The Chemistry of Tributyl Phosphate: A Review

Organic tanks safety program FY95 waste aging studies

“…This observation'is consistent with reported rates for TBP saponification to DBP (Burger 1955). Recoveries of DBP were only 6% from the unirradiated simulant.…”

“…The evidence suggests that the quantities of organic solvents added to the tanks rival the quantities of complexants. However, the fraction of organic solvents that have escaped the wastes via evaporation, or, in the case of phosphate esters, have been saponified in the alkaline wastes (Burger 1955) is not known. Sederburg and Reddick (1994) have pointed out that during early PUREX operations, the organic wash waste was combined with high-level wastes that generated enough thermal heat to cause the tank wastes to self-boil.…”

The Chemistry of Flammable Gas Generation

“…Ionic processes, which occur in the absence of radiation, include the base-catalyzed fragmentation reaction of citrate ion (Ashby et al 1994;Barefield et al 1995Barefield et al , 1996Camaioni et al 1998), the aluminate ion-catalyzed oxidation of complexants with hydroxyl groups (Delegard 1980(Delegard , 1987Ashby et al 1994;Barefield et al 1995Barefield et al , 1996Camaioni et al 1998;Camaioni and Autrey ZOOO), and the base-catalyzed oxidation of aldehydes that is responsible for most of the hydrogen generated in the waste (Ashby et al 1993(Ashby et al , 1994Barefield et al 1995Barefield et al , 1996Karpoor et al 1995). Reactions between the original organic complexants and water are not significant, but TBP reacts slowly with water in alkaline solution to form butanol and sodium dibutyl phosphate (DBP) (Burger 1955;Camaioni et al 1996a). Other hydrolysis reactions transform the intermediate nitrite and nitrate esters, nitroso and nitro compounds, acetals and ketals and their related nitrogen derivatives, oximes and hydroxamates, amides, and nitriles into alcohols, aldehydes and ketones, and sodium…”

“…The chemical literature indicates that the rate constants for hydrolysis of dialkyl esters are several orders of magnitude smaller than the rate constants for the hydrolysis of the corresponding trialkyl esters, and the rate constants for the hydrolysis of monoalkyl esters are also several orders of magnitude smaller than the rate constants for the dialkyl esters (Cox and Ramsay 1964;Wolfenden et al 1998). The rates of hydrolysis of TBP have been measured under heterogeneous conditions in the presence of 1M sodium hydroxide at temperatures from 30 "C to 100 "C by Burger (1955). The observed rate data were fit to the following expression by Camaioni et al (1996a: ln(R)=54.8 -2.55 x 104(l/T) + 2.69 x 106(1/T)'…”

Origins of volatile organic compounds emerging from tank 241-C-106 during sluicing

“…Burger (1955) discussed the rates of hydrolysis of pure TBP under heterogeneous conditions in the presence of 1 M sodium hydroxide at temperatures from 30 "C to 100 "C. The observed rate data were fit to the following expression by Camaioni and coworkers (1 996).…”