Thermodynamical and Structural Study of Protactinium(V) Oxalate Complexes in Solution

Mendes, Mickaël; Hamadi, Sena; Naour, C. Le; Roques, Jérôme; Jeanson, Aurélie; Auwer, Christophe Den; Moisy, Philippe; Topin, Sylvain; Aupiais, Jean; Hennig, Christoph; Giandomenico, Maria-Vita Di

doi:10.1021/ic101189w

Cited by 29 publications

(40 citation statements)

References 28 publications

(61 reference statements)

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“…In order to obtain some information about binding modes and bypass the contribution of dehydration of the oxalate ligand to the thermodynamic parameters (for second and third actinide complexation constants) [42], the thermodynamic data of stepwise reactions (Gibbs energy, enthalpy and entropy) are recalculated from the previously overall data gathered in the Tables 5 and 7. The results are given in the Table 8.…”

Section: Discussionmentioning

confidence: 99%

Actinide oxalate complexes formation as a function of temperature by capillary electrophoresis coupled with inductively coupled plasma mass spectrometry

et al. 2014

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confirmed the formation of the 1 : 1, 1 : 2 and 1 : 3 complexes for U(VI) and Am(III); the formation of the 1 : 1 and 1 : 2 complexes for Np(V) and the formation of only 1 complex for Pu(V). For each complex, the thermodynamic parameters (the Gibbs energy Δ r ( ), the molar entropy change Δ r ( ) and the molar enthalpy change Δ r ( 0 )) were fitted to the experimental data. The effect of the ionic medium was treated using the specific ion interaction theory and the thermodynamic parameters at zero ionic strength were compared to previously published data.

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Section: Discussionmentioning

confidence: 99%

Actinide oxalate complexes formation as a function of temperature by capillary electrophoresis coupled with inductively coupled plasma mass spectrometry

et al. 2014

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“…34 Oxalate and diethylenetriaminepentaacetate can also form complexes containing Pa−O bonds. 35 39 Theoretical studies have also examined essential aspects of the chemistry of Pa. 40−42 The calculated structure of PaO 2 + is linear and its electronic structure is similar to those of higher linear actinides, where the 5f orbital contribution to bonding is important. 3,4,40,41,43 Although complexing agents can stabilize reactive Pa in aqueous solution, these environments do not reflect the interaction of Pa(V) with water; hydrolysis reactions of Pa(V) occur too rapidly and result in too many possible species to allow assignments of rates and products.…”

Section: ■ Introductionmentioning

confidence: 99%

Elucidating Protactinium Hydrolysis: The Relative Stabilities of PaO₂(H₂O)⁺ and PaO(OH)₂⁺

2015

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It is demonstrated that the gas-phase oxo-exchange of PaO2(+) with water is substantially faster than that of UO2(+), indicating that the Pa-O bonds are more susceptible to activation and formation of the bis-hydroxide intermediate, PaO(OH)2(+). To elucidate the nature of the water adduct of PaO2(+), hydration of PaO2(+) and UO2(+), as well as collision induced dissociation (CID) and ligand-exchange of the water adducts of PaO2(+) and UO2(+), was studied. The results indicate that, in contrast to UO2(H2O)(+), the protactinium oxo bis-hydroxide isomer, PaO(OH)2(+), is produced as a gas-phase species close in energy to the hydrate isomer, PaO2(H2O)(+). CID behavior similar to that of Th(OH)3(+) supports the assignment as PaO(OH)2(+). The gas-phase results are consistent with the spontaneous hydrolysis of PaO2(+) in aqueous solution, this in contrast to later AnO2(+) (An = U, Np, Pu), which forms stable hydrates in both solution and gas phase. In view of the known propensity for Th(IV) to hydrolyze, and previous gas-phase studies of other AnO2(+), it is concluded that the stabilities of oxo-hydroxides relative to oxide hydrates decreases in the order: Th(IV) > Pa(V) > U(V) > Np(V) > Pu(V). This trend suggests increasing covalency and decreasing ionicity of An-O bonds upon proceeding across the actinide series.

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“…ACE has shown its capability to be used as a speciation tool for organic and inorganic systems with various detection systems. In the past few years, ACE has been widely used (i) to investigate chemical equilibria and measure stability constants of inorganic species and (ii) to determine the stable form of aqueous species . Models describing the formation of 1:1 complexes are often used as well as models describing the formation of successive complexes using nonlinear regressions .…”

Section: Introductionmentioning

confidence: 99%

Formation of MSeO₄(aq) complexes (M²⁺ = Mg²⁺, Co²⁺, Ni²⁺, Cu²⁺, Cd²⁺) studied as a function of temperature by affinity capillary electrophoresis

2013

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Complexation of divalent cations (Mg(2+), Co(2+), Ni(2+), Cu(2+), Cd(2+)) by selenate ligand was studied by ACE (UV indirect detection) in 0.1 mol/L NaNO(3) ionic strength solutions at various temperatures (15, 25, 35, 45 and 55°C). For each solution, a unique peak was observed as a result of a fast equilibrium between the free ion and the complex (labile systems). The migration time corresponding to this peak changed as a function of the solution composition, namely the free and complexed metal concentrations, according to the complexation reactions. The results confirmed the formation of a unique 1:1 complex for each cation. The thermodynamic parameters were fitted to the experimental data at 0.1 mol/L ionic strength: (25°C) = -(6.5 ± 0.3), -(7.5 ± 0.3), -(7.7 ± 0.3), -(7.7 ± 0.3), and -(8.1 ± 0.3) kJ/mol and = 2.5 ± 0.2, 4.7 ± 0.4, 4.5 ± 0.6, 8.4 ± 1.1, and 7.2 ± 0.6 kJ/mol for M(2+) = Mg(2+), Co(2+), Ni(2+), Cu(2+), and Cd(2+), respectively. Complexes with alkaline earth and transition metal cations could be distinguished by their relative stabilities. The effect of the ionic medium was treated using the specific ion interaction theory and the thermodynamic parameters at infinite dilution were compared to previously published data on metal-selenate, metal-sulfate, and metal-chromate complexes.

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Thermodynamical and Structural Study of Protactinium(V) Oxalate Complexes in Solution

Cited by 29 publications

References 28 publications

Actinide oxalate complexes formation as a function of temperature by capillary electrophoresis coupled with inductively coupled plasma mass spectrometry

Actinide oxalate complexes formation as a function of temperature by capillary electrophoresis coupled with inductively coupled plasma mass spectrometry

Elucidating Protactinium Hydrolysis: The Relative Stabilities of PaO₂(H₂O)⁺ and PaO(OH)₂⁺

Formation of MSeO₄(aq) complexes (M²⁺ = Mg²⁺, Co²⁺, Ni²⁺, Cu²⁺, Cd²⁺) studied as a function of temperature by affinity capillary electrophoresis

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Thermodynamical and Structural Study of Protactinium(V) Oxalate Complexes in Solution

Cited by 29 publications

References 28 publications

Actinide oxalate complexes formation as a function of temperature by capillary electrophoresis coupled with inductively coupled plasma mass spectrometry

Actinide oxalate complexes formation as a function of temperature by capillary electrophoresis coupled with inductively coupled plasma mass spectrometry

Elucidating Protactinium Hydrolysis: The Relative Stabilities of PaO2(H2O)+ and PaO(OH)2+

Formation of MSeO4(aq) complexes (M2+ = Mg2+, Co2+, Ni2+, Cu2+, Cd2+) studied as a function of temperature by affinity capillary electrophoresis

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Elucidating Protactinium Hydrolysis: The Relative Stabilities of PaO₂(H₂O)⁺ and PaO(OH)₂⁺

Formation of MSeO₄(aq) complexes (M²⁺ = Mg²⁺, Co²⁺, Ni²⁺, Cu²⁺, Cd²⁺) studied as a function of temperature by affinity capillary electrophoresis