Formation and High-order Carboxylic Acids (RCOOH) in Interstellar Analogous Ices of Carbon Dioxide (CO 2 ) and Methane(CH 4 )

Abstract

This laboratory study simulated the abiotic formation of carboxylic acids (RCOOH) in interstellar analogous ices of carbon dioxide (CO 2 ) and methane (CH 4 ) at 10 K upon exposure to energetic electrons. The chemical processing of the ices and the subsequent warm-up phase were monitored online and in situ, exploiting Fourier Transform Infrared Spectrometry and quadrupole mass spectrometry. Characteristic absorptions of functional groups of carboxylic acids (RCOOH) were observed in the infrared spectra of the irradiated ice. Two proposed reaction mechanisms replicated the kinetic profiles of the carboxylic acids along with the decay profile of the precursors during the irradiation via hydrocarbon formation, followed by carboxylation and/or through acetic acid along with mass growth processes of the alkyl chain. Mass spectra recorded during the warm-up phase demonstrated that these acids are distributed from acetic acid (CH 3 COOH) up to decanoic acid (C 9 H 19 COOH). High-dose irradiation studies (91 ± 14 eV) converted low-molecular-weight acids such as acetic acid (CH 3 COOH) and propionic acid (C 2 H 5 COOH) to higher-molecular-weight carboxylic acids, compared to low-dose irradiation studies (18 ± 3 eV). The traces of the  ( m/z  = 60) fragment—a link to linear carboxylic acids—implied that higher-order acids (C n H 2 n +1 COOH, n  ≥ 5) are likely branched, which correlates with the recent analysis of the structures of the monocarboxylic acids in the Murchison meteorite.