Radiolytic formation of the carbon dioxide radical anion in acetonitrile revealed by transient IR spectroscopy

Grills, David Charles; Lymar, Sergei

doi:10.1039/C8CP00977E

Radiolytic formation of the carbon dioxide radical anion in acetonitrile revealed by transient IR spectroscopy

Journal Article · Thu Mar 29 00:00:00 EDT 2018 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/C8CP00977E· OSTI ID:1430880

^[1]; Lymar, Sergei ^[1]

Brookhaven National Lab. (BNL), Upton, NY (United States). Chemistry Division

In this study, the solvated electron in CH₃CN is scavenged by CO₂ with a rate constant of 3.2 × 10¹⁰ M^–1 s^–1 to produce the carbon dioxide radical anion (CO₂^•–), a strong and versatile reductant. Using pulse radiolysis with time-resolved IR detection, this radical is unambiguously identified by its absorption band at 1650 cm^–1 corresponding to the antisymmetric CO₂^•– stretch. This assignment is confirmed by ¹³C isotopic labelling experiments and DFT calculations. In neat CH₃CN, CO₂^•– decays on a ~10 μs time scale via recombination with solvent-derived radicals (R•) and solvated protons. Upon addition of formate (HCO₂^–), the radiation yield of CO₂^•– is substantially increased due to H-atom abstraction by R• from HCO₂^– (R• + HCO₂^– → RH + CO₂^•–), which occurs in two kinetically separated steps. The rapid step involves the stronger H-abstracting CN•, CH₃•, and possibly, H• primary radicals, while the slower step is due to the less reactive, but more abundant radical, CH₂CN•. The removal of solvent radicals by HCO₂^– also results in over a hundredfold increase in the CO₂^•– lifetime. CO₂^•– scavenging experiments suggest that at 50 mM HCO₂^–, about 60% of the solvent-derived radicals are engaged in CO₂^•– generation. Finally, even under CO₂ saturation, no formation of the radical adduct, (CO₂)₂^•–, could be detected on the microsecond time scale.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0012704

OSTI ID:: 1430880

Alternate ID(s):: OSTI ID: 1434142

Report Number(s):: BNL--203439-2018-JAAM

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 15 Vol. 20; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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