THE NOx SYSTEM in NUCLEAR WASTE

Meisel, Dan; Camaioni, D.M.

doi:10.2172/828080

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Cited by 2 publications

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“…The most reactive compounds are about 35 times more reactive than the least reactive compound investigated. In addition, Meisel and Camaioni (1998) found that nitrogen dioxide reacts more rapidly with glycinate ion than formate ion and that nitrogen dioxide reacted more rapidly with IDA, NTA, and glycinate ion than with formate ion .…”

Section: Glvcinatementioning

confidence: 97%

The Chemistry of Flammable Gas Generation

Zach¹

2000

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Section: Glvcinatementioning

confidence: 97%

The Chemistry of Flammable Gas Generation

Zach¹

2000

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Cations impact radical reaction dynamics in concentrated multicomponent aqueous solutions

Nienhuis

Graham

Kowalska

et al. 2023

The Journal of Chemical Physics

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Ultraviolet (UV) photolysis of nitrite ions (NO2−) in aqueous solutions produces a suite of radicals, viz., NO·, O−, ·OH, and ·NO2. The O− and NO· radicals are initially formed from the dissociation of photoexcited NO2−. The O− radical undergoes reversible proton transfer with water to generate ·OH. Both ·OH and O− oxidize the NO2− to ·NO2 radicals. The reactions of ·OH occur at solution diffusion limits, which are influenced by the nature of the dissolved cations and anions. Here, we systematically varied the alkali metal cation, spanning the range from strongly to weakly hydrating ions, and measured the production of NO·, ·OH, and ·NO2 radicals during UV photolysis of alkaline nitrite solutions using electron paramagnetic resonance spectroscopy with nitromethane spin trapping. Comparing the data for the different alkali cations revealed that the nature of the cation had a significant effect on production of all three radical species. Radical production was inhibited in solutions with high charge density cations, e.g., lithium, and promoted in solutions containing low charge density cations, e.g., cesium. Through complementary investigations with multinuclear single pulse direct excitation nuclear magnetic resonance (NMR) spectroscopy and pulsed field gradient NMR diffusometry, cation-controlled solution structures and extent of NO2− solvation were determined to alter the initial yields of ·NO and ·OH radicals as well as alter the reactivity of NO2− toward ·OH, impacting the production of ·NO2. The implications of these results for the retrieval and processing of low-water, highly alkaline solutions that comprise legacy radioactive waste are discussed.

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THE NOx SYSTEM in NUCLEAR WASTE

Cited by 2 publications

References 8 publications

The Chemistry of Flammable Gas Generation

The Chemistry of Flammable Gas Generation

Cations impact radical reaction dynamics in concentrated multicomponent aqueous solutions

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