Role of alkyl substituent in room temperature ionic liquid on the electrochemical behavior of uranium ion and its local environment

A systematic study was carried out to understand the effect of structural modification of C_nmim⁺ moiety of C_nmimBr (n = 6, 8 or 10) on the electrochemical behavior of uranium. The cyclic voltammetric study of the above room-temperature ionic liquids (RTIL) media revealed that with increase in the chain length the electrochemical window extended more towards the negative potential. This resulted in the possibility of conversion of U(VI) to U(III) or even possibly to, U metal via U(IV) (as UO₂) when n ≥ 10. The diffusion coefficient of U(VI) was found to decrease from n = 6 to 8 to 10 due to the increasing order of viscosity of the RTIL. As a consequence, the activation energy was found to follow reverse order i.e. E _act(C₆mimBr) < E _act(C₈mimBr) < E _act(C₁₀mimBr). The conversion of UO₂ ²⁺ to UO₂ was found to be quasi reversible and also exothermic while the entropy was found to decrease due to the reduction reaction. An UV–Vis spectroscopic study was also carried out to understand the local environment around uranium in aqueous and RTIL media. Among several cationic and anionic species, the predominance of UO₂Cl₄ ^2? in 7 M HCl with D_4h coordination symmetry was observed. The decrease in symmetric stretching frequency of UO₂ ²⁺ in RTILs in comparison with aqueous system indicates that the bond strength of UO₂ ²⁺ in aqueous is less than that of UO₂ ²⁺ in RTILs.