STUDIES ON THE IDENTIFICATION OF HARMFUL RADIOLYTIC PRODUCTS OF 30% TBP-N-DODECANE-HNO₃BY GAS-LIQUID CHROMATOGRAPHY. II. FORMATION AND CHARACTERIZATION OF HIGH MOLECULAR WEIGHT ORGANOPHOSPHATES

Review Article: The Effects of Radiation Chemistry on Solvent Extraction: 1. Conditions in Acidic Solution and a Review of TBP Radiolysis

“…Methylated and hydroxylated phosphates, some of high molecular weight, have also been measured [66] probably due to addition of hydroxyl, methyl, or another TBP radical. For example, Adamov [67,68] irradiated 30% TBP in alkane solutions in the presence of 3 M nitric acid and measured the species produced.…”

“…[97] This is attributed to the accumulation of the higher molecular-weight species that have high organic phase solubility [57,113] and which can retain plutonium. [66] The result is a permanently degraded and contaminated solvent that is expensive to dispose.…”

A Pulse Radiolysis Investigation of the Reactions of Tributyl Phosphate with the Radical Products of Aqueous Nitric Acid Irradiation

“…In the PUREX (Plutonium Uranium Extraction) process, 30% TBP in alkane diluent is used to extract actinides from aqueous nitric acid. One of the major advantages of this ligand is its low nitric acid hydrolysis rate; for example, Williams and Wilkinson 1 reported no production of acid phosphates after several days of exposure of TBP to 5 M HNO 3 , and Egorov et al 2 reported a rate constant for TBP hydrolysis of 9 × 10 -7 h -1 for 30% TBP in decane refluxed with 1.5 M HNO 3 . Therefore, TBP thermal degradation is slow and can be safely neglected under the short-contact, moderate-temperature conditions often used in extractions.…”

Studies on Pu238 induced alpha radiolysis of the solvent TBP

“…These methods include ion chromatography [32], liquid chromatography [33], gas chromatography [34,35], and gas chromatography-mass spectrometry [36]. The most commonly studied degradation products are HDBP and H 2 MBP.…”