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Impacts of molecular architecture on the radiation-induced degradation and reaction kinetics of hydrophobic diglycolamides with the solvated electron and the dodecane radical cation

Journal Article · · Physical Chemistry Chemical Physics. PCCP
DOI:https://doi.org/10.1039/D5CP01332A· OSTI ID:3012204
 [1];  [2];  [3];  [4];  [2];  [3];  [5];  [2]
  1. Michigan State University, East Lansing, MI (United States); Idaho National Laboratory (INL), Idaho Falls, ID (United States)
  2. Idaho National Laboratory (INL), Idaho Falls, ID (United States)
  3. Brookhaven National Laboratory (BNL), Upton, NY (United States)
  4. California State University Long Beach, CA (United States)
  5. Michigan State University, East Lansing, MI (United States)
+ Show Author Affiliations
Given their proposed use as trivalent actinide–lanthanide separation ligands, the role of molecular architecture on the radiation robustness of diglycolamide (DGA) molecules has been investigated. This study examined three prototypical molecules with differences in their aliphatic chain architecture: N,N,N′,N′-tetra(n-octyl)diglycolamide (TODGA), N,N,N′,N′-tetra(2-ethylhexyl)diglycolamide (T2EHDGA), and N,N′-dimethyl-N,N′-dioctyldiglycolamide (DMDODGA). Rate coefficients and activation parameters are reported for the reactivity of each DGA with the solvated electron (esolv−) and the corresponding dodecane radical cation (RH˙+) over the temperature range of 10.0 to 44.1 °C. These measurements indicate that DMDODGA is the most chemically reactive with both transient radicals, which may be attributed to this molecule's more accessible backbone. Complementary gamma dose accumulation studies (≤ 600 kGy) under envisioned process conditions—50 mM DGA in n-dodecane solvent—afforded dose constants for the loss of DGA of d = (3.41 ± 0.07) × 10−3, (4.19 ± 0.09) × 10−3, and (4.65 ± 0.09) × 10−3 kGy−1 for T2EHDGA, DMDODGA, and TODGA, respectively. These dose constants indicate that varying DGA architecture affords subtle differences in chemical reactivity, leading to varying rates of radiolytic degradation under envisioned actinide–lanthanide separation conditions. However, more ambitious DGA frameworks, such as modifying the backbone, branching of the aliphatic chains, and/or changing the size of the chain may be required for larger gains in radiolytic longevity while optimizing actinide–lanthanide selectivity.
Research Organization:
Colorado School of Mines, Golden, CO (United States); Idaho National Laboratory (INL), Idaho Falls, ID (United States)
Sponsoring Organization:
USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Nuclear Energy (NE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
AC07-05ID14517; SC0012704; SC0024191
OSTI ID:
3012204
Alternate ID(s):
OSTI ID: 2581696
Report Number(s):
INL/JOU--24-82511-Rev002
Journal Information:
Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 30 Vol. 27; ISSN 1463-9076; ISSN 1463-9084
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

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Related Subjects

Arrhenius parameters
DGAs
DMDODGA
Diglycolamides
Dodecane
Radical cation
Radiolysis
Rate constants
Solvated electron
Steady-state irradiations
T2EHDGA
TODGA
Time-resolved pulse radiolysis