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Time-dependent mass spectra and breakdown graphs. 16–The methylnaphthalenes

✍ Scribed by I. Gotkis; C. Lifshitz

Publisher
John Wiley and Sons
Year
1993
Tongue
English
Weight
481 KB
Volume
28
Category
Article
ISSN
1076-5174

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✦ Synopsis

Time-resolved photoionization efficiency (PIE) curves were measured for [CllHlo] + and [C1,H9] + for 1-and Zmethylnaphthalene and for the ion-molecule reaction product [C12Hll] +. PIE curves were modelled by k(E) dependences via RRKM/QET calculations based on a model by Huang and Dunbar, with a critical energy E, = 2.41 eV and a lo00 K activation entropy A$ = -13.3 eu. Kinetic shifts are much higher than for the analogous H loss reaction in toluene. The crossover shift in the breakdown graphs between 24 p and 40 ms is 1.45 eV; the conventional shift is 2.05 eV and the intrinsic shift, due to radiative decay in the infrared, is 1.1 eV. The heat of formation of [C,,H,I+ is deduced to be AH,298(C,,H9+) < 890 f 20 kJ mol-'. The [C,,H9]+ population contains at least 20% of methylnaphthylium, the rest being benzotropylium.

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