{"title":"EDTA 溶液中钚（V）的歧化反应","authors":"A. M. Fedoseev, V. P. Shilov","doi":"10.1134/S1066362224030044","DOIUrl":null,"url":null,"abstract":"<p>The kinetics of disproportionation of Pu(V) in EDTA solutions with pH 2.5–4.8 at a temperature of 45°C was studied using the spectrophotometric method. Pu(V) was obtained by reduction of Pu(VI) with EDTA ions. The rate of disproportionation in the pH range 2.9–4.8 is described by the equation d[Pu(V)]/d<i>t</i> = 2<i>k</i>[Pu(V)]<sup>2</sup>. With increasing pH the value of 2<i>k</i> decreases. In a solution of 28 mM EDTA at pH 2.91, 45°С, and an ionic strength of 0.09 and 1.0 M, 2<i>k</i> is 0.064 and 0.040 M<sup>–1</sup> s<sup>–1</sup>, respectively. A dimer formed from PuO<sub>2</sub><sup>+</sup>·5H<sub>2</sub>O and the PuO<sub>2</sub>HY<sup>2–</sup>·<i>n</i>H<sub>2</sub>O complex becomes an activated complex. Its decomposition leads to the appearance of Pu(IV) and Pu(VI). The latter, being bound to Y, is reduced intramolecularly to Pu(V). The activation energy is 86 kJ/mol (25–45°C).</p>","PeriodicalId":747,"journal":{"name":"Radiochemistry","volume":"66 3","pages":"321 - 325"},"PeriodicalIF":0.9000,"publicationDate":"2024-07-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Disproportionation of Plutonium(V) in EDTA Solutions\",\"authors\":\"A. M. Fedoseev, V. P. Shilov\",\"doi\":\"10.1134/S1066362224030044\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>The kinetics of disproportionation of Pu(V) in EDTA solutions with pH 2.5–4.8 at a temperature of 45°C was studied using the spectrophotometric method. Pu(V) was obtained by reduction of Pu(VI) with EDTA ions. The rate of disproportionation in the pH range 2.9–4.8 is described by the equation d[Pu(V)]/d<i>t</i> = 2<i>k</i>[Pu(V)]<sup>2</sup>. With increasing pH the value of 2<i>k</i> decreases. In a solution of 28 mM EDTA at pH 2.91, 45°С, and an ionic strength of 0.09 and 1.0 M, 2<i>k</i> is 0.064 and 0.040 M<sup>–1</sup> s<sup>–1</sup>, respectively. A dimer formed from PuO<sub>2</sub><sup>+</sup>·5H<sub>2</sub>O and the PuO<sub>2</sub>HY<sup>2–</sup>·<i>n</i>H<sub>2</sub>O complex becomes an activated complex. Its decomposition leads to the appearance of Pu(IV) and Pu(VI). The latter, being bound to Y, is reduced intramolecularly to Pu(V). The activation energy is 86 kJ/mol (25–45°C).</p>\",\"PeriodicalId\":747,\"journal\":{\"name\":\"Radiochemistry\",\"volume\":\"66 3\",\"pages\":\"321 - 325\"},\"PeriodicalIF\":0.9000,\"publicationDate\":\"2024-07-16\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Radiochemistry\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://link.springer.com/article/10.1134/S1066362224030044\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Radiochemistry","FirstCategoryId":"1085","ListUrlMain":"https://link.springer.com/article/10.1134/S1066362224030044","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Disproportionation of Plutonium(V) in EDTA Solutions
The kinetics of disproportionation of Pu(V) in EDTA solutions with pH 2.5–4.8 at a temperature of 45°C was studied using the spectrophotometric method. Pu(V) was obtained by reduction of Pu(VI) with EDTA ions. The rate of disproportionation in the pH range 2.9–4.8 is described by the equation d[Pu(V)]/dt = 2k[Pu(V)]2. With increasing pH the value of 2k decreases. In a solution of 28 mM EDTA at pH 2.91, 45°С, and an ionic strength of 0.09 and 1.0 M, 2k is 0.064 and 0.040 M–1 s–1, respectively. A dimer formed from PuO2+·5H2O and the PuO2HY2–·nH2O complex becomes an activated complex. Its decomposition leads to the appearance of Pu(IV) and Pu(VI). The latter, being bound to Y, is reduced intramolecularly to Pu(V). The activation energy is 86 kJ/mol (25–45°C).
期刊介绍：
Radiochemistry is a journal that covers the theoretical and applied aspects of radiochemistry, including basic nuclear physical properties of radionuclides; chemistry of radioactive elements and their compounds; the occurrence and behavior of natural and artificial radionuclides in the environment; nuclear fuel cycle; radiochemical analysis methods and devices; production and isolation of radionuclides, synthesis of labeled compounds, new applications of radioactive tracers; radiochemical aspects of nuclear medicine; radiation chemistry and after-effects of nuclear transformations.
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