By R.G. Compton, C.H. Bamford, C.F.H. Tipper†
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Example text
It does indicate, perhaps, that given a constant form of ion-pair the effect - References p p . 6-65 40 of dielectric constant as supposed in classical theories of reactivity of ions and ion-pairs may be quite small. The data on isoprene suggest a similar interpretation [ 140, 1411 . There is little difference in the ki values in Table 5 between diethylether and tetrahydrofuran, and the difference would be even smaller if the results were corrected to the same temperature. It would seem that with this monomer solvent-separated ion-pairs are not easily formed even in the favourable case of Li+ counter-ions.
With butadiene and isoprene, the orders in lithium alkenyl are near one quarter (or perhaps even one sixth for butadiene [52, 631). Data exists where the reported order is nearer one half [59, 661, characterized by rates which are close t o those given in Fig. 10 a t initiator concentrations near 10-'M, but which become much lower as the concentration is decreased. In one case, later work has indicated that this is caused by increased initiator destruction at low concentrations and it seems reasonable t o suppose that this explanation is valid for the whole group of experiments.
Only in the presence of sodium tetraphenylboride did the distribution approach the expected Poisson distribution. 5 x l o 9 1 mole-' sec-' . The results imply that the equilibration between the two types of ion-pair is rapid under the experimental conditions. By working with tetrahydropyran solvent at different temperatures, however, some broadening of the distribution was observed even with sodium tetraphenylboride present which enabled estimates to be made of the rate of interconversion of the two types of ion-pairs [ 1101 'Detailed kinetic studies on other monomers than styrene are not numerous.