Laser photolysis study on the reaction of nitrate radical with tributylphosphate and its analogues—comparison with sulfate radical
Literature Information
Hui He, Mingzhang Lin, Yusa Muroya, Hisaaki Kudo, Yosuke Katsumura
Time resolved laser photolysis was carried out to study the reaction of NO3˙ radical toward a series of organic phosphates (tributylphosphate (TBP) and its analogues) with different length of side alkyl groups such as CH3, C2H5, C3H7, CH(CH3)2 and C4H9 in water, acetonitrile, and the mixtures of water and acetonitrile, respectively. For comparison, a similar investigation on SO4˙− radical was also conducted. The oxidation reaction of NO3˙ and SO4˙− radical with the phosphates was attributed to mainly an H-abstract reaction. The kinetics study shows that the rate constants of the reaction between the two radicals and phosphates increase remarkably with increasing of the length of the alkyl groups, e.g. in the case of NO3˙ radical in acetonitrile, the rate constant increases by almost 4 orders of magnitude from TMP (–CH3) to TBP (–C4H9). The composition of the solvent also greatly affects the reactivity but it exhibits an opposite effect of the two radicals, the rate constant of NO3˙ increases with the mole fraction of acetonitrile while that of SO4˙− decreases. The present study would be helpful for understanding the mechanism of deterioration of TBP in the Purex process.
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