ESR spectra of radicals at a low-temperature X-radiolysis of phosphates

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

“…[73,74] A possible fate of this peroxyl radical is superoxide elimination, followed by hydrolysis to produce HDBP and butyraldehyde, also a measured product. [ Alternately, Wilkinson and Williams [86] proposed a mechanism for HDBP formation based upon the decomposition of the TBP radical cation, the product of direct TBP radiolysis:…”

Radicals from tributyl phosphate decomposition: a combined electron paramagnetic resonance spectroscopic and computational chemistry investigation

“…The radical R2 (–CH 2 ˙CHCH 2 –) has five protons, which corresponds to the pattern of the experimental spectrum. Moreover, some previous papers 10,11 indicate up to 20% of the contribution of this radical to the entire signal. Conformational analysis reveals two conformers for radical R2 , as shown in Table 1.…”

“…9 A number of works were also devoted to the analysis of TBP neutral radicals under the action of X-rays and γ-rays. 8,10,11 The irradiation at a low temperature (77 K) made it possible to detect alkyl-type radicals with a radiation-chemical yield of 1.34 μmol J −1 (12.9 radicals/100 eV) 10 or 0.71 μmol J −1 (6.8 radicals/100 eV). 11 The main contribution to the EPR spectrum, apparently, is made by the CH 3 ˙CHCH 2 -type radical with hyperfine coupling (HFC) constants of 2.2, 3.5, and 5.0 mT, 10 but its precise nature is not entirely clear.…”

“…An advanced GC-MS-MS technique was used to identify minor decay products including oligomers and fragmentation products in the presence of air and nitric acid. 8 Mostafavi et al employed picosecond pulse radiolysis to probe the TBP solvated electron (e TBP yield of 1.34 mmol J À1 (12.9 radicals/100 eV) 10 or 0.71 mmol J À1 (6.8 radicals/100 eV). 11 The main contribution to the EPR spectrum, apparently, is made by the CH 3 CHCH 2 -type radical with hyperfine coupling (HFC) constants of 2.2, 3.5, and 5.0 mT, 10 but its precise nature is not entirely clear.…”

Crown ethers in radiochemistry. Advances and prospects

“…To some extent, this is explained by the complexity of experiments which require investigation of radiolysis of macrocyclic systems under conditions of matrix isolation of crown ethers or in adsorbed monolayers, e.g., on zeolites. An exception are the studies of Kuruc et al 63,64 who attempted to identify radicals and radical cations in g-irradiated crown ethers by the methods of spin traps and isolation in Freon matrices. However, it was impossible to interpret unambiguously the results obtained because of poor resolution of the EPR spectra.…”