Pulse radiolysis of HNO3 and HNO3(aq)

Kozlowska-Milner, E.; Broszkiewicz, R.K.

doi:10.1016/0146-5724(78)90105-x

Cited by 21 publications

(16 citation statements)

References 24 publications

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“…The radiolysis of aqueous nitric acid has included investigations of • NO 3 radical formation mechanisms and yields . Two major pathways have been identified.…”

Section: Introductionmentioning

confidence: 99%

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The Reactivity of the Nitrate Radical (^• NO₃ ) in Aqueous and Organic Solutions

Mezyk

Cullen

Rickman

et al. 2017

Int. J. Chem. Kinet.

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Rate constants for the nitrate ( • NO 3 ) radical reaction with alcohols, alkanes, alkenes, and several aromatic compounds were measured in aqueous and tert-butanol solution for comparison to aqueous and acetonitrile values from the literature. The measured trends provide insight into the reactions of the • NO 3 radical in various media. The reaction with alcohols primarily consists of hydrogen-atom abstraction from the alpha-hydroxy position and is faster in solvents of lower polarity where the diffusivity of the radical is greater. Alkenes react faster than alkanes, and their rate constants are also faster in nonpolar solution. The situation is reversed for the nitrate radical reaction with the aromatic compounds, where the rate constants in tert-butanol are slower. This is attributed to the need to solvate the NO 3 − anion and corresponding tropylium cation produced by the • NO 3 radical electron transfer reaction. A linear correlation was found between measured rate constants in water and acetonitrile, which can be used to estimate aqueous nitrate radical rate constants for compounds having low water solubility.

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“…The radiolysis of aqueous nitric acid has included investigations of • NO 3 radical formation mechanisms and yields . Two major pathways have been identified.…”

Section: Introductionmentioning

confidence: 99%

“…The reaction of nitrate anions with ionized water (H 2 O + ) can also produce this radical :

\begin{matrix} true \\ right H_{2} {normalO}^{+} + {NO}_{3}^{-} \to H_{2} normalO +^{•} {NO}_{3} \end{matrix}

…”

Section: Introductionmentioning

confidence: 99%

The Reactivity of the Nitrate Radical (^• NO₃ ) in Aqueous and Organic Solutions

Mezyk

Cullen

Rickman

et al. 2017

Int. J. Chem. Kinet.

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“…Moisy et al 92 showed that in concentrated solutions of HNO 3 , the G(H 2 O 2 ) decreases linearly with increasing HNO 3 concentrations. H 2 O 2 is mainly formed via recombination of cOH radicals, and increased concentrations of HNO 3 will lead to cOH scavenging via reaction ( 21) and (28). As the concentration of HNO 3 increases, the dissociation degree decreases, as shown in Fig.…”

Section: Resultsmentioning

confidence: 96%

“…Due to the multi-component aspect of spent nuclear fuel, a multidirectional approach is needed, taking into account the alpha, beta and gamma radiation induced degradation. Many studies were dedicated to the radiolytic degradation of HNO 3 soon aer the development of the PUREX process in the '50s, providing a wealth of information on the radiolytic mechanism and yields of H 2 , NO 3 c and NO 2 À /HNO 2 in the g 3,7-25 or b radiolysis 8,16,17,22,[26][27][28][29][30][31][32][33][34][35][36][37] of aqueous nitrate and nitric acid solutions. However, fewer studies have been dedicated to the a radiolysis of these solutions, and the majority of these investigations were performed in the radiolysis of HNO 3 in the presence of radionuclides ( 243 Am, 241 Am, 244 Cm, 210 Po, 240 Pu, 238 Pu).…”

Section: Introductionmentioning

confidence: 99%

New insight on the simultaneous H₂and HNO₂production in concentrated HNO₃aqueous solutions under alpha radiation

et al. 2021

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“…Under the acidic, aerated conditions of the nuclear solvent extraction process, the aqueous electrons produced would be scavenged according to the fast reactions in equation 39 and 40. [56] eaq + H…”

Section: Radiolysismentioning

confidence: 99%

Reactivity of Radiolytically-Produced Nitrogen Oxide Radicals Toward Aromatic Compounds

Elias¹

2010

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The nitration of aromatic compounds in the gas phase is an important source of toxic, carcinogenic, and mutagenic species in the atmosphere and has therefore received much attention. Gas phase nitration typically occurs by free-radical reactions. Condensed-phase free-radical reactions, and in particular nitrite and nitrate radical chemistry, have been studied far less. These condensed-phase free-radical reactions may be relevant in fog and cloud water in polluted areas, in urban aerosols with low pH, in water treatment using advanced oxidation processes such as electron beam (e-beam) irradiation, and in nuclear waste treatment applications. This study discusses research toward an improved understanding of nitration of aromatic compounds in the condensed phase under conditions conducive to free-radical formation. The results are of benefit in several areas of environmental chemistry, in particular nuclear waste treatment applications. The nitration reactions of anisole and toluene as model compounds were investigated in J-irradiated acidic nitrate, neutral nitrate, and neutral nitrite solutions. Cs-7SB, 1-(2,2,3,3,-tetrafluoropropoxy)-3-(4-sec-butylphenoxy)-2-propanol, is used as a solvent modifier in the fission product extraction (FPEX) formulation for the extraction of Cs and Sr from dissolved nuclear fuel. The formulation also contains the ligands calix[4]arene-bis-(tert-octylbenzo-crown-6) (BOBCalixC6) for Cs extraction and 4,4',(5')-di-(t-butyldicyclohexano)-18-crown-6 (DtBuCH18C6) for Sr extraction, all in Isopar L, a branched-chain alkane diluent. FPEX solvent has favorable extraction efficiency for Cs and Sr from acidic solution and was investigated at the Idaho National Laboratory (INL) for changes in extraction efficiency after J-irradiation. Extraction iv efficiency decreased after irradiation. The decrease in solvent extraction efficiency was identical for Cs and Sr, even though they are complexed by different ligands. This suggests that radiolysis of the modifier (Cs-7SB), which solvates both metal complexes, is responsible for this change. These reactions presumably occur due to reactions with radiolytically-produced nitrogen-centered radicals like • NO, • NO 2 and • NO 3. Anisole (C 6 H 5-OCH 3) was used in this study as a surrogate for Cs-7SB, since both are aryl ethers. Toluene was used as a surrogate for Cs-7SB because of the alkyl group on the benzene ring in both molecules. Anisole, highly reactive in acids, is a small molecule compared to Cs-7SB and the nitration products are easier to identify compared to those for the larger Cs-7SB molecule. Toluene is less reactive than anisole. Therefore, the highly reactive anisole and the less reactive toluene were considered in this study as model compounds to compare the reaction mechanisms and the nitrated products in acidic media under irradiation. Experiments were designed to elucidate the mechanism of the nitration of aromatic rings in J-irradiated aqueous nitric acid. Since a suite of radical and ionic reactive species are produced in this conden...

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Pulse radiolysis of HNO3 and HNO3(aq)

Cited by 21 publications

References 24 publications

The Reactivity of the Nitrate Radical (^• NO₃ ) in Aqueous and Organic Solutions

The Reactivity of the Nitrate Radical (^• NO₃ ) in Aqueous and Organic Solutions

New insight on the simultaneous H₂and HNO₂production in concentrated HNO₃aqueous solutions under alpha radiation

Reactivity of Radiolytically-Produced Nitrogen Oxide Radicals Toward Aromatic Compounds

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Pulse radiolysis of HNO3 and HNO3(aq)

Cited by 21 publications

References 24 publications

The Reactivity of the Nitrate Radical (• NO3 ) in Aqueous and Organic Solutions

The Reactivity of the Nitrate Radical (• NO3 ) in Aqueous and Organic Solutions

New insight on the simultaneous H2and HNO2production in concentrated HNO3aqueous solutions under alpha radiation

Reactivity of Radiolytically-Produced Nitrogen Oxide Radicals Toward Aromatic Compounds

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The Reactivity of the Nitrate Radical (^• NO₃ ) in Aqueous and Organic Solutions

The Reactivity of the Nitrate Radical (^• NO₃ ) in Aqueous and Organic Solutions

New insight on the simultaneous H₂and HNO₂production in concentrated HNO₃aqueous solutions under alpha radiation