Abstract
The reactions of Ti + with ethane and propane are studied as a function of translational energy in a guided ion beam tandem mass spectrometer. By varying the conditions for forming Ti +, the effect of electronic excitation is studied. In contrast to previous results for reaction of Ti + with methane, little change in reactivity with electronic state is seen here. With ethane, TiC 2H + 2 and TiC 2H + 2 are formed in exothermic reactions. Endothermic processes observed are formation of TiH + and TiCH + n , n = 1–3. With propane, the same products as well as TiC 2H + 3, TiC 2H + 5, and TiC 3H + n , n = 2, 4, 6, are observed. Analyses of the kinetic energy dependence of these reactions are used to derive the following 298 K thermochemistry: D ⦵(Ti + CH) = 5.27 ± 0.15 eV, D ⦵(Ti + CH 3) = 2.33 ± 0.08 eV, D ⦵(Ti + C 2H 2) ⩾ 3.08 eV, D ⦵(Ti + C 2H 3) = 3.46 ± 0.25 eV, D ⦵(Ti + C 2H 4) ⩾ 1.38 eV, D ⦵(Ti + C 2H 5) = 2.28 ± 0.07 eV, D ⦵(Ti + C 3H 4) = 2.85 ± 0.15 eV, and D ⦵(Ti + C 3H 6) ⩾ 1.16 eV. The reaction of Ti + with trans-2-butene is also studied to derive thermochemistry for the dimethylitanium ion, D ⦵(H 3CTi + CH 3) = 2.80 ± 0.26 eV.
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