Short Communicationssaid that no attempt was made to correct the Ivalues in this particular stationary phase for interfacial adsorption; in that case an entirely different picture might be observed.The Ivalues obtained at 12OOC on the more nonpolar stationary phases used (squalane, Apiezon L, and methylvinylsilicone) decreases while the 0-0 bond stretching vibrational (Raman) frequencies (VO-0) of the diperoxide molecules [7] increases ( Figure 4). This latter parameter corresponds to the peroxidic bond force constant and the geometry of the molecules of the solutes considered. As a matter of fact, significant differences in the activation parameters for the unimolecular homolyses of the above kind of diperoxides had been observed [8], behavior which can be related with the VO-0 Raman frequencies of those molecules. On the more polar stationary phases used (Ucon Oil LB 550X and Carbowax 20M) the linear correlationis no longer maintained, probably due to specific interactions between the diperoxide molecules and the characteristics of the stationary phases.
References[l] M. V.
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