Alpha radiolysis and other factors affecting hydrolysis of tributyl phosphate
The primary purpose of this study was to identify the principal degradation products produced by Pu(IV) loading in 30% tributyl phosphate/dodecane (TBP-DD) solutions and to determine the formation rates of these species as a function of temperature. Experiments were also conducted to evaluate HNO/sub 3/ hydrolysis of TBP as a function of temperature and to compare the effects resulting from plutonium solvent loading with effects due to loading with uranium and zirconium. The results indicate that four factors are of particular significance: (1) dibutyl phosphate (DBP) is the principal plutonium-complexing species formed at temperatures of 50/sup 0/C or lower, while significant concentrations of monobutyl phosphate (MBP) are also formed at higher temperatures; (2) the TBP degradation rate due to alpha radiolysis or chemical hydrolysis is strongly dependent on temperature; (3) plutonium promotes TBP hydrolysis by two mechanisms, alpha radiolysis and metal-ion-induced hydrolysis, and, of these, metal-ion-induced hydrolysis can be the major effect; and (4) small amounts of an unidentified plutonium-complexing species are formed in experiments using plutonium of high specific activity (about 4 x 10/sup 8/ counts per minute per milligram (c/min dot mg)). This species cannot be removed from 30% TBP-DD by Na/sub 2/CO/sub 3/ washing or other solvent cleanup procedures. The TBP degradation rates (determined as grams of plutonium complexed by degradation products) increased from 0.125 mg Pu/L dot h at 25/sup 0/C to 47.9 mg Pu/L dot h at 80/sup 0/C in 30% TBP-DD solutions that contained only 0.68 M HNO/sub 3/. In solutions that additionally contained approx.20 g/L of plutonium (specific activity = 9 x 10/sup 7/ c/min dot mg) TBP degradation rates increased from 2.46 mg Pu/L dot h at 25/sup 0/C to 127.1 mg Pu/L dot h at 80/sup 0/C. 10 refs., 8 figs., 4 tabs.
- Research Organization:
- Oak Ridge National Lab., TN (USA)
- DOE Contract Number:
- AC05-84OR21400
- OSTI ID:
- 5534740
- Report Number(s):
- ORNL/TM-9565; ON: DE85015071
- Country of Publication:
- United States
- Language:
- English
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ACTINIDE COMPLEXES
ACTINIDES
ALKANES
BUTYL PHOSPHATES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
DBP
DECOMPOSITION
DODECANE
ELEMENTS
ESTERS
EXPERIMENTAL DATA
HYDROCARBONS
HYDROGEN COMPOUNDS
HYDROLYSIS
INFORMATION
INORGANIC ACIDS
LYSIS
MEDIUM TEMPERATURE
METALS
NITRIC ACID
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC PHOSPHORUS COMPOUNDS
PHOSPHORIC ACID ESTERS
PLUTONIUM
PLUTONIUM COMPLEXES
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIOLYSIS
SOLVOLYSIS
TBP
TEMPERATURE DEPENDENCE
TIME DEPENDENCE
TRANSITION ELEMENTS
TRANSURANIUM COMPLEXES
TRANSURANIUM ELEMENTS
URANIUM
YIELDS
ZIRCONIUM