Issue 42, 2023

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

Abstract

The radiation- and chemically-induced radicals from tributyl phosphate (TBP) have been characterized by EPR spectroscopy and theoretical calculations. The yield of X-ray-generated TBP radicals measured by a PBN spin trap is 0.22 μmol J−1 (2.1 radicals/100 eV) at room temperature (298 K). The EPR spectra obtained by irradiating TBP with an electron beam at 77 K are in close agreement with literature data for samples irradiated with gamma- and X-rays [https://doi.org/10.1007/BF02165504, https://doi.org/10.1016/1359-0197(89)90319-6]. Possible conformers of alkyl-type, TBP-derived radicals were analyzed by Density Functional Theory calculations. The main contribution to the experimental spectrum at 77 K is shown to be made by a conformer of the CH3˙CHCH2-radical, which contains all carbon atoms of the butyl group in the same plane. The EPR spectra of TBP radicals induced by the OH radical in aqueous solution were measured for the first time using a continuous flow system. The formation of the alkyl-type TBP radicals CH3˙CHCH2-, ˙CH2CH2-, and -CH2˙CHO- in the ratio of 5/4/1 was detected; their spectral assignment was based on quantum chemical calculations with rotational averaging of HFC constants for the corresponding beta- and alpha-protons.

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

Supplementary files

Article information

Article type
Paper
Submitted
27 Jul 2023
Accepted
19 Oct 2023
First published
19 Oct 2023

Phys. Chem. Chem. Phys., 2023,25, 29350-29357

Author version available

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

I. S. Sosulin, D. H. Ryan and A. Lisouskaya, Phys. Chem. Chem. Phys., 2023, 25, 29350 DOI: 10.1039/D3CP03584K

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