Temperature dependence of complex formation constants in aqueous solutions of metal acetates

The equilibrium constants of formation of inner- and outer-sphere cation-anion complexes (ion pairs) in aqueous solutions of different metal acetates in a wide temperature range have been calculated by integrating the density function of distribution of ligands around the cation. The standard Gibbs energies, enthalpies, and entropies of formation of 1: 1 complexes have been calculated. It has been shown that, in all solutions under consideration, contact and solvent-separated ion pairs coexist. A conclusion has been drawn that the temperature dependence of ion association constants is mainly determined by the temperature dependence of the water dielectric constant.     

Temperature dependence of ion association constants in nonaqueous solutions of metal perchlorates

The ion association constants in nonaqueous solutions of singly and doubly charged metal perchlorates in organic solvents in a wide range of temperatures have been calculated by integrating the ligand distribution density function. The standard Gibbs energies, entropies, and enthalpies of formation of ion pairs have been calculated. Comparison with experimental data have shown that diluted solutions of doubly charged metal perchlorates are dominated by solvent-separated ion pairs, whereas such pairs coexist with contact ion pairs in solutions of alkali metal perchlorates. It has been demonstrated that the dielectric continuum approximation satisfactorily predicts the temperature dependence of ion association constants.     

The influence of polar solvents on ions and ion pairs in the anionic polymerization of styrene

In the rather polar organic solvents dimethoxyethane, tetrahydrofuran and 3-methyltetrahydrofuran, the behaviour of contact ion pairs, solvent-separated ion pairs and free carbanions of polystyryl sodium has been investigated by kinetic and conductivity measurements. Both the equilibrium between the two kinds of ion pairs and the dissociation of solvent-separated ion pairs to free anions are followed over a wide range of temperature. Thereby, conditions can be found under which the polymerization takes place almost exclusively via one of the two types of ion pairs.The thermodynamic parameters of the equilibria and the Arrhenius parameters of the propagation rate constants of the different kinds of propagating chain ends are reported. The equilibria between these species are strongly influenced by the solvent whereas the individual propagation rate constants are scarcely affected by the solvent. The “effective charge distance” in the solvent-separated ion pair can be estimated from the corresponding dissociation constant. The mobility of the polymer carbanion is discussed.     

Hydrogen bonding mediated ion pairs of some aprotic ionic liquids and their structural transition in aqueous solution

Ion pair speciation of ionic liquids(ILs) has an important effect on the physical and chemical properties of ILs and recognition of the structure of ion pairs in solution is essential. It has been reported that ion pairs of some ILs can be formed by hydrogen bonding interactions between cations and anions of them. Considering the fact that far-IR(FIR) spectroscopy is a powerful tool in indicating the intermolecular and intramolecular hydrogen bonding, in this work, this spectroscopic technique has been combined with molecular dynamic(MD) simulation and nuclear magnetic resonance hydrogen spectroscopy(~1H NMR) to investigate ion pairs of aprotic ILs [Bmim][NO_3], [BuPy][NO_3], [Pyr_(14)][NO_3], [PP_(14)][NO_3] and [Bu-choline][NO_3] in aqueous IL mixtures. The FIR spectra have been assigned with the aid of density functional theory(DFT) calculations, and the results are used to understand the effect of cationic nature on the structure of ion pairs. It is found that contact ion pairs formed in the neat aprotic ILs by hydrogen bonding interactions between cation and anion, were still maintained in aqueous solutions up to high water mole fraction(say 0.80 for [BuPy][NO3]). When water content was increased to a critical mole fraction of water(say 0.83 for [BuPy][NO3]), the contact ion pairs could be transformed into solvent-separated ion pairs due to the formation of the hydrogen bonding between ions and water. With the further dilution of the aqueous ILs solution, the solvent-separated ion pairs was finally turned into free cations and free anions(fully hydrated cations or anions). The concentrations of the ILs at which the contact ion pairs were transformed into solvent-separated ion pairs and solvent-separated ion pairs were transformed into free ions(fully hydrated ion) were dependent on the cationic structures. These information provides direct spectral evidence for ion pair structures of the aprotic ILs in aqueous solution. MD simulation and ~1H NMR results support the conclusion drawn from FIR spectra investigations.     

HPLC separation of heterocyclic beta-diketonates of actinide, lanthanide and transition metals

Liquid-chromatography conditions for the separation of neutral chelates of 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone with transition metals, lanthanides and actinides have been established. The use of reverse-phase liquid chromatography, instead of ion-exchange, is a novel approach for actinide separation. The high molar absorptivities of the beta-diketonates in the ultraviolet region allow for their detection at the nanogram level. The potential exists, therefore, for the rapid solvent extraction, concentration and determination of traces of actinides and other metals.     

Sequential separation of actinides and lanthanides by extraction chromatography using a CMPO-TBP/XAD7 column

CMPO/TBP sorbed on Amberlite XAD7 resin was used for the separation of actinides and lanthanides from nitric acid solutions by extraction chromatography. The distribution ratios of actinides and lanthanide fission products (Ce, Eu) as a function of acid concentration and some complexing agents were determined. In strong HNO₃ medium (>1 mol/l) the tri-, tetra- and hexavalent actinides as well as the lanthanides have shown great affinity for the CMPO/TBP/XAD7 sorbent. The same behavior was found in HCl medium except for trivalent actinides and lanthanides which show lower distribution values in the same acid range. The effect of some complexing agents as DTPA and ammonium oxalate were also investigated. In DTPA only hexavalent actinides showed higher distribution value. On the basis of these differences, an alternative procedure for actinide-lanthanide separation and actinides from each other is proposed.     

Direct detection of ion pair formation and collapse in a migration reaction of a beta-phosphate radical

In solutions of trifluorotoluene or toluene containing 2,2,2-trifluoroethanol, the beta-phosphate radical heterolyzed to give a detectable ion pair, identified as a solvent-separated species. Rate constants for the radical fragmentation reaction forming the ion pair, for ion pair collapse, and for diffusive escape to free ions were measured. The kinetics and entropy of activation for fragmentation indicate that the rearrangement reaction occurs by a heterolysis pathway in all solvents. [reaction: see text]     

Adsorption behaviors of trivalent actinides and lanthanides on pyridine resin in lithium chloride aqueous solution

The adsorption behaviors of trivalent actinides and lanthanides on pyridine resin in lithium chloride aqueous solution were investigated. The adsorbed amounts of lanthanides and the degree of mutual separation of lanthanides increased with an increase in the concentration of lithium chloride in aqueous solution. The group separation of the trivalent actinides and lanthanides was observed. This separation phenomenon is similar in a hydrochloric acid solution. However, the adsorption behavior of lanthanides in lithium chloride is different from their behavior in a hydrochloric acid solution. This fact shows that the adsorption mechanisms of lanthanides in a lithium chloride aqueous solution and in a hydrochloric acid solution are different; the adsorption mechanisms are attributed to the ion exchange in a hydrochloric acid solution, and to the complex formation with pyridine group in a lithium chloride solution.     

The EURO-GANEX Process: Current Status of Flowsheet Development and Process Safety Studies

A new hydrometallurgical grouped actinide extraction process has been developed to separate the transuranic actinide ions from dissolved spent fuel solution (after an initial uranium extraction cycle). This “EURO-GANEX” process is aimed towards the homogeneous recycling of plutonium and minor actinides in a future closed fuel cycle. The separation process is based on the co-extraction of actinides and lanthanides from aqueous nitric acid into an organic phase followed by selective co-stripping of actinides. A suitable organic phase has been formulated and distribution ratios determined for lanthanides, actinides and some problematic fission products under extraction and stripping conditions. The process flowsheet has been proven on surrogate feed solutions as well as with spent fast reactor fuel; excellent recoveries of the actinides and good decontamination factors from the lanthanides and other fission products were obtained. A variation on the EURO-GANEX flowsheet (the “TRU-SANEX” process) has now been designed to produce separate Pu+Np and Am+Cm products for heterogeneous recycling. Progress on underpinning process chemistry and safety studies as well as flowsheet tests are summarized.     

State in solution, structure, and regioselectivity of reactions of the lithium 1-(2-methoxyphenyl)-3,3-diphenylpropyne derivative

According to the spectrophotometric data, the lithium 1-(2-methoxyphenyl)-3,3-diphenylpropyne derivative in diethyl ether exists as contact ion pairs, while in THF, according to the spectrophotometric and¹³C NMR data, solvent-separated ion pairs are predominantly formed. According to the¹³C NMR data, the carbanion in the solventseparated ion pairs has a structure close to the propargylic type. The regioselectivity of reactions of the lithium derivative with ethyl halides in diethyl ether, THF, and hexamethyphosphoramide, with benzyl chloride in the first two solvents, and with methanol in THF were studied. The protonation with methanol proceeds exclusively at the allenylic center (C-1) while the ethylation and especially benzylation proceed predominantly at the propargylic center (C-3). The selectivity of ethylation of the propargylic center of both solvent-separated ion pairs in THF and contact ion pairs in diethyl ether increases as the hardness of the ethylating agent increases, and in the case of the same ethyl halide, the selectivity increases from the solvent-separated ion pairs to the contact ion pairs. The spectral data obtained and the data on changes in the regioselectivity do not allow one to believe that the contact ion pairs of the lithium derivative in ether exhibit the intramolecular coordination of the lithium cation to the methoxy group, which might lead to the allenylic structure of contact ion pairs of this derivative. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2043–2051, November, 1997.     

Charge separation distance for flexible donor-bridge-acceptor systems after electron-transfer quenching

Photoinduced transient dipole experiments are used to measure the effective charge separation distance, which is equivalent to the photoinduced change in dipole moment divided by the electron charge of flexible electron-donor/acceptor systems, D-(CH2)n-A, where D is 4- N,N-dimethylaniline, A is 9-anthryl, and n = 3, 4. We find that the dipole moments increase strongly with solvent polarity. For the compound with n = 4 (DBA4), analysis of dipole signals indicates that the effective charge separation distances in toluene, 1,4-dioxane, ethyl acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 2-methylpentanone-3, 3-pentanone, and benzonitrile are 2.2, 2.5, 4.5, 4.7, 5.5, 5.5, 4.8, and 6.3 A, respectively. These values can be understood as the root-mean-square charge separation distance in the solutions of different solvents. We assume that the folded contact configuration has a separation distance of 3.5 A, the extended, solvent-separated configuration has a separation distance of 8.0 A, and that they are the only two stable species after electron-transfer quenching. The formation efficiencies of contact radical ion pairs (CRIPs) and solvent-separated radical ion pairs (SSRIPs) are estimated in different solvents. The results indicate that a significant fraction of the ion pairs exist as solvent-separated ion pairs when the dielectric constant of the solvent is larger than 10. These results indicate that electron-transfer quenching can indeed happen at large separations in polar solvents. They also reveal that there is a barrier for ion pairs formed at large separations, hindering collapse to a contact separation of around 3.5 A.     

Conductance and ion association in dimethylsulfite

The electrolytic conductances of LiClO₄, LiAsF₆, NaClO₄ and the n-butylammonium salts Bu₄NCl, Bu₄NClO₄, and Bu₄NBPh₄ (tetraphenylborate) have been determined in dimethylsufite at 25°C. Ion association constants calculated from these data are interpreted in terms of solvent-separated ion pairs (for LiClO₄, LiAsF₆, and NaClO₄), and contact ion pairs (for the n-butyl-ammonium salts). Comparisons are made for analogous electrolytes in acetone, and in which all salts form contact ion pairs.     

Sorption Characteristics of Radioeuropium on Bentonite and Kaolinite

The factors affecting the sorption of radioeuropium(III) by bentonite and kaolinite were studied with the aim to assess the important factors which should be included in modeling of radioeuropium(III) migration in soils and sediments. Europium(III) is an analogue of trivalent actinides. The distribution coefficients of radioeuropium for sorption on bentonite and kaolinite from aqueous solutions were determined by using the batch method, and it was found that they were sensitive to the loading, the pH, the humic substance and the sorption direction. Thus, these sorption characteristics of radioeuropium on bentonite and kaolinite were found to be different from those of radiocobalt¹, and the mathematical modeling of trivalent lanthanides and actinides migration will be more complicated than that of radiocobalt. It is improbable that the migration modeling with a constant distribution coefficient will be successful in the case of trivalent lanthanides and actinides.     

Direct observation of the “special” salt effect in the dynamics of transient ion pairs by time-resolved spectroscopy

Intimate ion pairs [A⁺,T⁻] are generated by specific excitation of the charge transfer band of the electron donor—acceptor complex of anthracene and tetranitromethane. Time-resolved spectroscopy in three distinct time regimes (ps, ns and μs) reveals the presence of a second “loose” or solvent-separated ion pair [A⁺//T⁻], the dynamic behavior of which is strongly modulated by added salts. The “special” salt effect is quantitatively evaluated, together with all the rate constants involved in ion-pair dynamics.     

Dynamic nature of the transition state for the SN1 reaction mechanism of diphenylmethyl acetates

Picosecond absorption spectroscopy is employed in the study of the reaction dynamics for the contact ion pairs produced upon the photolysis of a series of substituted diphenylmethyl acetates in the solvents acetonitrile, dimethyl sulfoxide, and 2,2,2-trifluoroethanol. From the temperature dependence of the rate constants, the activation parameters associated with covalent bond formation and diffusional separation to the solvent-separated ion pair are obtained. The activation parameters for bond formation are examined within the context of the Hynes theory for solvent dynamical effects on the passage through the transition state; deviations from the transition-state theory are found to be large. Factors that control nucleophilicity are discussed. Finally the validity of applying the Marcus equation to the SN1 reaction mechanism is addressed.     

Application of chelation ion chromatography to the determination of lanthanides in agriculture

Lanthanides are widely present in soil and plant. In this paper, it is the first time that chelation ion chromatography is applied to analyse lanthanides in a series of samples in agriculture. This technique can eliminate bulk quantity of alkali, alkaline earth metals on chelating concentrator column (MetPac CC-1) and eliminate transition metals on cation exchange column (TMC-1) from complex matrices with ammonium acetate buffer while lanthanides are concentrated. It is shown to be capable of separating and determining all lanthanides on mixed-bed ion exchange column (CS5) in a wide variety of sample types with high accuracy. Elution is carried out with a concentration gradient of oxalic acid (Ox) and diglycolic acid (DGA), coupled with post-column spectrophotometric detection with 4-(2-pyridylazo)resorcinol (PAR) at 520 nm. It can determined ng ml(-1) scales of lanthanides. The whole run time after sample injection is about 55 min.     

On the mechanism of trivalent actinide extraction in the system HDEHP—Lactic acid with DTPA

The dependence of the distribution coefficients on the hydrogen ion concentration and HDEHP concentration in the process of extraction from lactic acid solutions in the presence of DTPA and without it has been investigated. It has been shown that when the lactate ion concentration is higher than 0.01M, Cm is extracted predominantly as the first lactate complex. The presence of DTPA does not change the extraction mechanism. Similarity of the observed regularities for trivalent actinides and lanthanides is confirmed by the extraction of Bk(III), Ce(III), and Eu(III). It is suggested that the nature of carbonic acid used in TALSPEAK-process greatly influences the efficiency of group separation of TPE and lanthanides. It is supported by some experimental data. The extraction and stability constants of the first lactate complex (Cm Lact²⁺) have been found to be: K_e=2, β ₁ ⁰ = 7,7 · 10³. In the practical lactic acid concentration range (1 M) the unextractable complex, Cm Lact₃, is also formed in the aqueous phase. The stability constant of this complex has been found to be β ₃ ⁰ = 1.2 · 10⁷.     

Comparison of the Chemical Properties of 4f, 5f,and 6d Elements

Similarities and differences in the chemical properties of lanthanides, actinides, and transactinides are analyzed. The general tendency of the change in the thermodynamic properties of trivalent lanthanides and actinides is established. The validity of the hypothesis of the pair analogy of trivalent lanthanides and actinides is revised. The oxidation-reduction properties of actinides and transactinides Pu–Hs and Np–Bh are compared.     

Types,Symbolism of Representation of Steric Structure,and Conformations of Ion Pairs. Stereochemical Version of the Generalized Rule of Elimination

Analysis of published data from the standpoint of the generalized rule of elimination demonstrated that in addition to contact and solvent-separated ion pairs, in elimination a species of a third type is generated, called spatially separated ion pair. This is an intermediate formed on the pathway of transformation of a contact ion pair to a solvent-separated one. Each of these ion pairs preserves its initial configuration of the bond C-nucleofuge starting from its origination to transformation into an elimination product, demonstrating discrete and inherent regio- and stereoselectivity: a contact ion pair shows nucleophilically controlled syn reactivity, and spatially- and solvent-separated ion pairs, electrophilically controlled syn and anti reactivity, respectively. The generalized rule of elimination allows almost faultless prediction of regio- and stereo- selectivity, being applicable to interpretation of even those published data which appear surprising or abnormal from the standpoint of the modern theoretical views.     

On the mechanism of extraction of trivalent actinides and lanthanides with alkylamine hydrochlorides

The method to study the mechanism of actinides (III) and lanthanides (III) liquid-liquid amine extraction from chloride media has been suggested. The technique is based on the determination of distribution coefficients for extraction of these elements from mixed salting-out agent solutions with common anion. Distribution coefficients were found to be independent of mean ion activity of lithium cation at constant water activity, when extraction of trace amounts of Eu (III) and Cm(III) by tri-n-octylammonium hydrochloride from mixed LiCl−CaCl₂ solutions occurred. It has been concluded that lithium cation does not enter into the complexed extracted.