Impact of Lanthanide Complexation and Temperature on the Chemical Reactivity of N,N,N',N'-tetraoctyl diglycolamide (TODGA) with the Dodecane Radical Cation
S&T Accomplishment Report
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OSTI ID:1968307
- Idaho National Laboratory
- Florida State University
- Brookhaven National Laboratory
- California State University Long Beach
- Colorado School of Mines
The impact of lanthanide (Ln) metal ion complexation and temperature on the chemical reactivity of N,N,N',N'-tetraoctyl diglycolamide (TODGA) with the dodecane radical cation (RH?+) has been measured by electron pulse radiolysis. Complexation of trivalent neodymium (Nd), gadolinium (Gd), and ytterbium (Yb) by TODGA yielded [Ln(TODGA)3(NO3)3] complexes that exhibited significantly increased reactivity (up to 9.3×) with the RH?+ radical cation, relative to the “free” ligand: k([Ln(TODGA)3(NO3)3] + RH?+) = (8.99 ± 0.93) × 1010, (2.88 ± 0.40) × 1010, and (1.53 ± 0.34) × 1010 M–1 s–1, for Nd(III), Gd(III), and Yb(III), respectively. The kinetic enhancement measured for both ligands exhibited a dependence on atomic number. Arrhenius parameters—specifically activation energies (Ea) and pre-exponential factors (A)—were determined for the reaction of “free” TODGA ligand with the RH?+ radical cation, giving: Ea(TODGA) = 17.43 ± 1.64 kJ mol–1, and A(TODGA) = (1.08 ± 0.02) × 1013 M–1 s–1. This draft manuscript has been prepared in fulfillment of Milestone M4FT-22IN030402024.
- Research Organization:
- Idaho National Laboratory (INL), Idaho Falls, ID (United States)
- Sponsoring Organization:
- USDOE Office of Nuclear Energy (NE)
- DOE Contract Number:
- AC07-05ID14517
- OSTI ID:
- 1968307
- Report Number(s):
- INL/JOU-22-69290-Rev000
- Country of Publication:
- United States
- Language:
- English
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Impact of lanthanide ion complexation and temperature on the chemical reactivity of N,N,N',N'-tetraoctyl diglycolamide (TODGA) with the dodecane radical cation
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Thu Jun 08 20:00:00 EDT 2023
· Physical Chemistry Chemical Physics. PCCP
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OSTI ID:1985789