Abstract
AbstractUltrasonic relaxation spectra of LiClO4 plus the open chain polyether triglyme (TG) at CLiClO4 ≃ 0.8 M, molar ratio R = [TG]/[LiClO4] = 1, and at temperatures of 15, 25, 35, and 45°C in dry acetonitrile are reported. Corresponding spectra for LiClO4 plus the macrocycle 12‐crown‐4 (12C4) at R = [12C4]/[LiClO4] = 1, at 10, 15, 20, 25, 30, and 40°C, and CLiClO4 = 0.32 M in acetonitrile are also reported.Both relaxation envelopes, for the two systems, have been fitted by two Debye relaxation processes and interpreted by the Eigen‐Winkler reaction scheme: where “PE” symbolizes the polyether, Li+ … PE is a solvent separated species and LiPE+ and (LiPE)+ are two complex species. The temperature dependence of the relaxation spectra permits the calculation of the activation parameters for the forward and reverse processes for the system LiClO4 + TG and for one of the two processes for the LiClO4 + 12C4 system.Comparisons between the two sets of data lead to the conclusion that the much slower second relaxation process, in the case of the macrocycle, is attributable to a combination of an enthalpic and an entropic effect on the energy barrier for the present systems.
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