KINETICS AND MECHANISMS FOR THE OXIDATION OF TRIVALENT PLUTONIUM BY NITROUS ACID

Journal Article · Fri Jan 01 04:00:00 EST 1960 · Journal of the American Chemical Society (U.S.)

DOI:https://doi.org/10.1021/ja01486a003· OSTI ID:4187800

Dukes, E K

The rate of oxidation of plutonium(III) by nitrous acid was investigated in nitric, hydrochloric, and perchloric acids. The rate expressions obtained were in HCl or HClO/sub 4/, - dSTAPu(III)!/dt = KtSTAPu(III)! STAH+!STAHNO/sub 2/ !; in HNO/sub 3/, dSTAPu(III)!/dt = K/sub 2/STAPu(III)!STAH+!STANO/sub 3/-!STAHNO/ sub 2/! where K/sub 1/ = 1 8 plus or minus 3.5 moles/sup -2/ min/sup -1/ and K/ sub 2/ = 90 plus or minus 20 moles min/sup -1/. The proposed mechanisms for the oxidation of Pu(III) by nitrous acid involve N/sub 2/O/sub 4/ as an intermediate in HNO/sub 3/ and NO+ as an intermediate in HCl or HClO/sub 4/. Activation energies of 14.0 plus or minus 0.5 and 6.0 plus or minus 0.3 kcal/ mole were found for K/sub 1/ and K/sub 2/. Studies were made with solutions 10/ sup -5/ to 10/sup -6/ molar in plutonium and the change in distribution coefficient of plutonium into 30 vol% tributyl phosphate (TBP) was used to follow the reaction. (auth)

• Research Organization: E.I. du Pont de Nemours & Co., Aiken, S.C.
• Sponsoring Organization: USDOE
• NSA Number: NSA-14-007338
• OSTI ID: 4187800
• Journal Information: Journal of the American Chemical Society (U.S.), Journal Name: Journal of the American Chemical Society (U.S.) Vol. Vol: 82; ISSN JACSA
• Country of Publication: Country unknown/Code not available
• Language: English

Related Subjects

BUTYL PHOSPHATES
CHEMISTRY
DISTRIBUTION
HYDROCHLORIC ACID
MINERAL ACIDS
NITRIC ACID
NITROGEN OXIDES
NITROUS ACID
OXIDATION
PERCHLORIC ACID
PLUTONIUM
REACTION KINETICS