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Radiochemistry

, Volume 44, Issue 2, pp 114–120 | Cite as

Formation of Unusual U, Pu, and Cf Oxide Species under Conditions of Gas Thermochromatography

  • V. P. Domanov
  • G. V. Buklanov
  • Yu. V. Lobanov
Article

Abstract

Experiments were performed on the preparation of volatile oxidation products from trace amounts of plutonium and on thermochromatographic (TC) separation of these species, taking into account the previously obtained data on different behaviour of some micro- and macrocomponents in the gas phase. The volatility of products formed by thermal oxidation of traces of U and 249Cf with an He-O2 (1 : 1 vol.) mixture was studied with the aim to simulate the behavior of Pu(IV) and Pu(VI) oxides. Hollow quartz columns were used. Under the experimental conditions, volatile UO2, UO3, and 249CfO2 were formed; the dioxides were deposited at 450±25°C, and UO3, at 250±25°C. The enthalpies of adsorption -ΔHa0 of these compounds on quartz were calculated. Experimental evidence of existence in the gas phase of volatile uranic acid was obtained. The TC behavior of 238,239Pu traces was studied under conditions of thermal oxidation in an He-O2 flow at the oxygen concentration cO2 varied from 50 to 10-7%. In the cO2 range of 50-5 × 10-2%, deposition of volatile Pu species at 460±25 and 250±25°C was observed. The identical deposition temperatures and close values of -ΔHa0 of the products of U and Pu oxidation suggest the transfer of Pu in the form of PuO2 and PuO3. In the cO2 range from 50 to 1%, an abnormally volatile Pu species was detected, which was deposited at -105±25°C. Its -ΔHa0, 41±6 kJ mol-1, was close to that of OsO4. The deposition zones of 185OsO4 and of the highly volatile Pu species were superimposed. As cO2 decreased, the yield of the highly volatile Pu species decreased; a similar trend is also characteristic of OsO4. This volatile Pu species was tentatively identified as Pu(VIII) oxide, PuO4.

Keywords

Uranic Acid Volatility Plutonium Thermal Oxidation Deposition Temperature 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

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Copyright information

© MAIK “Nauka/Interperiodica” 2002

Authors and Affiliations

  • V. P. Domanov
    • 1
  • G. V. Buklanov
    • 1
  • Yu. V. Lobanov
    • 1
  1. 1.Flerov Laboratory of Nuclear ReactionsJoint Institute for Nuclear ResearchDubna, Moscow oblastRussia

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