Effect of temperature on the hydrolysis of actinide elements in solution

Recent experimental data on the hydrolysis of U(VI), Pu(VI), Np(V), and Th(IV) at variable temperatures are summarized in this review. Data indicate that the hydrolysis reactions of U(VI), Pu(VI), Np(V), and Th (IV) are all enhanced when temperature is increased from 283 to 358 K. In general, the tendency of actinide elements in different oxidation states toward hydrolysis follows the order: An(IV) > An(VI) > An(V), which can be well described by the electrostatic model. The enhancement of hydrolysis at higher temperatures can be attributed to the increase of ionization of water with the increase of temperature. A few theoretical thermodynamic approaches for predicting the effect of temperature, including the constant enthalpy approach, the constant heat capacity approach, the DQUANT equation, and the Ryzhenko-Bryzgalin model, are tested with the experimental data

Cu(i) and Ag(i) complex formation with the hydrophilic phosphine 1,3,5-triaza-7-phosphadamantane in different ionic media. How to estimate the effect of a complexing medium

The complexes of Cu(i) and Ag(i) with 1,3,5-triaza-7-phosphadamantane (PTA) are currently studied for their potential clinical use as anticancer agents, given the cytotoxicity they exhibited in vitro towards a panel of several human tumor cell lines. These metallodrugs are prepared in the form of [M(PTA)4]+ (M = Cu+, Ag+) compounds and dissolved in physiological solution for their administration. However, the nature of the species involved in the cytotoxic activity of the compounds is often unknown. In the present work, the thermodynamics of formation of the complexes of Cu(i) and Ag(i) with PTA in aqueous solution is investigated by means of potentiometric, spectrophotometric and microcalorimetric methods. The results show that both metal(i) ions form up to four successive complexes with PTA. The formation of Ag(i) complexes is studied at 298.15 K in 0.1 M NaNO3 whereas the formation of the Cu(i) one is studied in 1 M NaCl, where Cu(i) is stabilized by the formation of three successive chloro-complexes. Therefore, for this latter system, conditional stability constants and thermodynamic data are obtained. To estimate the affinity of Cu(i) for PTA in the absence of chloride, Density Functional Theory (DFT) calculations have been done to obtain the stoichiometry and the relative stability of the possible Cu/PTA/Cl species. Results indicate that one chloride ion is involved in the formation of the first two complexes of Cu(i) ([CuCl(PTA)] and [CuCl(PTA)2]) whereas it is absent in the successive ones ([Cu(PTA)3]+ and [Cu(PTA)4]+). The combination of DFT results and thermodynamic experimental data has been used to estimate the stability constants of the four [Cu(PTA)n]+ (n = 1-4) complexes in an ideal non-complexing medium. The calculated stability constants are higher than the corresponding conditional values and show that PTA prefers Cu(i) to the Ag(i) ion. The approach used here to estimate the hidden role of chloride on the conditional stability constants of Cu(i) complexes may be applied to any Cu(i)/ligand system, provided that the stoichiometry of the species in NaCl solution is known. The speciation for the two systems shows that the [M(PTA)4]+ (M = Cu+, Ag+) complexes present in the metallodrugs are dissociated into lower stoichiometry species when diluted to the micromolar concentration range, typical of the in vitro biological testing. Accordingly, [Cu(PTA)2]+, [Cu(PTA)3]+ and [Ag(PTA)2]+ are predicted to be the species actually involved in the cytotoxic activity of these compounds. \ua9 2017 The Royal Society of Chemistry

Alkali-metal ion coordination in uranyl(VI) poly-peroxo complexes in solution, inorganic analogues to crown-ethers. Part 2. Complex formation in the tetramethyl ammonium-, Li+-, Na+- and K+-uranyl(VI)-peroxide-carbonate systems

he constitution and equilibrium constants of ternary uranyl(VI) peroxide carbonate complexes [(UO2)(p)(O-2)(q)(CO3)(r)](2(p-q-r)) have been determined at 0 degrees C in 0.50 M MNO3, M = Li, K, and TMA (tetramethyl ammonium), ionic media using potentiometric and spectrophotometric data; O-17 NMR data were used to determine the number of complexes present. The formation of cyclic oligomers, "[(UO2)(O-2)(CO3)](n)", n = 4, 5, 6, with different stoichiometries depending on the ionic medium used, suggests that Li+, Na+, K+ and TMA ions act as templates for the formation of uranyl peroxide rings where the uranyl-units are linked by mu-eta(2)-eta(2) bridged peroxide-ions. The templating effect is due to the coordination of the M+-ions to the uranyl oxygen atoms, where the coordination of Li+ results in the formation of Li[(UO2)(O-2)(CO3)](4)(7-), Na+ and K+ in the formation of Na/K[(UO2)(O-2)(CO3)](5)(9-) complexes, while the large tetramethyl ammonium ion promotes the formation of two oligomers, TMA[(UO2)(O-2)(CO3)] 5 9-and TMA[(UO2)(O-2)(CO3)](6)(11-). The NMR spectra demonstrate that the coordination of Na+ in the five-and six-membered oligomers is significantly stronger than that of TMA(+); these observations suggest that the templating effect is similar to the one observed in the synthesis of crown-ethers. The NMR experiments also demonstrate that the exchange between TMA[(UO2)(O-2)(CO3)](5)(9-) and TMA[(UO2)(O-2)(CO3)](6)(11-) is slow on the O-17 chemical shift time-scale, while the exchange between TMA[(UO2)(O-2)(CO3)](6)(11-)and Na[(UO2)(O-2)(CO3)](6)(11-) is fast. There was no indication of the presence of large clusters of the type identified by Burns and Nyman (M. Nyman and P. C. Burns, Chem. Soc. Rev., 2012, 41, 7314-7367) and possible reasons for this and the implications for the synthesis of large clusters are briefly discussed

Chemical equilibria in the binary and ternary uranyl(vi)\u2013hydroxide\u2013peroxide systems

The composition and equilibrium constants of the complexes formed in the binary U(VI)-hydroxide and the ternary U(VI)-hydroxide-peroxide systems have been studied using potentiometric and spectrophotometric data at 25 degrees C in a 0.100 M tetramethylammonium nitrate medium. The data for the binary U(VI) hydroxide complexes were in good agreement with previous studies. In the ternary system two complexes were identified, [UO2(OH)(O-2)](-) and [(UO2)(2)(OH)(O-2)(2)](-). Under our experimental conditions the former is predominant over a broad p[H+] region from 9.5 to 11.5, while the second is found in significant amounts at p[H+] < 10.5. The formation of the ternary peroxide complexes results in a strong increase in the molar absorptivity of the test solutions. The absorption spectrum for [(UO2)(2)(OH) (O-2)(2)](-) was resolved into two components with peaks at 353 and 308 nm with molar absorptivity of 16200 and 20300 M-1 cm(-1), respectively, suggesting that the electronic transitions are dipole allowed. The molar absorptivity of [(UO2)(OH)(O-2)](-) at the same wave lengths are significantly lower, but still about one to two orders of magnitude larger than the values for UO22+(aq) and the binary uranyl(VI) hydroxide complexes. It is of interest to note that [(UO2)(OH)(O-2)](-) might be the building block in cluster compounds such as [UO2(OH)(O-2)](60)(60-) studied by Burns et al. (P. C. Burns, K. A. Kubatko, G. Sigmon, B. J. Fryer, J. E. Gagnon, M. R. Antonio and L. Soderholm, Angew. Chem. 2005, 117, 2173-2177). Speciation calculations using the known equilibrium constants for the U(VI) hydroxide and peroxide complexes show that the latter are important in alkaline solutions even at very low total concentrations of peroxide, suggesting that they may be involved when the uranium minerals Studtite and meta-Studtite are formed by alpha-radiolysis of water. Radiolysis will be much larger in repositories for spent nuclear fuel where hydrogen peroxide might contribute both to the corrosion of the fuel and to transport of uranium in a ground water system

The thermodynamics of 1,4,7,10,13 - pentaazatridecane complexes of silver(I) in dimethyl sulfoxide.

The thermodynamic parameters Delta G degrees, Delta H degrees and Delta S degrees for the formation of silver(I) mononuclear (AgL(+)) and polynuclear ([Ag(2)L](2+), [Ag(3)L(2)](3+)) complexes with 1,4,7,10,13-pentaazatridecane (L = tetren) have been obtained in dimethyl sulfoxide (dmso) at 25 degrees C and in an ionic medium of 0.1 mol dm(-3). The complexes are enthalpy stabilized while the entropy contributions oppose their formation. Tetren, differently from other linear polyamines which have only aminoethylenic subunits and less than Eve nitrogens, is able to form polynuclear species in dmso. Structures and stabilities of the complexes are discussed in relation to the characteristics of the ligan

The crystal structure of a chelate silver(I) complex: {Ag[Ph2P(CH2 )2 SCH2CH3 ]2}ClO4.

A single crystal of the {Ag[Ph(2)P(CH2)(2)SCH2CH3)ClO4 complex, [Ag(PSEt)(2)]ClO4, has been isolated from anhydrous propylene carbonate solution containing AgClO4 and the ligand in a 1:2 ratio. An X-ray diffraction analysis, carried out by adopting the heavy-atom method, shows that no solvent molecules are present in the adduct, enabling the PSEt ligand to behave as a chelating agent, both P and S atoms being coordinated to the metal ion. The coordination geometry around silver(I) can be described as a distorted tetrahedron with a P-Ag-P' angle of 148.9(1)degrees; this is most likely due to the repulsion between two phenyl rings (C4...C4'=3.96 Angstrom) which has the further consequence of lowering the S-Ag-P bond angle to 82.5(1)degrees