Evidence for complex formation in the reactions of CH+3 and CD+3 with CH3OH, CD3OD, and C2H5OH

✍ Scribed by Richard D. Smith; Jean H. Futrell

• Publisher: Elsevier Science
• Year: 1976
• Tongue: English
• Weight: 447 KB
• Volume: 41
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(76)85248-7

✦ Synopsis

Product distributions for the reactions of CH$ and CDf with methanol, methanol-da, and ethanol studied in a tandemkm CpdOtrOTl resonance mass SpeCtrOmeter are reported. The major reaction pathways may 5c rationalized in terms of 3x1 intermediate species havving a pro&mated ether structure. The reactions of simple carbonium ions, such as CFi$, are often difficult to son out because of the simultaneous occurrence of reactions of other ionic species. In view of the importance of these reactions in liquid phase ion chemistry and of some empirical evidence (extensive H, D randomization) for complex formation in the gas phase [I 41, we have undertaken a tandem-ICR study of CI-35 (CDS) reactions with 2 rmmber of alcohols. Here we report product distributions for the reactions with CH,OH, CD,OD and C2 H5 OH.

This work used a tandem-ICR mass spectrometer, described elsewhere IS], to stud51 the thermal energy (SG 0.1 eV translational energy) reactions of massselected CH$ and CD; ions. Such studies, under single collision conditions, avoid mass discrimination effects of most tandem instruments, the integrations required in crossed-beam experiments, and the artifacts common to mare conventional @X-double resonance studies.

Ctl$ (CDS) reactant ions were prepared by 25 eV electron impact on CH, (CD& The ions are probably internally excited, although recent work [6] indicates that electronic excitation is unlikely ok the present reaction time scale f1W3 s). IWife CH$ vibrational energy may affect the product distributions prelimi-