Combined effects of structure and temperature on kinetics of reactions between 4-nitriphenyloxirane and arenesulfinic acids in dioxane.
DOI:
https://doi.org/10.31558/2617-0876.2017.1.2Keywords:
4-nitrophenyloxirane, arenesulfinic acids, correlation analysis, isoparametrical points, compensation effectAbstract
The effects of structure and temperature on the rate and free activation energy of reactions between 4-nitrophenyloxirane and Y-substituted arenesulfinic acids YC6H4SO2H in dioxane at 298, 308, and 323 K have been studied. Cross-correlation analysis of kinetic data was conducted. It was found that as a result of the nonadditivity of the joint effects of substituents Y and temperature, the cross reaction series exhibits isoparametric properties, the quantitative characteristics of which are isoparametrical points with respect to the constant of substituents Y (σYIP = 1.02; σYIP(G) = -0.58) and to temperature (T IP = 367 K; TIP(G) = 410 K). At the isoparametric temperature the rate of the process and the free activation energy should not depend on the effects of substituents Y, due to the full compensation in the change of the enthalpy and entropy components: δYΔH≠ = T IP(G) δYΔS ≠ , δYΔG≠IP = 0, and ΔGYT ≠IP = const (log kYT = const, ρY T = 0). At the isoparametrical point σY IP = 1.02, the rate of the process should not depend on temperature, сonsequently ΔHY ≠ = 0. At the isoparametrical point σY IP(G) = -0.58, free activation energy ΔGYT ≠ does not depend on a temperature, that is why ΔSY≠ = 0 and ΔGYT ≠IP = ΔHY ≠ . All these isoparametrical points fall outside experimental attainability.References
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