Synergistic extraction of uranyl ion with 1-phenyl-3-methyl-4-benzoylpyrazolone-5 (HPMBP) and diphenyl sulfoxide (DPSO), tri-n-butyl phosphate (TBP) or tri-n-octylphosphine oxide (TOPO)

Synergistic extraction of uranyl ion with 1-phenyl-3-methyl-4-benzoyl-pyrazolone-5 (HPMBP) and oxo donors with widely varying basicity, viz. diphenyl sulfoxide (DPSO), tri-n-butyl phosphate (TBP) and tri-n-octylphosphine-oxide (TOPO) has been studied at various fixed temperatures. Results indicate that the equilibrium constants in the organic phase for addition reactions (K_S) with these donors follow their order of basicity (K_H) viz. DPSO (0.033)<TBP (0.16)TOPO (8.9) with log K_S values of 3.70, 4.28 and 6.45, respectively. The thermodynamic parameters associated with the formation of these systems have been evaluted by the temperature coefficient method. The results indicate that the complex in the organic phase for DPSO and TBP is stabilized only by enthalpy, whereas both enthalpy and entropy contribute to the stabilization of the TOPO complex. Also, enthalpy contribution is more prominent as compared with the UO ₂ ²⁺ /HTTA/TOPO system, where both enthalpy and entropy contribute almost equally.     

Studies on extraction of thorium(IV) from sulfate media with mixtures of long-chain primary amines and tributyl phosphate

The partition of Th(IV) from H₂SO₄ solutions with extractant mixtures of long-chain primary amine (Primene JMT, PrJT) and tributyl phosphate (TBP) is described. Exraction was optimized at PrJT/TBP molar ratio of about 3. The dependence of extraction on acidity, salting agent, extractant concentration, diluent type and temperature, was investigated. From the results obtained, the extracted species are suggested and enthalpy data determined.     

Synergistic extraction of uranium(VI) with tri-n-butyl phosphate and i-butyldodecylsulfoxide

Summary The synergistic extraction of uranium(VI) from aqueous nitric acid solution with a mixture of tri-n-butyl phosphate (TBP) and i-butyldodecylsulfoxide (BDSO) in toluene was investigated. The effects of the concentrations of extractant, nitric acid, sodium nitrate and sodium oxalate on the distribution ratios of uranium(VI) have been studied. The values of enthalpy change for the extraction reactions with BDSO, TBP and a mixture of TBP and BDSO in toluene were -23.2±0.8 kJ/mol, -29.2±1.4 kJ/mol and -30.6±0.6 kJ/mol, respectively. It has been found that the maximum synergistic extraction effect occurs when the molar ratio of TBP to BDSO is close to 1. The composition of the complex of the synergistic extraction is UO₂(NO₃)₂ ^. BDSO ^. TBP.     

Enthalpies of Dilution of D-p-Hydroxyphenylglycine in Buffer Solutions at Different pH

The effect of pH on the dilution enthalpies of D-p-hydroxyphenylglycine in phosphate buffer solutions has been investigated by isothermal titration microcalorimetry at 298.15 K. The corresponding homogeneous enthalpic interaction coefficients have been calculated according to the excess enthalpy concept. The results show that the enthalpies of dilution of D-p-hydroxyphenylglycine in phosphate buffer solutions at different pH are all positive. The overall trend is that enthalpies of dilution become more positive with an increase of pH, but there is a minimum of the enthalpy of dilution at pH = 7.0. The enthalpic pair interaction coefficients, h ₂, all have negative values. The results are interpreted from the point of view of solute-solute and solute-solvent interactions involved in the solvent effects.     

Extraction of uranium(VI) from nitric acid medium by 1.1M tri-n-butylphosphate in ionic liquid diluent

Summary A systematic study on the extraction of U(VI) from nitric acid medium by tri-n-butylphosphate (TBP) dissolved in a non-traditional diluent namely 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF₆) ionic liquid (IL) is reported. The results are compared with those obtained using TBP/n-dodecane (DD). The distribution ratio for the extraction of U(VI) from nitric acid by 1.1M TBP/bmimPF₆ increases with increasing nitric acid concentration. The U(VI) distribution ratios are comparable in the nitric acid concentration range of 0.01M to 4M, to the ratios measured using 1.1M TBP/DD. In contrast to the extraction behavior of TBP/DD, the D values continued to increase with the increase in the concentration of nitric acid above 4.0M. The stoichiometry of uranyl solvate extracted by 1.1M TBP/IL is similar to that of TBP/DD system, wherein two molecules of TBP are associated with one molecule of uranyl nitrate in the organic phase. Ionic liquid alone also extracts uranium from nitric acid, albeit to a small extent. The exothermic enthalpy accompanying the extraction of U(VI) in TBP/bmimPF₆ decreases with increasing nitric acid and with TBP concentrations.     

Thermodynamics of solvent extraction of thorium by solutions of HHTA and mixtures of HHTA and TBP

The changes in free energy, enthalpy and entropy for the extraction of thorium by solutions of thenoyltrifluoroacetone (HTTA) and mixtures of solutions of HTTA and tri-n-butylphosphate (TBP), in three diluents, viz. cyclohexane, benzene and chloroform, were determined using the solvent extraction data obtained at different temperatures. From these data the thermodynamic parameters associated with the formation of Th(TTA)₄ · TBP in the respective organic diluents were evaluated. Trends in the enthalpy changes were attributed to different degrees of association of the diluents with themselves and with the solutes present in them.     

Extraction of actinides with tropolone

The partition coefficient of tropolone in xylene, dichloroethane and chloroform was determined from 0.05M HCl medium. The values obtained were 5.6, 25.5 and 43, respectively. In the extraction of UO ₂ ²⁺ using tropolone (HT) in xylene from an aqueous medium of ionic strength 0.05, the species UO₂T₂·HT was established. The species extracted in presence of a neutral donor was found to be UO₂T₂·S[S+dioctyl sulfide (DOS), dibutylhexanamide (DBHA), tri-n-butyl phosphate (TBP), dioctyl sulfoxide (DOSO), and tri-n-octylphosphine oxide (TOPO)]. The equilibrium constant of complex formation between the self-adduct and the neutral donor was calculated and was found to follow the basicity order (DOS«DBHA<TBP<DOSO»TOPO). The thermodynamic parameters of the adduct UO₂T₂·DOSO were also calculated by the temperature coefficient method. The values of free energy, enthalpy and entropy changes obtained were ?1.26 kJ·mol^?1, ?1.98 kJ/mol and ?2.5 J·mol^?1·deg^?1, respectively.     

Calorimetric studies on the thermal decomposition of tri n-butyl phosphate-nitric acid systems

Thermal decomposition of neat TBP, acid-solvates (TBP·1.1HNO₃, TBP·2.4HNO₃) (prepared by equilibrating neat TBP with 8 and 15.6?M nitric acid) with and without the presence of additives such as uranyl nitrate, sodium nitrate and sodium nitrite, mixtures of neat TBP and nitric acid of different acidities, 1.1?M TBP solutions in diluents such as n-dodecane (n-DD), n-octane and isooctane has been studied using an adiabatic calorimeter. Enthalpy change and the activation energy for the decomposition reaction derived from the calorimetric data wherever possible are reported in this article. Neat TBP was found to be stable up to 255?°C, whereas the acid-solvates TBP·1.1HNO₃ and TBP·2.4HNO₃ decomposed at 120 and 111?°C, respectively, with a decomposition enthalpy of ?495.8?±?10.9 and ?1115.5?±?8.2?kJ?mol^?1 of TBP. Activation energy and pre exponential factor derived from the calorimetric data for the decomposition of these acid-solvates were found be 108.8?±?3.7, 103.5?±?1.4?kJ?mol^?1 of TBP and 6.1?×?10¹⁰ and 5.6?×?10⁹?S^?1, respectively. The thermochemical parameters such as, the onset temperature, enthalpy of decomposition, activation energy and the pre-exponential factor were found to strongly depend on acid-solvate stoichiometry. Heat capacity (C _p ), of neat TBP and the acid-solvates (TBP·1.1HNO₃ and TBP·2.4HNO₃) were measured at constant pressure using heat flux type differential scanning calorimeter (DSC) in the temperature range 32?C67?°C. The values obtained at 32?°C for neat TBP, acid-solvates TBP·1.1HNO₃ and TBP·2.4HNO₃ are 1.8, 1.76 and 1.63?J?g^?1?K^?1, respectively. C _p of neat TBP, 1.82?J?g^?1?K^?1, was also measured at 27?°C using ??hot disk?? method and was found to agree well with the values obtained by DSC method.     

Determination of trace elements in wool fibre by instrumental neutron activation analysis and relation between trace element contents and quality of wool

Synergistic extraction of uranyl ion with 2-thenoyltrifluoroacetone (HTTA) and aliphatic amides with varying basicities, viz. dibutyl hexanamide (DBHA), dibutyloctanamide (DBOA) or dibutyldecanamide (DBDA) has been studied at various fixed temperatures of 20, 30, 40 and 50±0.1°C. Results indicate that the equilibrium constants of the organic phase addition reaction (Ks) with these amides follow their order of basicity (Kh) viz. DBHA (0.09)<0.10) H DBOA (0.13) with log Ks values of 4.91, 4.99 and 5.02, respectively. These values are much higher than those with TBP (3.8) or sulfoxides (4) as donors. This may be attributed to the existence of a resonance form of the amide, which has higher electron density on the carbonyl oxygen. The thermodynamic parameters associated with these systems evaluated by the temperature coefficient method indicate that the organic phase addition reaction with all the three amides is stabilized by both enthalpy and entropy changes as against UO ₂ ²⁺ /HTTA/TBP system, where only the enthalpy change contributes to the stabilization.     

Studies on liquid–liquid extraction of La(III) from acidic nitrate medium using TBP in petrofin

The present study aims at investigating the capability of tri-n-butyl phosphate (TBP) in petrofin as extracting agent for La(III) from acidic nitrate medium. The concentrations of TBP and sodium nitrate have positive influence while temperature shows a negative impact on the extraction. The values of standard enthalpy change and entropy change confirm the extraction process as exothermic with a decrease in randomness due to complexation. Regression analysis results fit well with the experimental data in the cases of TBP and nitrate concentration variation.     

Enthalpies of solution in water of urotropine as function of concentration and temperature

Enthalpies of solution of Hexamethylenetetramine in water at several molal concentrations and at four temperatures (278.15, 288.15, 298.15, and 308.15) K were determined. The values of enthalpy of solution at infinite dilution were combined with the enthalpy of sublimation to get the corresponding enthalpies of hydration. The change in heat capacity at infinite dilution was calculated.     

Enthalpy changes upon dilution and ionization of poly(L-glutamic acid) in aqueous solutions

The enthalpy changes accompanying the dilution and ionization of poly(L-glutamic acid) in water have been measured at 25 degrees C for two degrees of polymerization (DP = 115 and DP = 480) at various degrees of ionization, alpha, for a concentration range from about 0.2 to 0.002 monomol/L. The heat of dilution displays an unusual dependence on the degree of ionization, which is in sharp contrast to the behavior of other weak carboxylic polyelectrolytes, such as poly(acrylic acid). The exothermic heat effects observed at low values of alpha become endothermic for the region where the helix-coil transition is most pronounced, and for high degrees of ionization, they are exothermic again. Evidently, an endothermic heat effect, produced by an additional conformational transition in the dilution process, is superimposed on the exothermic enthalpy of dilution, and it overweighs the latter in the region of alpha where the conformational transition is prevailing. The calorimetric titration curve, which gives the dependence of the heat of ionization, deltaH(i), on alpha, has a maximum and is typical for poly(carboxylic acids) which undergo pH-induced conformational transition, such as poly(methacrylic acid). The values of deltaH(i) obtained at two polymer concentrations indicate that the enthalpy of ionization depends on the polypeptide concentration.     

Standard enthalpy of formation of lithium diphosphate

Lithium carbonate (Li₂CO₃) and ammonium dihydrogen phosphate (NH₄H₂PO₄) were used for synthesizing lithium diphosphate (Li₄P₂O₇). The purity of the latter compound was checked up by X-ray diffraction. The heat of dissolution of (Li₄P₂O₇) in phosphoric acid solution was measured in a C-80 SETARAM calorimeter. Many dilution and mixing processes in acid solutions of several concentrations (w/w) H₃PO_4, were also realized in the calorimeter in order to get the standard enthalpy of formation of this product. Two thermochemical cycles were investigated and the obtained values for the enthalpy of formation are: (−3383.4 and −3147) kJ · mol⁻¹. The former one is in better agreement with literature data.     

Extraction of Am(III) by mixture of dihexyl N,N-diethylcarbamoylmethyl phosphonate and tributyl phosphate in benzene from nitric acid solutions

Extraction of Am(III) by dihexyl N,N-diethylcarbamoylmethyl phosphonate (CMP) in benzene from nitric acid solutions (pH 2.0 to 6.0M) has been studied. High extraction of Am(III) by CMP from 2–3M HNO₃ was observed. The species extracted was found to be Am(NO₃)₃·3CMP. The extraction was also done with mixtures of CMP+TBP and CMP+TOPO, where mixed species were extracted in the organic phase. The back-extraction experiments gave an efficient back-extraction of Am(III) by pH 2.0 (HNO₃) from the loaded CMP+TBP phase but a poor back-extraction from the loaded CMP+TOPO phase. The loading of Nd(III) by mixture of CMP and TBP was 50% of the CMP concentrations at a total Nd(III) concentration of 0.182M. The thermodynamic parameters of Am(III) extraction by a mixture of CMP and TBP were evaluated by temperature variation method, which suggests that the two-phase reaction is stabilized by enthalpy and opposed by entropy.     

Standard enthalpy of formation of disodium hydrogen phosphate hexahydrate and sodium diphosphate

Commercial disodium hydrogen phosphate dodecahydrate (Na₂HPO₄·12H₂O) was used as a precursor for synthesizing disodium hydrogen phosphate hexahydrate (Na₂HPO₄·6H₂O) and sodium diphosphate (Na₄P₂O₇). The purity of the synthesized products was checked up by IR spectroscopy and X-ray diffraction. The heat of dissolution of these compounds, in acid solutions of several concentrations (w/w) of H₃PO₄ was measured in a C-80 SETARAM calorimeter. Many dilution and mixing processes were also realized in the calorimeter in order to get the standard enthalpy of formation of these products. The values obtained for the enthalpies of formation are: (?3210.5) and (?3516.5) kJ · mol^?1 for sodium diphosphate (Na₄P₂O₇) and disodium hydrogen phosphate hexahydrate (Na₂HPO₄·6H₂O), respectively.     

Synergistic extraction of trivalent Am,Cm, Bk and Cf with HTTA+TBP in xylene

The synergistic extraction of trivalent actinides Am, Cm, Bk and Cf with thenoyltrifluoro acetone (HTTA) and tributyl phosphate (TBP) has been studied in xylene at 30°C. Correction for the HTTA-TBP interaction has been applied to get the free TBP concentration in the organic phase. Plots of log D vs. log [HTTA] give straight lines with a slope of 3 only after correcting for the HTTA-TBP interaction; without this correction the slope varies from 3 to 1 with increasing HTTA concentrations. The presence of two synergistic species M(TTA)₃·TBP and M(TTA)₃·2TBP simultaneously has been observed. The equilibrium constants for the organic phase synergistic reactions have been calculated.     

1H n.m.r. study of the self-association of acetone phenylhydrazone by hydrogen bonding

Proton magnetic resonance dilution studies of acetone phenylhydrazone were carried out in n-heptane, carbon disulphide and hexachlorobutadiene solutions. Equilibrium constants and enthalpy values for the predominant self-associated species are reported. Linear trimeric aggregates predominate in n-heptane solutions. The monomeric units are associated by intermolecular hydrogen bonding of the NH proton to the iminic nitrogen. The enthalpy per hydrogen bond is 10.04 kJ (2.4 kcal). In carbon disulphide and hexachlorobutadiene solutions complexation of acetone phenylhydrazone with the solvent competes with self-association.     

The apparent molar heat capacities and volumes of aqueous NaCl from 0.01 to 3 mol kg−1 in the temperature range 274.65 to 318.15 K

The heat capacities per unit volume of aqueous solutions of NaCl were measured with a flow microcalorimeter. The molality and temperature range covered were 0.01 to 3 mol kg^?1 and 274.65 to 318.15 K. The derived apparent molar heat capacities C₂, φ, when extrapolated to infinite dilution, give standard partial molar heat capacities C₂^o which are in excellent agreement with those of Criss and Cobble. The excess apparent molar heat capacities (C₂, φ - C₂^o) can be used to predict the temperature dependence of (H₂, φ - H₂^o), the excess apparent molar enthalpy. The calculated values of ΔH₂, φ agree within experimental uncertainty with the integral enthalpies of dilution of Ensor and Anderson and of Messikomer and Wood up to 323.15 K. Above this temperature significant differences are observed. The densities of the solutions were also remeasured in the same range of temperature and molality with a flow densimeter, and the derived apparent molar volumes agree with the literature values.     

Enthalpy Relaxation in Glasses: Regression analysis of integral DSC data

A new method of calculation of parameters of enthalpy relaxation models is proposed. Regression analysis treatment compares the experimental and calculated values of relaxation enthalpy. The experimental values of relaxation enthalpy are obtained by numerical integration of the difference between the two DSC curves. Contrary to the overall shape of the DSC curve the integral values are not affected by particular heat flow conditions during the DSC experiment. The Narayanaswamy's numerical model based on the Kohlrausch—William—Watts relaxation function was used to calculate the theoretical values of relaxation enthalpy. The application of the proposed method on the DSC experimental data of enthalpy relaxation of As₂Se₃ is shown.This revised version was published online in November 2005 with corrections to the Cover Date.     

Some studies on synergic extraction of mixed ligand species of uranium(VI)

The extraction of U(VI) by mixtures of HTTA and TBP from aqueous thiocyanate medium has been studied. From the data obtained it was observed that the predominant uranium species extracted, causing synergic enhancement in the extraction of U(VI), is UO₂(SCN)TTA · 2TBP when benzene and cyclohexane are used as diluents, and that at a very low concentration of TBP the contribution of additional species, viz. UO₂(TTA)₂ · TBP becomes significant. With chloroform as diluent, however, both of these species are contributing to the synergic enhancement. The extraction of a quaternary uranium species, UO₂(SCN)TTA · 2TBP, involving the participation of the aqueous anion is thus established. Equilibrium constants for the various extraction equilibria involved are calculated.