Kazuo Takahashi, A. Kunz, and Dirk Woiki
May 13, 2000
Citations
0
Influential Citations
16
Citations
Journal
Journal of Physical Chemistry A
Abstract
The kinetics of the thermal decomposition of tin tetrachloride has been studied experimentally and theoretically. Ab initio MO calculations showed that SnCl4 finally decomposed into Sn(3P) and four chlorine atoms through four subsequent Sn−Cl bond dissociation channels. Two sets of kinetic experiments were performed using a shock tube equipped with atomic resonance absorption spectroscopy (ARAS). Chlorine atoms were first measured over the temperature range of 1250−1700 K and the total density range of 1.7 × 1018 to 8.9 × 1018 molecules cm-3. The rate coefficient for the initial reaction step, SnCl4 (+M) → SnCl3(2A1) + Cl (+M) (eq 1a), was found to be in the falloff region fairly close to the low-pressure limit under the present conditions. The second-order rate coefficient based on the Cl-atom measurements was determined to be k1a2nd = 10-5.37±0.62 exp[−(285 ± 18) kJ mol-1/RT] cm3 molecule-1 s-1 (error limits at the 2 standard deviation level). The second group of experiments was carried out by detecting...