dependence of the rate of the arising and evolution of spontaneous surface convection (SSC) on various effects during the extraction of rare-earth metals (REMs) with heptane (or toluene) solutions of di-(2-ethylhexyl)phosphoric acid (D2EHPA) (HA) was studied. The intensity of SSC in heptane was higher than in toluene systems. In the same solvent, it was higher for the elements from the cerium subgroup. At low concentrations of a REM salt in the starting aqueous solution, the modulus of the surface rate of liquid flow in the dynamic interphase layer (DIL) was high because low-solubility salt particles experienced sedimentation, and the interphase surface was renewed. It was concluded that, at higher REM concentrations in the aqueous phase, the modulus of the surface flow rate was considerably higher because of the accumulation of LnA₃ and structure formation in the interphase layer. For comparison, we give the moduli of surface flow rates of liquids during the re-extraction of acids in a toluene, HNO₃/water system, in which the rate is higher than in aqueous REM(III) salt/D2EHPA solution in an organic diluent. Original Russian Text ? N.F. Kizim, E.N. Golubina, 2009, published in Zhurnal Fizicheskoi Khimii, 2009, Vol. 83, No. 7, pp. 1384–1390.     

Mass spectrometric study of the radiolysis of di-(2-ethylhexyl)phosphoric acid

A mass spectrometric study on DEHPA was carried out and compared with radiolysis data on DEHPA for γ-irradiation in the liquid phase. The mass spectra of DEHPA show an extremely low intensity of parent ion and the presence of double rearrangement ions of (RO)P(OH) ₃ ⁺ and P(OH) ₄ ⁺ , where R is the 2-ethylhexyl group. The appearance potentials of the principal ions in the mass spectrum were determined and the dissociation processes of DEHPA in the phase discussed. The fragment ions show good agreement with the results in the liquid phase where the mono-ester, orthophosphoric acid, octane and heptane were formed by the dealkylation, however, the peak intensities of some fragment ions in the mass spectrum differ from the radiolytic yields of the corresponding products. These differences imply the significant role of neutralization and recombination reactions in the liquid phase radiolysis.     

Determinations of traces of calcium in phosphoric acid and its salts by atomic-absorption spectrometry

A method for the determination of traces of calcium by atomic-absorption spectrometry after extraction into an organic solvent, has been investigated for the determination of traces of calcium in phosphoric acid and its salts. Calcium is extracted as the hydroxy-quinolate complex, the extract is introduced into the flame, and the calcium atomic-absorption is measured. The effects of pH, concentration of reagent, and diverse ions on the calcium extraction were investigated.     

Kinetic studies on the extraction of uranium(VI) from phosphoric acid medium by bulk liquid membrane containing di-2-ethylhexyl phosphoric acid

To go through the first stage of industrial solvent extraction process in order to recover uranium from phosphate rocks by liquid membrane techniques, as a simple model, the kinetics of facilitated transport of uranium(VI) from a dilute phosphoric acid medium into more concentrated phosphoric acid media as a receiving phase through a bulk liquid membrane containing di-2-ethylhexyl phosphoric acid as a carrier was studied. The influence of phosphoric acid concentration in the source and receiving phases, carrier concentration, type of solvent, stirring speed and temperature were investigated. The kinetic parameters (k _e, k _s, t _max, J _max) were calculated for the interface reactions assuming two consecutive, irreversible first-order reactions. The activation energy values were calculated as 29.40 and 19.51 kJ mol^?1 for extraction and stripping, respectively. The values of calculated activation energy indicated that both the extraction and stripping processes were controlled by mixed regime (both kinetic and diffusion). In addition, the influence of adding trioctyl-phosphine oxide into the membrane phase as a synergic agent on the transport kinetics was determined.     

The preparation of mono- and di-[4-(n-octyl)phenyl]- and -[4-(1,1,3,3-tetramethylbutyl)phenyl]phosphoric acids for use in PVC calcium ion-selective electrodes

The synthesis of mono- and di-[4-(n-octyl)phenyl] phosphoric acids, and mono- and di-[4-(1,1,3,3-tetramethylbutyl)phenyl]phosphoric acids and their calcium salts are described as well as certain, IR, NMR, pK_a, and chromatographic characteristics.     

PVC ion-selective electrodes based on calcium bis-[dialkyl- and di-(4-alkylphenyl) phosphates] and mixed solvent mediators

PVC calcium ion-selective electrodes based on either calcium bis-di(n-decyl)phosphate or calcium bis-di[4-(1,1,3,3-tetramethylbutyl)phenyl]phosphate with various solvent mediators (alone or in pairs) have been evaluated with particular respect to interference from Na(+), K(+), Mg(2+), Sr(2+), Ba(2+), Mn(2+), Cu(2+), Ni(2+) and Zn(2+) ions. PVC calcium ion-selective electrodes based on calcium bis-di[4-(n-octyl)phenyl]phosphate with varied amounts of decan-l-ol plus di-n-octyl phenylphosphonate showed a continuous gradation in selectivity coefficients on going from a high fraction of decan-l-ol to a high fraction of the second mediator. Thus, k(pot)(Ca,Mg) changed from 1.6 for an electrode based exclusively on decan-l-ol to 4.9 x 10(-4) for one based completely on di-n-octyl phenylphosphonate. The corresponding k(pot)(Ca,Na) values were 7.0 x 10(-2) and 1.1 x 10(-3).     

Solvent extraction of neodymium,europium and thulium by di-(2-ethylhexyl)phosphoric acid

The extraction of Na³⁺, Eu³⁺ and Tm³⁺ by di-(2-ethylhexyl)phosphoric acid, HDEHP has been studied from various aqueous acidic solutions. The extraction of these elements is inversely proportional to the third power of the hydrogen ion concentration. Antagonistic effects were observed when the extraction was studied by mixtures of HDEHP and tributyl phosphate, TBP, or trioctylphosphine oxide, TOPO. The presence of water-miscible alcohols and acetone generally increases the extraction of these three elements from HCl solutions. Reaction mechanisms have been suggested and discussed in the light of the data obtained.     

Studies on the solvent extraction behaviour of Pu(IV) from sulfuric acid medium into di-2-ethylhexyl phosphoric acid (HDEHP)

Extraction of plutonium(IV) from aqueous sulfuric and sulfuric-nitric acid into di-2-ethylhexyl phosphoric acid (HY) in the diluents n-dodecane, toluene or chloroform has been investigated. The composition of the Pu(IV) species extracted from H₂SO₄ was found to be PuH₂Y₆, which changed to Pu(NO₃)H₂Y₅ and Pu(NO₃)₂H₂Y₄ with increasing concentration of nitrate ion in the aqueous medium. These three species can be represented as PuY₂(HY₂)₂, Pu(NO₃)Y(HY₂)₂ and Pu(NO₃)₂(HY₂)₂, respectively, where Y represents the anion of monomeric HY, and HY₂ the anion of dimeric H₂Y₂. Synergism in the extraction of Pu(IV) by the addition of thenoyltrifluoroacetone (HTTA) to HY was also investigated and attributed to extraction of the additional species, Pu(TTA)Y(HY₂)₂ and Pu(TTA)₂(HY₂)₂. The addition of the neutral extractant tri-n-octylphosphine oxide (TOPO) to HY did not result in synergism in the extraction of Pu(IV) from aqueous sulfuric acid. With aqueous nitric acid under similar conditions, however, synergism was observed. The possible equilibria in these systems were identified and the corresponding equilibrium constants were determined.     

Effect of radiolysis products of di-(2-ethylhexyl)phosphoric acid upon the extraction of lanthanides

In order to clarify the influence of radiation degradation of DEHPA upon the extraction of lanthanides, the extraction of neodymium(III) was studied using DEHPA, MEHPA, 2-ethylhexanol and γ-ray irradiated DEHPA. The most significant effect of DEHPA radiolysis on the extraction was found to be the enhacement of extraction capability mainly due to the primary radiolysis product MEHPA. 2-Ethylhexanol, another radiolysis product, showed a depressant effect on DEHPA-Nd(III) extraction. However, the mixture of MEHPA and 2-ethylhexanol improved the extraction. The mixed solvent DEHPA-MEHPA was found to be more effective than the individual components for lanthanide extraction.     

Extraction chromatographic separation of uranium and fission products in the system di-(2-ethylhexyl)phosphoric acid-hydrochloric acid

An elution scheme has been developed for obtaining separate fission product and uranium fractions using extraction chromatographic techniques with di-(2-ethylhexyl)phosphoric acid as a stationary phase and HCl of varying concentration as eluting agent. The investigations have been concentrated on the fission products cerium, europium, molybdenum and zirconium. The elution of zirconium by oxalic acid is characterized by a peak broadening and has been explained by considering extraction kinetics. Experiments on column performance with different support materials have proved Ftoroplast-4 and Celite Hyflo Super Cel to be capable of giving column fillings with equal separation ability.     

Determination of radiocerium in fission products by extraction chromatography using di-(2-ethylhexyl)phosphoric acid

An extraction chromatographic method is described for the determination of cerium in a fission product mixture. Cerium(IV) is separated on a column of siliconized kieselguhr saturated with di-(2-ethylhexyl)phosphoric acid (HDEHPA). After washing the column with a mixture of sodium bromate and nitric acid, cerium is eluted by a mixture of 5M HNO₃ and 0.1M ascorbic acid. The optimum conditions for the quantitative sorption and elution of cerium were found, and the reproducibility of the yield was verified. The influence of other fission and corrosion products (Mg, Fe, Al, U) on the sorption and elution of cerium was studied. The method has been successfully applied for the determination of cerium in artificial and natural mixtures of fission products.     

Synthesis of hydroxyapatite by using calcium carbonate and phosphoric acid in various water-ethanol solvent systems

The purpose of the present study is to synthesize hydroxyapatite by using CaCO₃ and H₃PO₄ in various water-ethanol solvent systems. It was observed from experiments that formation of ammonium phosphate compounds hindered the formation of calcium phosphates in ethanol medium. Although the reactivity was better in aqueous medium, the carbonate contents of the products obtained were above 8.5%. Best results with a carbonate content as low as 3.82% was obtained in 50% ethanol containing mixed-aqueous medium at 80°C and the FTIR analysis showed that the product was a carbonated apatite with a calculated composition of 14CaO·4.2P₂O₅·CO₃·7.2H₂O. The amorphous and porous phosphate compound obtained with a BET surface area of 106.6 m² g⁻¹ seems to be useful as adsorbent in wastewater treatment. Upon sintering of the amorphous product at 750°C, crystalline hydroxyapatite with a BET surface area of 25.9 m² g⁻¹ is obtained that may be used in biomedical applications.      

Influence of rare earth elements on extraction of actinium with di-(2-ethylhexyl)phosphoric acid from inorganic acid solutions

The extraction of actinium by HDEHP solutions in n-heptane as a function of mineral acids and some lanthanides (Ln) in the aqueous phase has been studied. It was found that the actinium extraction coefficient in the absence of Ln decreased linearly with acid concentration with the slope of –3 in the whole investigated range of its concentration. In the presence of Ln the extraction coefficient decreased with a smaller slope than in the absence of Ln. This slope decreased with the Ln salt concentration. The extraction coefficient of Ac decreased with a slope of –3 at acid concentrations above 0.1N, regardless of the Ln concentration in the extraction system.     

Mono- and di-(2-nitroguanidino)benzenes and some of their amino and nitro derivatives

A method was developed for the synthesis of mono- and di-(2-nitroguanidino)benzenes and some of their amino and nitro derivatives, based on the reaction of aniline and phenylenediamines with S-methylisothionitrourea, followed by oxidation of the aminophenyl-2-nitroguanidines or by nitration of aryl-2-nitroguanidines. It was shown that o-phenylenediamine reacts with S-methylisothionitro-urea to form 2-nitraminobenzimidazole.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2581–2587, November, 1991.     

The solubility of tri-n-octylamine in water and phosphoric acid solutions

The solubility of tri-n-octylamine (TOA) in water and phosphoric acid is reported. Equilibration is achieved by circulating the solutioin through PVC pieces saturated with the absorbed amine in a glass tube. The dissolved TOA is determined by capillary gas chromatography which can detect amine concentrations down to 10 μg l^?1. The solubility of TOA in water is 0.039 mg l^?1 and in 5.5 M phosphoric acid 0.82 mg l^?1; these values are much lower than those reported in the literature.     

A Raman investigation of some metal (II) hexafluorosilicate (IV) and hexafluorotitanate (IV) salts

Raman data on M(II)(H₂O)₆SiF₆ (MNi, Fe, Mg, Zn) and M(II)(H₂O)₆TiF₆ (MNi, Zn) are presented. The results allow a positive identification of the symmetric MO stretch for the first time in these salts; other band assignments are also discussed. Low temperature (300⩽TK⩽15) results are also presented and a discussion of the mechanism of the phase transition at 120 K in NiTiF₆·6H₂O is given. It is shown that the phase transition in this salt has a different origin from that in the hexafluorosilicate salts.     

Extraction of certain actinide and lanthanide elements from different acid media by polyurethane foams loaded with di-(2-ethylhexyl)phosphoric acid (HDEHP)

The effect of added TBP on the extraction of uranium(VI) with a solution of di-(2-ethylhexyl)-phosphoric acid (HDEHP) in o-dichlorobenzene from nitric acid solutions has been investigated at varying concentrations of nitric acid, HDEHP, TBP and uranium(VI). The mechanism of the synergistic effect of TBP is discussed on the basis of the results and can be summarized in the following equation: UO _2(aq) ²⁺ +0.67(HX)_3(o)+2TBP_(o)UO₂X₂·2TBP_(o)+2H _(aq) ⁺ where HX denotes HDEHP and the HDEHP loaded on the foam is trimerized.