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Temperature and ionic strength influence on U(VI/V) and U(IV/III) redox potentials in aqueous acidic and carbonate solutions

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Abstract

Redox potentials: E(UO 2+2 /UO +2 )=60±4 mV/NHE, E(U4+/U3+)=−630±4mV/NHE measured at 25°C in acidic medium (HClO4 1M) using cyclic voltametry are in accordance with the published data. From 5°C to 55°C the variations of the potentials of these systems (measured against Ag/AgCl electrode) are linear. The entropies are then constant: [ΔS(UO 2+2 /UO +2 )−ΔS(Ag/AgCl)]/F=0±0.3 mV/°C, [ΔS(U4+/U3+)−ΔS(Ag/AgCl)]/F=1.5±0.3 mV/°C. From 5°C to 55°C, in carbonate medium (Na2CO3=0.2M), the Specific Ionic Interaction Theory can model the experimental results up to I=2M (Na+, ClO −4 , CO 2−3 ): E(UO2(CO3) 4−3 /UO2(CO3) 5−3 )=−778±5 mv/NHE (I=0, T=25°C, Δ∈(25°C)=∈(UO2(CO3) 4−3 , Na+)−∈(UO2(CO3) 5−3 , Na+)=0.92 kg/mole, ΔS(UO2(CO3) 4−3 /UO2(CO3) 5−3 =−1.8±0.5 mV/°C (I=0), Δ∈=∈(Cl−, Na+)=(1.14−0.007T) kg/mole. The U(VI/V) potential shift, between carbonate and acidic media, is used to calculate (at I=0,25°C):

$$\log \frac{{\beta _3 U(V)}}{{\beta _3 U(VI)}} = - 14.7 \pm 0.5$$

and then

$$\log \beta _3 U(V) = 6.6 \pm 0.3.$$

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  1. Laboratoire de Chimie CEA IRDI/DERDCA/DRDD/SESD/SCPCS, 92265, Fontenay aux Roses, Cedex, France

    H. Capdevila & P. Vitorge

Authors
  1. H. Capdevila
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  2. P. Vitorge
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Capdevila, H., Vitorge, P. Temperature and ionic strength influence on U(VI/V) and U(IV/III) redox potentials in aqueous acidic and carbonate solutions. Journal of Radioanalytical and Nuclear Chemistry, Articles 143, 403–414 (1990). https://doi.org/10.1007/BF02039609

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