Reactions of nitriles in ices relevant to Titan, comets, and the interstellar medium: formation of cyanate ion, ketenimines, and isonitriles

• Published in: Icarus (New York, N.Y. 1962) Vol. 172; no. 2; pp. 466 - 478
• Main Authors: Hudson, R.L., Moore, M.H.
• Format: Journal Article
• Language: English
• Published: San Diego, CA Elsevier Inc 01.12.2004; Elsevier
• Subjects: Astronomy; Comets; Earth, ocean, space; Exact sciences and technology; Ices; Photochemistry; Radiation chemistry; Solar system; Titan; Comets; Radiation chemistry; Ices; Titan; Photochemistry; Ice; Comets: Ices; Acetonitrile; Saturn satellite; Cometary coma; Prebiotic condition; Solar system; Interstellar matter; Low temperature
• ISSN: 0019-1035; 1090-2643
• DOI: 10.1016/j.icarus.2004.06.011

Motivated by detections of nitriles in Titan's atmosphere, cometary comae, and the interstellar medium, we report laboratory investigations of the low-temperature chemistry of acetonitrile, propionitrile, acrylonitrile, cyanoacetylene, and cyanogen (CH 3CN, CH 3CH 2CN, CH 2CHCN, HCCCN, and NCCN, respectively). A few experiments were also done on isobutyronitrile and trimethylacetonitrile ((CH 3) 2CHCN and (CH 3) 3CCN, respectively). Trends were sought, and found, in the photo- and radiation chemical products of these molecules at 12–25 K. In the absence of water, all of these molecules isomerized to isonitriles, and CH 3CN, CH 3CH 2CN, and (CH 3) 2CHCN also formed ketenimines. In the presence of H 2O, no isonitriles were detected but rather the cyanate ion (OCN −) was seen in all cases. Although isonitriles, ketenimines, and OCN − were the main focus of our work, we also describe cases of hydrogen loss, to make smaller nitriles, and hydrogen addition (reduction), to make larger nitriles. HCN formation also was seen in most experiments. The results are presented in terms of nitrile ice chemistry on Titan, in cometary ice, and in the interstellar medium. Possible connections to prebiotic chemistry are briefly discussed.