4 5 6 7 8 E (~1 0~c m -l ) Figure 7. Observed dissociation rate constants [reported in this work and ref 5 (O), refs 1 and 4 (+), and refs 3, 6, and 7 (X)] and theoretically predicted values of the rate constant for C-H bond fission reported in ref 4 (---) for toluene, p-xylene, and mesitylene.For mesitylene, our kobo is about one-third of the predicted value. Thus, the difference between the kl obtained from our observation and the prediction is larger than that for toluene.
V. ConclusionsToluene, p-xylene, deuterated pxylene (CsDlo), and mesitylene under low-pressure conditions were irradiated with a 158-nm laser. The dissociations of all the alkylbenzenes follow the hot molecule mechanism for this irradiation energy, as observed at 193 nm. The dissociation rate constants via the hot molecule mechanism are as follows: 9.3 (f0.7) X lo7 s-' for toluene, 1.5 (h0.3) X lo7 s-l for p-xylene, 4.6 (h0.4) X lo6 s-' for deuterated p-xylene, and 3.0 (f0.9) X lo6 s-l for mesitylene. In comparison with previous data, the constant for mesitylene is two-thirds of that reported by Park and others. For toluene the dissociation rate constant of the C-H bond in the methyl group (k,) is estimated to be 6.8 X lo7 s-'. The rate constants kl are predictable with an accuracy of within a few times in terms of SACM calculations made by Brand et al., if the same order of branching ratios is assumed for p-xylene and mesitylene.Registry No. FZ,(1) Hippler, H.; Schubert, V.; Troe, J.; Wendelken, H. (9) Bolovinos, A.; Philis, J.; Pantos, E.; Tsekeris, P.; Andritsopoulos, G.Past experiments on Turing patterns have all been conducted using the chlorite-iodide-malonic acid (CIMA) reaction with Thiodsne from Prolabo as an indicator. In this work two other indicators have been examined and found to yield Turing patterns similar to those obtained with Thiodbne: soluble starch and poly(viny1 alcohol) (PVA). The present work shows that Thiodbne is not simply a soluble starch, as previously assumed, but is probably made by mixing about 7% starch with 93% molten urea. To determine whether the indicators might also affect the chemical kinetics, the effect of the indicators was examined in batch studies of two CIMA systems: the minimal CIMA system (chlorine dioxide-iodine-malonic acid) and the CIMA-Cl system (chlorine dioxide-iodomalonic acid-chloride). It was found that starch and poly(viny1 alcohol) affect the dynamics of the minimal CIMA oscillator but they have no effect on the CIMA-Cl system. On the other hand, in the same or even larger weight/volume concentration glucose and 2-propanol had no effect on the minimal CIMA system. These findings prove that starch and poly(viny1 alcohol) participate exclusively in triiodide complex-forming reactions: they react with an enzymelike selectivity. ThiodEne, however, had an effect on the CIMA-Cl reaction because of its urea content.